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水中阿替洛尔去除的氧化处理:通过质谱法阐明及降解产物的毒性评估

Oxidative treatments for atenolol removal in water: Elucidation by mass spectrometry and toxicity evaluation of degradation products.

作者信息

Quaresma Amanda V, Sousa Bianca A, Silva Karina T S, Silva Silvana Q, Werle Alceni A, Afonso Robson J C F

机构信息

Environmental Engineering Post-Graduate Programme (ProAmb), Universidade Federal de Ouro Preto, Ouro Preto, MG, 35400-000, Brazil.

Chemistry Department, Universidade Federal de Ouro Preto, Ouro Preto, MG, 35400-000, Brazil.

出版信息

Rapid Commun Mass Spectrom. 2019 Feb 15;33(3):303-313. doi: 10.1002/rcm.8338.

Abstract

RATIONALE

The presence of pharmaceuticals in water is a worldwide concern due to potential damage to human and environmental health. For example, compounds such as the β-blocker atenolol (ATE), widely used for the treatment of cardiac disease, are detected in drinking water since conventional water treatment plants are not designed to remove them. Thus, the evaluation of ATE removal at different water oxidative treatment processes, identification of its degradation products and evaluation of their toxicity is necessary.

METHODS

Aqueous solutions of ATE (10 mg/L) were submitted to oxidative treatments of chlorination ([NaClO] = 10 mg/L), ozonation ([O ] = 8 mg/L), photocatalysis ([TiO ] = 120 mg/L and UV-C light) and photolysis (UV-C light). The removal of ATE and formation of degradation products (DPs) were monitored by mass spectrometry. To assess acute cytotoxicity, DPs were submitted to colorimetric MTT assay using HepG2 cells. The Ecological Structure Activity Relationships (ECOSAR) software was applied to estimate the acute and chronic toxicity of identified DPs at different trophic levels.

RESULTS

Photocatalysis was the treatment that demonstrated greater efficiency, removing 94% of the initial ATE. For the four tested treatments, 12 DPs were confirmed after 30 min. Moreover, some of the identified DPs were unpublished in the literature. Through high-resolution mass spectrometry (HRMS), it was possible to elucidate the structure of the DPs. Solutions of DPs were not considered to be toxic to HepG2 cells. Only the DP with a molecular formula of C H NO (m/z 238.1438) could be considered detrimental to daphnid and green algae.

CONCLUSIONS

Low rates of organic matter removal and high rates of ATE degradation were obtained in the applied treatments after 30 min. Although the treated solutions were not toxic to HepG2 cells, one of the degradation products can be considered an environmental concern since it presents chronic toxicity to daphnid and green algae.

摘要

原理

水中存在药物是一个全球性问题,因为这可能对人类和环境健康造成损害。例如,β受体阻滞剂阿替洛尔(ATE)等广泛用于治疗心脏病的化合物在饮用水中被检测到,因为传统的水处理厂并非设计用于去除这些物质。因此,有必要评估不同水氧化处理工艺对阿替洛尔的去除效果,鉴定其降解产物并评估其毒性。

方法

将阿替洛尔(10 mg/L)的水溶液进行氯化([NaClO]=10 mg/L)、臭氧化([O]=8 mg/L)、光催化([TiO]=120 mg/L和紫外光-C)和光解(紫外光-C)氧化处理。通过质谱监测阿替洛尔的去除和降解产物(DPs)的形成。为了评估急性细胞毒性,使用HepG2细胞对降解产物进行比色MTT测定。应用生态结构活性关系(ECOSAR)软件估计已鉴定的降解产物在不同营养水平下的急性和慢性毒性。

结果

光催化是表现出更高效率的处理方法,去除了94%的初始阿替洛尔。对于四种测试处理,30分钟后确认了12种降解产物。此外,一些已鉴定的降解产物在文献中尚未发表。通过高分辨率质谱(HRMS),可以阐明降解产物的结构。降解产物溶液对HepG2细胞无毒。只有分子式为C H NO(m/z 238.1438)的降解产物可被认为对水蚤和绿藻有害。

结论

在30分钟的应用处理后,获得了较低的有机物去除率和较高的阿替洛尔降解率。尽管处理后的溶液对HepG2细胞无毒,但其中一种降解产物可被视为环境问题,因为它对水蚤和绿藻具有慢性毒性。

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