Institut für Energie - und Umwelttechnik e. V., (IUTA, Institute of Energy and Environmental Technology), Bliersheimer Str. 58-60, 47229 Duisburg, Germany; University of Duisburg-Essen, Instrumental Analytical Chemistry, Universitätsstrasse 5, 45141 Essen, Germany; Centre for Water and Environmental Research (ZWU), University of Duisburg-Essen, Universitätsstrasse 2, 45141 Essen, Germany.
Federal Institute of Hydrology (BfG), Am Mainzer Tor 1, 56068 Koblenz, Germany.
Sci Total Environ. 2018 May 15;624:1443-1454. doi: 10.1016/j.scitotenv.2017.12.181. Epub 2017 Dec 27.
To reduce the discharge of micropollutants, advanced wastewater treatment methods were investigated in the last years. Estrogenic effects were found to be reduced by ozonation. These activities are usually measured using genetically modified cell-based tests. As these bioassays are representing a sum parameter, also inhibitory effects such as antagonistic effects need to be further investigated as they are potentially reducing the detected activities. Therefore, a direct comparison of chemical target analysis and biological equivalent concentrations measured by bioassays is often difficult. To investigate the fate of antagonistic activities and their role in mixtures with agonistic activities, two hospital wastewater treatment plants were studied after different treatment steps. Thereby highly enriched samples were analyzed by a combination of bioassays with chemical target and non-target analyses. In order to achieve an in-depth characterization of the antagonistic activities a fractionation of the enriched samples was performed. To identify relevant compounds an effect directed identification approach was used by combining high-resolution mass spectrometry and bioassays. The results showed a high reduction for estrogene and androgene activities. However, a constant antagonistic activity after membrane bioreactor and ozone treatment was observed. A reduction of the antagonistic activity was observed after passing an activated carbon filter. The fractionation approach showed a specific finger-print of each sample of the different treatment steps. Hereby we could show that the composition of agonistic and antagonistic active compounds is changing after each treatment step while the overall measured activity stays the same. Using fractionation and the combination of bioassays the number of relevant features detected by chemical non-target screening could be reduced by >85%. As a result the phosphorous flame retardant TCEP could be identified as anti-estrogene active. Future research should be done to identify more antagonistic active compounds and potentially active transformation products after ozone treatment.
为了减少微污染物的排放，近年来研究了先进的废水处理方法。发现臭氧氧化可以降低雌激素效应。这些活性通常使用基于基因改造的细胞生物测定法来测量。由于这些生物测定法代表了总和参数，因此还需要进一步研究抑制作用，如拮抗作用，因为它们可能会降低检测到的活性。因此，化学靶标分析与生物测定法测量的生物等效浓度之间的直接比较通常很困难。为了研究拮抗活性的命运及其在与激动剂活性混合物中的作用，研究了两个医院废水处理厂在不同处理步骤后的情况。因此，通过生物测定法与化学靶标和非靶标分析相结合的方法分析了高度浓缩的样品。为了深入表征拮抗活性，对浓缩样品进行了分级。为了鉴定相关化合物，采用了结合高分辨率质谱和生物测定法的定向识别方法。结果表明，雌激素和雄激素活性有很高的降低。然而，在膜生物反应器和臭氧处理后观察到恒定的拮抗活性。通过活性炭过滤器后，拮抗活性降低。分级方法显示了不同处理步骤的每个样品的特定指纹。由此可以看出，在每个处理步骤之后，激动剂和拮抗剂活性化合物的组成都在发生变化，而总的测量活性保持不变。通过分级和生物测定法的结合，可以将通过化学非靶标筛选检测到的相关特征数量减少>85%。结果表明，可以鉴定出作为抗雌激素活性的磷系阻燃剂 TCEP。未来的研究应致力于确定臭氧处理后更多的拮抗活性化合物和潜在的活性转化产物。
