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藻类和浮萍废水处理系统中雌酮、17α-乙炔基雌二醇和 17β-雌二醇的去除。

Removal of estrone, 17alpha-ethinylestradiol, and 17beta-estradiol in algae and duckweed-based wastewater treatment systems.

机构信息

State Key Laboratory of Urban Water Resources and Environment, School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin, 150090, People's Republic of China.

出版信息

Environ Sci Pollut Res Int. 2010 May;17(4):824-33. doi: 10.1007/s11356-010-0301-7. Epub 2010 Mar 7.

Abstract

BACKGROUND, AIM, AND SCOPE: Many pollutants have received significant attention due to their potential estrogenic effect and are classified as endocrine disrupting compounds (EDCs). Because of possible ecological effects and increased attention for water reuse schemes, it is important to increase our understanding of the EDC removal capacities of various wastewater treatment systems. However, there has so far been little research on the fate and behavior of EDCs in stabilization pond systems for wastewater treatment, which represent an important class of wastewater treatment systems in developing countries because of their cost-effectiveness. The aim of this work is to study the fate and behavior of EDCs in algae and duckweed ponds. Because the synthetic hormone 17alpha-ethinylestradiol (EE2) and the natural hormones estrone (E1), as well as 17beta-estradiol (E2), have been detected in effluents of sewage treatment plants and been suggested as the major compounds responsible for endocrine disruption in domestic sewage; E1, E2, and EE2 were therefore chosen as target chemicals in this current work.

MATERIALS AND METHODS

Both batch tests and continuous-flow tests were carried out to investigate the sorption and biodegradation of estrogens in algae and duckweed pond systems. The applied duckweed was a Lemna species. The applied algae was a mixture of pure cultures of six different algae genera, i.e., Anabaena cylindrica, Chlorococcus, Spirulina platensis, Chlorella, Scenedesmus quadricauda, and Anaebena var. Synthetic wastewater were used in all tests. The concentrations of estrogens were measured with three different enzyme-linked immunosorbent assay kits specific for E1, E2, or EE2. When the concentrations of estrogens in water samples were below the lowest quantitative analysis range (0.05 microg/l), preconcentration of the water samples were performed by means of solid phase extraction (SPE) with C18 cartridges.

RESULTS

The 6-day batch tests show that the presence of algae or duckweed accelerated the removal of the three estrogens from the synthetic wastewater. More estrogens were removed in the tests with duckweed than in tests with algae or with wastewater. In the sorption tests, a swift sorption of the three estrogens was observed when the estrogens were contacted with duckweed or algae, while the estrogen concentrations in tap water kept unchanged during the 3-h sorption tests. The mass balances indicated that only about 5% of the estrogens were bound to the algae sediment or duckweed at the end of the 6-day tests. Results of the continuous-flow tests revealed that the algae and duckweed ponds effectively removed E1, E2, and EE2 even at nanograms per liter level. Interconversion of E1 and E2 occurred both in batch and continuous-flow tests. E2 could be readily transformed to E1, especially in the tests with algae.

DISCUSSION

Different processes like sorption, biodegradation and photolytic degradation might play an important role in the removal of estrogens from the aquatic phase. The 3-h sorption tests support the importance of sorption for estrogen removal, in which a rapid initial sorption was observed over the first 2 min for E1/E2/EE2 to both duckweed and algae. In the 6-day batch tests, estrogens were sorbed by algae or duckweed during the early stage when algae and duckweed were contacted with the synthetic wastewater and the sorbed estrogens were further biodegraded by the microorganisms developed in the wastewater. The persistent estrogen concentrations in tap water, however, implied that no sorption, biodegradation, or photolytic degradation occurred in tap water under the specific experimental conditions. Under aerobic or anoxic conditions, E2 could be first oxidized to E1, which is further oxidized to unknown metabolites and finally to CO(2) and water. Under anaerobic conditions, E1 can also be reduced to E2. However, the interconversion might be much more complex especially in the tests with algae because both aerobic and anaerobic conditions occurred in these tests due to the variation of the dissolved oxygen concentration induced by the light regime.

CONCLUSIONS

This study shows that estrogens, E1, E2, and EE2, can be effectively removed from the continuous-flow algae and duckweed ponds even when their concentrations are at nanograms per liter level. The presence of algae and duckweed accelerate the removal of estrogens from the synthetic wastewater because estrogens can be quickly sorbed on duckweed or algae. The sorbed estrogens are subsequently degraded by microorganisms, algae, or duckweed in the wastewater treatment system. E1 and E2 are interconvertible in both duckweed and algae pond systems. E2 can be readily transformed to E1, especially in the tests with algae.

RECOMMENDATION AND PERSPECTIVES

Based on the tests performed so far, one can conclude that both sorption and biodegradation are important to the estrogens removal from stabilization pond systems for wastewater treatment. Further research using, e.g., radioimmunoassay is needed to investigate the biodegradation pathway of estrogens in algae and duckweed ponds.

摘要

背景、目的和范围:由于许多污染物具有潜在的雌激素效应,因此被认为是内分泌干扰化合物(EDCs),受到了广泛关注。由于可能产生的生态影响以及对水再利用方案的日益关注,增加我们对各种废水处理系统去除内分泌干扰物能力的了解变得非常重要。然而,目前为止,关于稳定塘系统中内分泌干扰物的命运和行为的研究还很少,因为这些系统在发展中国家具有成本效益,是一种重要的废水处理系统。本研究的目的是研究藻类和浮萍池塘中内分泌干扰物的命运和行为。由于在污水处理厂的污水中已经检测到合成激素 17alpha-乙炔雌二醇(EE2)和天然激素雌酮(E1)以及 17beta-雌二醇(E2),并被认为是造成生活污水内分泌干扰的主要化合物;因此,在目前的工作中选择 E1、E2 和 EE2 作为目标化学物质。

材料和方法

进行了批处理试验和连续流试验,以研究藻类和浮萍池塘系统中雌激素的吸附和生物降解。应用的浮萍是一种浮萍属植物。应用的藻类是六种不同藻类属的纯培养物混合物,即鱼腥藻、小球藻、螺旋藻、绿藻、四尾栅藻和鱼腥藻。所有试验均采用合成废水。使用三种针对 E1、E2 或 EE2 的不同酶联免疫吸附试剂盒测量雌激素的浓度。当水样中的雌激素浓度低于最低定量分析范围(0.05μg/L)时,通过 C18 小柱固相萃取(SPE)对水样进行预浓缩。

结果

为期 6 天的批处理试验表明,藻类或浮萍的存在加速了合成废水中三种雌激素的去除。浮萍试验中去除的雌激素比藻类试验或废水试验中去除的雌激素多。在吸附试验中,当雌激素与浮萍或藻类接触时,观察到三种雌激素迅速吸附,而在 3 小时的吸附试验中,自来水中的雌激素浓度保持不变。质量平衡表明,在 6 天的试验结束时,只有约 5%的雌激素结合到藻类沉积物或浮萍中。连续流试验的结果表明,即使在纳克/升水平,藻类和浮萍池塘也能有效地去除 E1、E2 和 EE2。在批处理和连续流试验中均发生了 E1 和 E2 的相互转化。E2 可以很容易地转化为 E1,特别是在藻类试验中。

讨论

不同的过程,如吸附、生物降解和光降解,可能在雌激素从水相去除中发挥重要作用。3 小时的吸附试验支持了吸附在雌激素去除中的重要性,其中在最初的 2 分钟内观察到 E1/E2/EE2 对浮萍和藻类的快速初始吸附。在为期 6 天的批处理试验中,当藻类和浮萍与合成废水接触时,雌激素被藻类或浮萍吸附,而在废水中发育的微生物进一步降解了吸附的雌激素。然而,自来水中持续存在的雌激素浓度意味着在特定的实验条件下,自来水中没有发生吸附、生物降解或光降解。在有氧或缺氧条件下,E2 首先可以氧化为 E1,E1 进一步氧化为未知代谢物,最终氧化为 CO2 和水。在厌氧条件下,E1 也可以还原为 E2。然而,特别是在藻类试验中,这种相互转化可能更为复杂,因为由于光周期引起的溶解氧浓度的变化,同时存在有氧和无氧条件。

结论

本研究表明,即使在纳克/升水平,雌激素、E1、E2 和 EE2 也可以有效地从连续流藻类和浮萍池塘中去除。藻类和浮萍的存在加速了合成废水中雌激素的去除,因为雌激素可以迅速吸附在浮萍或藻类上。在废水处理系统中,吸附的雌激素随后被微生物、藻类或浮萍降解。E1 和 E2 在浮萍和藻类池塘系统中是可相互转化的。E2 可以很容易地转化为 E1,特别是在藻类试验中。

建议和展望

基于目前进行的试验,可以得出结论,吸附和生物降解对稳定塘系统中雌激素的去除都很重要。需要进一步使用放射性免疫测定法等研究雌激素在藻类和浮萍池塘中的生物降解途径。

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