2,4-二羟基二苯甲酮在（光）氯消毒处理中的转化机 制及毒性评价研究
文献类型：学位论文
| 作者 | 刘伟 |
| 学位类别 | 硕士 |
| 答辩日期 | 2016-04 |
| 授予单位 | 中国科学院研究生院 |
| 授予地点 | 北京 |
| 导师 | 魏东斌 |
| 关键词 | BP-1，氯化消毒，光-氯联合处理，转化机理，遗传毒性 BP-1, chlorination desinfection, light-chlorine combined treatment, transformation mechanism, genotoxicity |
| 其他题名 | The transformation and the toxicity evaluation of 2,4-dihydroxybenzophenone during the (photo-induction) chlorination disinfection process |
| 学位专业 | 分析化学 |
| 中文摘要 | 2,4-二羟基二苯甲酮（BP-1）是一种重要的紫外防晒剂，在个人护理品与工业产品中都有广泛应用。其在环境水样、人血清、尿液等样本中都有检出。氯化消毒工艺是水处理中重要的环节，由于其具有廉价、高效、操作简单等特点，在饮用水、再生水、游泳池水消毒等领域具有非常广泛的应用。本文主要研究了 BP-1作为前体物质在氯化消毒过程中的转化机理以及毒性变化特征。另外，由于光在水处理过程中是不可避免的因素，因此本研究在 BP-1氯化转化机理的基础上进一步探索了 BP-1在光-氯联合作用下的转化机理与毒性变化，主要结论如下： （1）、揭示了 BP-1在氯化消毒过程中的转化机理和毒性变化规律。首先借助高效液相色谱-质谱联用技术对 BP-1的氯化转化产物进行了分离和鉴定，共鉴定出 16种 BP-1的氯化转化产物，其中包括一些氯代苯醌类产物、联苯类产物等。在分析这些产物结构的基础上结合实验现象和有机化学反应机理，提出了 BP-1在氯化转化过程中的转化路径。BP-1的氯化转化过程主要包括以下六类反应：苯环上氢原子的氯化取代反应、酮的 Baeyer-Villiger氧化成酯反应、酯类化合物的水解反应、羧基脱除反应、苯环偶联反应、对羟基苯酚氧化成醌反应等。正交实验发现 BP-1的氯化过程中 pH主要影响发生反应的类型，氯剂量主要影响反应进行的程度。毒性测试结果表明，在酸性与中性、5倍氯当量反应条件下，BP-1氯化产物的混合液的遗传毒性较 BP-1母体有明显的升高，表明在此过程中有具有较高遗传毒性产物生成。 （2）、BP-1在光-氯联合作用下，其转化产物的种类与氯化条件下相同。但其两种转化产物 P7与P10的产量较氯化过程中有明显的升高。转化产物P7是P1经过Baeyer-Villiger氧化反应生成的。P10是P2’经过苯环偶联与Baeyer-Villiger氧化反应生成的。这一结果表明 BP-1在氯化过程中，光很可能促进 Baeyer-Villiger氧化反应与苯环的偶联反应的发生。 |
| 英文摘要 | The 2,4-dihydroxybenzophenone（BP-1） is an important UV filter, which is widely used in personal care products and industrial products. It has been detected in environmental water, human serum and human urine samples and so on. Chlorination process is an important part in water treatment. Because of its low cost, high effeciency and confident operation, chlorination process has been widely used in drinking water treatment, reclaimed water and swimming water treatment all over the world. This study has explored the transformation process of BP-1 and the change of the genotoxicity during chlorination process. In addition, light irradiation is an unavoidable factor in the treatment process of water, so this study explored the transformation of BP-1 under photo induction chlorine combined treatment on the basis of BP-1 chlorination transformation. The main results of this study include: (1) The chlorination process of BP-1 and the change of genotoxicity has been discovered. The transformation products of BP-1 was separated and identified by UPLC-MS. And 16 transformation products were identified, including a series of chlorobenzoquinone-type transformation products and biphenyl-type transformation products and so on. Based on analyzing the mass spectrum of the transformation products and the organic chemical reaction principals, a transformation pathway of BP-1 during chlorination process was proposed. Six type of reactions occoured in this process. The first one is the chlorinated substitution of the hydrogen atom in the benzene ring. The second one is a Baeyer-Villiger-Type oxidation. The third one is the hydrolysis of the ester. The fourth one is the decarboxylation reaction. The fifth one is the oxidation of the p-dihydroxybenzene to generate benzoquinone type transformation products. The sixth one is the coupling of the two benzenes in BP-1 molecule. The orthogonal experiment indicates that the pH mainly influences the type of the reaction, while the dose of the chlorine mainly influences the extent of the transformation process. The genotoxicity of the reaction mixture has an obvious increase under acid and neutral pH conditions, 5-equivalent chlorine dose, which indicates that some transformation products with high genotoxicity generates under these conditions. (2) The type of the transformation products under photo induction chlorine combined treatment was the same as under chlorination treatment. But, the yield of two transformation products P7 ans P10 was higher than in chlorination process. P7 was generated from P1 through Baeyer-Villiger-Type oxidation, and P10 was generated from P2’ through the benzene- coupling reaction and Baeyer-Villiger-Type oxidation. This result indicates that the benzene-coupling reaction and Baeyer-Villiger-Type oxidation can be probably promoted by the light. |
| 源URL | [http://ir.rcees.ac.cn/handle/311016/36898]  |
| 专题 | 生态环境研究中心_环境化学与生态毒理学国家重点实验室 |
| 推荐引用方式 GB/T 7714 | 刘伟. 2,4-二羟基二苯甲酮在（光）氯消毒处理中的转化机 制及毒性评价研究[D]. 北京. 中国科学院研究生院. 2016. |
入库方式： OAI收割
来源：生态环境研究中心
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