Background

The European Commission Implementing Decision EU 2015/495 included three steroidal estrogens, namely 17α-ethinyl estradiol, 17β-estradiol, and estrone, in the so-called “watch list” of the EU Water Framework Directive (WFD). The monitoring of these compounds is difficult because the detection limits of the majority of the available analytical methods cannot achieve the very low target concentrations required to meet proposed environmental quality criteria. In 2014, a combined Science-Policy Interface/Chemical Monitoring of Emerging Pollutants project was launched to meet this monitoring challenge. The project involved 24 research organizations and environmental agencies from 12 different countries.

Methods

Sixteen surface water (SW) and 17 wastewater (WW) samples were collected across Europe and analysed using five in vitro effect-based and three chemical analytical methods. A general description of the project and data evaluation is provided by Könemann and colleagues in the companion publication 2018. In our study, we compared bioanalytical and chemical analytical results with regard to their application for aquatic status assessment. Therefore we considered the potential to predict population-relevant risks for aquatic organisms and the specificity and sensitivity of the various methods used in both approaches. Finally we tested and discussed the applicability and relevance of previously suggested effect-based trigger values (EBT).

Results

and discussion: Results of the risk assessment based on chemical analytical data correlated highly with estrogenic activities (expressed as 17β-estradiol equivalents (EEQ) determined using effect-based methods), demonstrating the ability of the bioassays to predict mixture risk caused by steroidal estrogens. For about 15 % of SW and 40 % of WW samples detection limits of chemical-analytical methods were too high to allow a status assessment, while detection limits of all effect-based methods were below proposed EBT. This demonstrates that effect-based methods are suitable for status assessment of surface waters. The in vitro effect-based methods were quite specific for steroidal estrogens and highly sensitive, meaning they have a low probability to detect false positive or negative results. After testing of three alternative EBT proposals, we concluded to use preliminary 400 pg/L EEQ as screening EBT corresponding to the AA-EQS of E2. Further test specific refinements in the application of this value are not excluded.

Conclusions

We conclude that water quality assessment can progress from a purely analytical approach to effect-based monitoring, from single substance to known and unknown mixture assessment and from in vitro screening to population-relevant risk assessment. Despite a few limitations, effect-based in vitro methods are recommendable for monitoring steroidal estrogens under the WFD because they, a) are able to sensitively quantify the activity of steroidal estrogens in all surface and wastewater samples, b) are able to detect the combined effect of estrogen mixtures including unknown chemicals with estrogen receptor activating properties, c) allow an ecotoxicological status assessment using EBT to calculate risk quotients. This approach is similar to the risk ratio used in regulatory environmental risk assessments, but allows for an integrated mixture assessment.

Outlook

The results of this study support the introduction of a holistic approach for the regulation of chemicals in the aquatic environment under the EU WFD, as proposed recently by EU Water Directors. An ecotoxicological status assessment for one of the most relevant modes of action of endocrine disruption will allow authorities responsible for water quality assessment to focus available monitoring resources and to improve the ecological status of EU waterbodies.

中文翻译：

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表面和废水中甾体雌激素的筛选和风险管理解决方案

背景

欧盟委员会实施决定EU 2015/495包括三个类固醇雌激素，即17α-炔雌醇，17β-雌二醇和雌酮，列为欧盟水框架指令（WFD）的所谓“观察名单”。这些化合物的监测非常困难，因为大多数可用分析方法的检测限都无法达到满足提议的环境质量标准所需的非常低的目标浓度。2014年，启动了科学政策界面/新兴污染物化学监测相结合的项目，以应对这一监测挑战。该项目涉及来自12个不同国家的24个研究组织和环境机构。

方法

在欧洲范围内收集了16个地表水（SW）和17个废水（WW）样本，并使用了五种基于效果的体外分析方法和三种化学分析方法进行了分析。Könemann及其同事在随附出版物2018中提供了该项目的一般说明和数据评估。在我们的研究中，我们比较了生物分析和化学分析结果与它们在水生状况评估中的应用。因此，我们考虑了预测与水生生物有关的种群相关风险的潜力，以及在这两种方法中使用的各种方法的特异性和敏感性。最后，我们测试并讨论了先前建议的基于效果的触发值（EBT）的适用性和相关性。

结果

与讨论：基于化学分析数据的风险评估结果与雌激素活性高度相关（表示为17β-雌二醇当量（EEQ），采用基于效果的方法确定），证明了生物测定法能够预测类固醇雌激素引起的混合风险。对于大约15％的SW和40％的WW样品，化学分析方法的检出限过高，无法进行状态评估，而所有基于效果的方法的检出限均低于建议的EBT。这表明基于效果的方法适用于地表水状态评估。在体外基于效果的方法对甾体雌激素非常专一且高度敏感，这意味着它们检测假阳性或阴性结果的可能性很小。在测试了三个替代性EBT提案之后，我们得出结论，初步使用400 pg / L EEQ作为与E2的AA-EQS相对应的EBT筛选。不排除对该值的应用进行进一步的测试特定改进。

结论

我们得出结论，水质评估可以从纯粹的分析方法发展到基于效果的监测，从单一物质到已知和未知混合物的评估，再从体外筛选到与人群相关的风险评估。尽管有一些局限性，但基于效果的体外建议在WFD下监测甾体雌激素的方法，因为它们：a）能够灵敏地定量所有表面和废水样品中甾体雌激素的活性，b）能够检测雌激素混合物的综合作用，包括未知的具有雌激素受体的化学物质c）允许使用EBT进行生态毒理状况评估以计算风险商。这种方法类似于监管环境风险评估中使用的风险比率，但是允许进行综合的混合物评估。

外表

这项研究的结果支持根据欧盟水务署（EU Water Directors）的最新建议，采用一种整体方法来监管欧盟WFD下的水生环境中的化学物质。对最相​​关的内分泌干扰作用方式之一进行生态毒理学状态评估，将使负责水质评估的当局能够集中可用的监测资源并改善欧盟水体的生态状况。