Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental and Biological Engineering, Nanjing University of Science and Technology, Nanjing 210094, China.
School of Environment, Tsinghua University, Beijing 100084, China; Zhejiang Provincial Key Laboratory of Water Science and Technology, Zhejiang, Jiaxing 314006, China.
Sci Total Environ. 2017 Oct 1;595:702-710. doi: 10.1016/j.scitotenv.2017.03.272. Epub 2017 Apr 11.
Environmental antiandrogenic (AA) contaminants in effluents from wastewater treatment plants have the potential for negative impacts on wildlife and human health. The aim of our study was to identify chemical contaminants with likely AA activity in the biological effluents and evaluate the removal of these antiandrogens (AAs) during advanced treatment comprising adsorption onto granular activated carbon (GAC). In this study, profiling of AA contaminants in biological effluents and tertiary effluents was conducted using effect-directed analysis (EDA) including high performance liquid chromatography (HPLC) fractionation, a recombinant yeast screen containing androgen receptor (YAS), in combination with mass spectrometry analyses. Analysis of a wastewater secondary effluent from a membrane bioreactor revealed complex profiles of AA activity comprising 14 HPLC fractions and simpler profiles of GAC effluents with only 2 to 4 moderately polar HPLC fractions depending on GAC treatment conditions. Gas chromatography-mass spectrometry and ultra-high performance liquid chromatography-nanospray mass spectrometry analyses of AA fractions in the secondary effluent resulted in detection of over 10 chemical contaminants, which showed inhibition of YAS activity and were potential AAs. The putative AAs included biocides, food additives, flame retardants, pharmaceuticals and industrial contaminants. To our knowledge, it is the first time that the AA properties of N-ethyl-2-isopropyl-5-methylcyclohexanecarboxamide (WS3), cetirizine, and oxcarbazepine are reported. The EDA used in this study was proven to be a powerful tool to identify novel chemical structures with AA activity in the complex aquatic environment. The adsorption process to GAC of all the identified antiandrogens, except WS3 and triclosan, fit well with the pseudo-second order kinetics models. Adsorption to GAC could further remove most of the AAs identified in the biological effluents with high efficiencies.
污水处理厂废水中的环境抗雄激素 (AA) 污染物有可能对野生动物和人类健康造成负面影响。我们的研究目的是确定生物废水中具有潜在 AA 活性的化学污染物，并评估在包括颗粒活性炭 (GAC) 吸附在内的高级处理过程中去除这些抗雄激素 (AA) 的效果。在这项研究中，使用包括高效液相色谱 (HPLC) 分级、含有雄激素受体 (YAS) 的重组酵母筛选在内的基于效应的分析 (EDA) 对生物废水和三级废水进行了 AA 污染物分析，并结合质谱分析。对来自膜生物反应器的废水二级出水的分析显示，AA 活性包含 14 个 HPLC 级分的复杂图谱，以及根据 GAC 处理条件，仅包含 2 到 4 个中等极性 HPLC 级分的 GAC 流出物的简单图谱。对二级出水中 AA 级分的气相色谱-质谱和超高效液相色谱-纳米喷雾质谱分析导致检测到超过 10 种化学污染物，这些污染物显示出对 YAS 活性的抑制作用，并且是潜在的 AA。推测的 AA 包括杀生物剂、食品添加剂、阻燃剂、药物和工业污染物。据我们所知，这是首次报道 N-乙基-2-异丙基-5-甲基环己烷甲酰胺 (WS3)、西替利嗪和奥卡西平的 AA 性质。本研究中使用的 EDA 被证明是一种强大的工具，可用于在复杂的水生环境中识别具有 AA 活性的新型化学结构。除 WS3 和三氯生外，所有鉴定出的抗雄激素在 GAC 上的吸附过程均符合准二级动力学模型。吸附到 GAC 上可以进一步去除生物废水中大多数已鉴定的 AA，效率很高。
