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含氮消毒副产物生成势及消毒副产物毒性
甘国娟
学位类型博士
导师梁岩
2017-05-01
学位授予单位中国科学院大学
学位授予地点新疆乌鲁木齐
学位专业理学博士
关键词含氮消毒副产物 水源水 亚硝氮 金属离子 卤代硝基甲烷 生理毒性 生殖毒性
摘要饮用水消毒副产物(DBPs)是近 40 年来饮用水安全的研究热点之一。虽然在饮用水消毒过程中含氮消毒副产物(N-DBPs)生成势低于含碳消毒副产物(C-DBPs),但因其具有较高的细胞毒性及基因毒性而被广泛研究。本论文通过野外采样分析与实验室化合物模拟分析相结合,研究了不同水源水 N-DBPs 生成势特征、水质及氯化条件对DBPs 生成势的影响、消毒副产物对小鼠的生理毒性和生殖毒性。初步得出如下结果:1. 新疆和广东两地水源水的氯化和氯胺化结果说明氯胺消毒可降低 N-DBPs 的生成势;从地域而言,新疆地区水源水 HNMs 生成势高于广东地区,广东水源 HANs生成势高于新疆水源,N-DBPs 生成势为广东水源高于新疆水源,原因是广东地区人类活动和水生生物代谢活动高于新疆地区;从季节而言,夏季新疆水源水 HNMs、HANs、N-DBPs 的生成势均高于冬季,这与气温影响水生生物生命活动有关。2. 在氯化糖类和酚类过程中,得出亚硝酸氮是氯化酚类形成 TCNM 的氮源,而并非氯化糖类形成 TCNM 的氮源。TCNM 的生成量受苯环上所连接官能团种类、数量及位置的影响。邻苯二酚、间苯二酚和间苯三酚的正交实验结果表明,pH 是影响TCNM 形成的关键因子,反应时间和反应温度影响较微弱。3. 在氯化消毒邻苯二酚与亚硝酸根过程中,首次发现了金属离子对 TCNM 形成具有明显的增强效果,促进作用顺序为 Fe3+>Ti4+>Al3+,且促进强度与金属离子浓度呈正比例相关。氯化条件的影响:金属离子对 TCNM 形成的促进作用在弱碱性条件(pH 8-9)高于弱酸性和中性;无论是延长反应时间还是提高反应温度,都未明显影响金属离子对 TCNM 形成的促进效果。此外,多种金属的共同作用效果与其中具有最高促进作用的金属离子相接近。4. 在氯化消毒色氨酸过程中,随着投氯量由 10 mg/L 增加到 75 mg/L,HAAs、HKs 生成势随之升高,HANs 生成势先降低再升高后降低,HNMs 生成势先升高后降低,对 THMs 生成势无影响,最佳适宜投氯量为 50 mg/L,DBPs 的生成势为 HAAs>THMs>HNMs>HANs>HKs。pH 升高会提高 HANs、HKs、HNMs 生成势,降低HAAs 生成势,对 THMs 生成势影响不明显。在有余氯存在情况下,亚硝酸氮添加会促使 HNMs 生成势增加,对 THMs、HAAs、HANs、HKs 生成势影响不明显。亚硝酸氮要成为 N-DBPs 的氮源,需要满足两个条件:一是水体具有较高的芳香性,二是亚硝酸氮是水体的主要氮源。随着溴离子浓度增加,THMs、HAAs、HNMs 生成势随之增加,HANs 和 HKs 的生成势无明显变化规律;溴代消毒副产物呈正比例增加,但氯代消毒副产物并未呈正比例下降。5. 色氨酸氯化消毒溶液会抑制小鼠的发育,pH=9 消毒溶液对小鼠血液代谢影响最大且对肝脏发育抑制最强。在 pH 和 Br-的影响下,色氨酸和色氨酸消毒溶液都对小鼠的肝脏细胞造成了氧化损伤且色氨酸溶液的损伤程度高于其消毒溶液,氯化处理可降低色氨酸溴离子添加组对肝脏的氧化损伤。色氨酸消毒溶液会对小鼠的肾脏细胞造成损伤,pH=9 消毒溶液对肾脏的氧化损伤高于其它处理组,氯化处理可增强色氨酸溴离子添加组对肾脏的损伤。pH=9 消毒溶液对小鼠具有较高的生理毒性。受检 28种 DBPs 引起的肝脏和肾脏损伤并不显著。6. 在 pH 和 Br-的影响下,色氨酸溶液和色氨酸消毒溶液会影响小鼠的发育,色氨酸溶液对小鼠整体和睾丸发育的抑制作用强于其消毒溶液,氯化处理降低了溴离子添加组对小鼠发育的抑制。pH=7 色氨酸消毒溶液对小鼠睾丸组织的损伤高于其它处理组,pH 降低和溴离子添加可显著降低消毒溶液对睾丸组织的损伤。色氨酸消毒溶液对精母细胞和睾丸骨架细胞损伤高于色氨酸溶液,特别是 pH=9、pH=7 和 Br-=5mg/L 消毒溶液。pH=7 消毒溶液会抑制小鼠精子的活力,弱酸性和弱碱性消毒溶液均不利小鼠精子生成,pH=5 和 pH=7 的消毒溶液会增加精子的畸形率,pH 升高和溴离子添加会降低消毒溶液对小鼠精子的损害。在 pH 和 Br-的影响下,色氨酸溶液和其消毒溶液对小鼠具有轻微的生殖毒性,色氨酸消毒溶液对小鼠生殖毒性强于色氨酸溶液。目前的结果并不能说明色氨酸消毒溶液的生殖毒性是由受检的 28 种 DBPs 引起的。
其他摘要Over the last 40 years, drinking water disinfection by-products (DBPs) is one of research hotspots of drinking water safety. Although the formation potential of nitrogenous disinfection by-products (N-DBPs) are lower than carbon disinfection by-products (C-DBPs) during drinking water disinfection, however, due to the cytotoxicity and genotoxicity of N-DBPs are higher than C-DBPs, so they have been widely studied. The N-DBPs formation potential of source water, the effect of water quality and chlorination condition on DBPs formation potential, physiological toxicity and reproduction toxicity of disinfection by-products in mice were investigated by the field sampling analysis and simulation analysis of laboratory compounds. The main results were as follows:1. The results showed that, compared with chlorination, the N-DBPs formation potential of source water of Xinjiang and Guangdong could be reduced by chloramination. From the perspective of geography, the HNMs formation potential of source water in Xinjiang was higher than Guangdong, while the HANs and N-DBPs formation potential of source water in Guangdong were higher than Xinjiang, due to the human activities and metabolic activity of aquatic organism in Guangdong were higher than Xinjiang. From the perspective of season, due to the life activities of aquatic organism in summer was higher than winter, the HNMs, HANs and N-DBPs formation potential of source water were summer higher than winter. 2. During chlorination, the phenols were easier to react with the nitrite to form TCNM precursors, as compared to the sugars, so nitrite was the nitrogen source of TCNM formation for the phenols, but it wasn't the nitrogen source of TCNM formation for the sugars. While among the phenols, the type, number and positions of functional groups on benzene ring were also key factors determining the contribution of nitrite to TCNM formation. Further studies also showed that during chlorination of poly-hydroxy phenols (catechol, resorcinol and phloroglucinol), the pH exhibited great influence for nitrite participating in TCNM molecules, while the reaction time and temperature had little influence to the this process. 3. During the chlorination of catechol and nitrite, metal ions had a significant enhancement effect on the formation of TCNM. It was found for the first time, and the promotional effect ranked as Fe 3+>Ti4+>Al3+, was directly proportional to the concentration of metal ions. The effect of chlorination conditions on TCNM formation were as follows:the enhancement effect was generally higher under basic pH 8-9 than neutral or acidic conditions, and neither the reaction time nor the temperature exerted any obvious influences. Additionally, the enhancement effect of a multiple-metal-ion mixture was similar to that of the single metal with the highest enhancement effect. 4. During chlorination of tryptophan, HAAs and HKs formation potential were increased with the chlorine dose rose from 10 mg/L to 75 mg/L, and the formation potential of HANs was decreased firstly and then increased, finally decreased, HNMs was increased firstly and decreased subsequently, none obvious change on THMs, the best chlorine dose was 50 mg/L, the formation potential of DBPs was HAAs>THMs>HNMs> HANs > HKs. HANs, HKs, HNMs formation potential were increased with pH increasing, while HAAs was decreased, none obvious change on THMs. With nitrite addition, the formation potential HNMs was increased with nitrite concentration increasing, but none effect on the formation potential of THMs, HAAs, HANs, HKs in the present of residual chlorine. Nitrite need to meet two conditions to be the nitrogen source of N-DBPs, one was high aromaticity of water, the other was that nitrite nitrogen was the main source of nitrogen in water. With bromide ion addition, THMs, HAAs, HNMs formation potential were increased with the biomide ion concentration increasing, and none obvious change on the formation potential of HANs and HKs; the formation potential of bromide by-products were directly proportional to the concentration of bromide ions, but the formation potential of chlorinated by-products had not been directly proportional decreased with the concentration of bromide ions increasing. 5. Mice growth could be inhibited by the tryptophan chlorination solution. The chlorinated solution at pH=9 exerted maximum influence on mice blood metabolism and the strongest inhibition on the liver growth. Under pH and Br - influence, tryptophan solution and its disinfectants had oxidative damage on mice liver cells, damage level was tryptophan solution higher than its disinfectants. The oxidative damage on liver cells of adding bromide ions tryptophan groups could be reduced by chlorination. Chlorination solution of tryptophan had a damage on kidney cells of mice, pH=9 chlorination solution was the most serious in all treatment groups, bromide ion addition could be increased the damage of tryptophan solution by chlorination. pH=9 chlorination solution played a higher physiological toxicity on mice. There was non-significant damage of liver and kidney cuased by 28 DBPs which were detected in this research. 6. Under pH and Br - influence, the mice growth could be inhibited by tryptophan solution and its disinfectants, and the inhibition level on development of body and testis were tryptophan solution higher than its disinfectants, the inhibition level of bromide ion addition groups reduced by chlorination. The damage level of pH=7 chlorination solution was the most serious to testicular tissue in all treatment groups, pH decrease and bromide ion addition can significantly reduced the damage of testicular tissue during chlorination. The damage level of spermatocyte and sertoli cells in testis were chlorination solution higher than non-chlorination solution, in particular pH=9, pH=7, and Br -=5 mg/L chlorination solution. pH=7 chlorination solution could to inhibit the motility of sperm, chlorination solution of weak acid and weak alkaline had adverse effect on sperm production, pH=5 and pH=7 chlorination solution could to increase the abnormality rate of sperm, pH increase and bromide ion addition could to reduce the damage of sperm from chlorination solution. Under pH and Br- influence, tryptophan solution and its disinfectants had weak reproductive toxicity on mice, and the reproductive toxicity of tryptophan chlorination solution was higher than tryptophan solution. So far, the results cannot suggest that the reproductive toxicity of tryptophan chlorination solution were caused by 28 DBPs which were detected in this research.
学科领域生态学
语种中文
文献类型学位论文
条目标识符http://ir.xjlas.org/handle/365004/14780
专题研究系统_荒漠环境研究室
作者单位中国科学院新疆生态与地理研究所
推荐引用方式
GB/T 7714
甘国娟. 含氮消毒副产物生成势及消毒副产物毒性[D]. 新疆乌鲁木齐. 中国科学院大学,2017.
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