城市污水中天然激素结合体的快速分析方法及其去除规律研究

Both natural hormones and their conjugates exist in municipal wastewater. Natural hormones are main compounds in wastewater with large proportion and strong estrogenic or androgenic potencies, which have been widely studied; while natural hormone conjugates are minor compounds in wastewater with low proportion and weak estrogenic or androgenic potencies, which are hardly studied. Based on our preliminary research results on natural estrogen conjugates and summarization, it is suggested that existence of natural hormone conjugates is the main reason for the bad removal performance of municipal wastewater treatment systems for natural hormones. As we are lack of understanding on natural hormone conjugates and the difficulty in their analytical method, the two main contents of this project are to: (1) develop fast determination method for the analysis of natural androgen conjugates and phytoestrogen conjugates based on our previous work on the fast analysis of natural estrogen conjugates; (2) understand the levels of the above mentioned three natural hormone conjugates in municipal wastewater and their removal properties by wastewater treatment systems. The main objective is to elucidate the environmental behavior of natural hormone conjugates during municipal wastewater treatment system; meanwhile, crucial factors for the fast removal of natural hormone conjugates are preliminary determined. The scientific significance of this project would facilitate to develop municipal wastewater treatment system with stable and well removal performance on natural hormones.

污水中存在天然激素和天然激素结合体。前者具有较强生物活性且存在比例大,是关注的热点；而后者的生物活性低且存在比例少，同时因其分析方法耗时长、分析不便，很少被关注。基于项目申请者对天然雌激素结合体的初步研究结果及文献整理后推断，天然激素结合体可能是当前生物污水处理工艺对天然激素去除效果不好的主因，理应重点关注。针对目前仍缺乏对天然激素结合体在污水处理过程中环境行为的了解、以及其分析方法耗时长的难点问题，本研究将:(1)以天然雌激素结合体的快速分析方法为基础，建立快速测定污水中天然雄激素结合体和植物雌激素结合体的分析方法:(2)阐明城市生活污水中上述3类天然激素结合体的存在特性，及其在污水处理过程中的去除规律。研究的主要目的是掌握天然激素结合体在污水生物处理系统中的环境行为，并初步掌握快速去除天然激素结合体的关键因素。本研究的展开将有助于提高现行生物污水处理工艺对天然激素的去除效果和稳定性。

在面上基金项目的支持下，在环境激素类物质的研究方面取得了一些发现和重要进展。具体如下：（1）基于人体尿液数据，绘制了全球人体双酚A暴露量水平地图，以及年暴露量趋势;（2）建立基于GC-MS测定10种双酚A类物质的分析方法，并系统比较了我国瓶装水和桶装水中双酚A类物质的浓度水平，研究结果指出经常饮用桶装水存在一定的雌激素活性干扰的影响；（3）基于瓶装水和食用油中常见塑化剂的浓度水平，合理评估了人体塑化剂暴露量水平及潜在风险；（4）系统研究了城市污水中的芳基硫酸酯酶和beta-葡萄糖苷醛酸酶，发现它们是两种耐重金属和叠氮钠的极端酶，但它们对高pH较为敏感，当pH=11时，两种酶都可以被抑制。基于此发现，我们建立了一种有效保存污水样品硫酸酯结合体和葡萄糖苷醛酸结合体的方法；（5）建立了在线SPME-GCMS等分析技术测定19种致水体嗅味物质的分析方法，可用于此类饮用水异味物质的快速筛查。(6)初次发现过氧乙酸等多个小分子物质可有效抑制芳基硫酸酯酶和葡萄糖苷醛酸酶，本发现在乳腺癌等治疗方面有一定的应用潜能。以第一作者或者通讯作者发表SCI研究论文14篇，其中Water Research论文1篇，Science of the Total Environment论文6篇，Environmental Pollution论文 1篇。论文发表以来得到了美国化学理事会和国外30余家媒体的关注。申请国家发明专利10项，含一项PCT专利申请，以第一作者在科学出版社出版学术专著1本，并获得国家科学技术学术著作出版基金的资助。