水中溴酸盐的急性生物毒性及致毒机理

发布时间：2018-04-25 20:24

  本文选题：臭氧氧化 + 溴酸盐　； 参考：《哈尔滨工业大学》2016年博士论文

【摘要】：由于臭氧氧化工艺在水处理过程中具有许多优点而得到了广泛应用,但是如果水中含有溴离子,则经臭氧氧化后会产生能够诱导试验鼠发生肾脏细胞肿瘤的副产物-溴酸盐,因此对水质安全产生了较大的威胁。本文针对水中溴酸盐的毒性风险开展系统的研究,通过几种不同营养级的典型毒理学检测生物,分析溴酸盐的急性生物毒性以及毒性作用规律和特征,寻找对溴酸盐毒性效应较敏感的检测生物和检测指标,探讨溴酸盐对敏感检测生物的致毒机理,利用较敏感的检测指标对含溴水经臭氧氧化后的水质综合毒性效应进行评价。本文的研究结果对深入研究溴酸盐的毒性作用规律及其致毒机理提供理论支持,为保障水质安全的生物毒理学标准体系的建立提供重要参考依据。由于溴酸盐对不同检测生物的毒性效应之间可能存在差异,因此为全面评价溴酸盐的毒性效应,寻找对溴酸盐毒性效应较敏感的检测生物,需要利用多种生物,多种指标进行综合评价。本文分别以不同营养级的几种典型的毒性检测生物作为研究对象进行试验研究。研究发现,溴酸盐(以溴酸钾为例)对斜生栅藻的96 h EC_(50)为738.18 mg/L,对微囊藻的96 h EC_(50)为195.39 mg/L,对大型蚤的48 h EC_(50)和LC_(50)分别为154.01 mg/L和198.52 mg/L,对裸腹蚤的48 h EC_(50)和LC_(50)分别为161.80 mg/L和175.68 mg/L,对斑马鱼的96 h LC_(50)为931.4mg/L,对Wistar大鼠和ICR小鼠的14天LD50分别为215 mg/kg和464 mg/kg。由此可见,不同检测生物对溴酸盐毒性效应的敏感性不同,其中大型蚤、裸腹蚤和微囊藻非常敏感,斜生栅藻次之,然后是斑马鱼,而普通小球藻和发光菌对溴酸盐的毒性效应不敏感。溴酸盐没有明显的蓄积毒性和遗传毒性,对试验大鼠的生长发育、脏器发育和组织形态以及肝脏功能均没有显著影响,但溴酸盐会引起试验大鼠白细胞计数显著降低,并且对试验大鼠的肾脏功能、糖代谢和脂代谢具有一定程度的影响。针对微囊藻和大型蚤对溴酸盐毒性效应较敏感的结果,本文考察了溴酸盐对藻细胞和大型蚤的致毒机理。研究发现造成藻细胞生长及大型蚤运动受到抑制或死亡的原因是溴酸盐毒性综合作用的结果。溴酸盐引起藻细胞产生过多活性氧导致藻细胞发生过氧化损伤、生理功能异常和细胞结构受损是其对藻细胞重要的致毒机理,溴酸盐引起大型蚤抗氧化系统、神经系统以及能量代谢的异常是其对大型蚤的重要致毒机理。在试验所考察的检测生物和检测指标中,溴酸盐对大型蚤Ca~(2+)/Mg~(2+)-ATP酶活性的影响显著,它可以作为评价溴酸盐毒性效应的重要指标。由于在含溴水臭氧氧化过程中,不只产生溴酸盐这一种副产物,因此仅仅考察溴酸盐的毒性效应不能反映水质真实的毒性效应。本文以二溴乙酸作为臭氧氧化含溴水的另一种副产物,考察了溴酸盐和二溴乙酸对大型蚤的联合毒性,结果发现有协同作用和部分相加作用两种联合毒性作用,说明副产物之间的联合作用有增加水质毒性效应的风险,有必要对水质的综合毒性效应进行研究。针对溴酸盐对大型蚤Ca~(2+)/Mg~(2+)-ATP酶活性影响显著的结果,本文利用大型蚤存活率和Ca~(2+)/Mg~(2+)-ATP酶活性为指标,以淀粉、牛血清白蛋白和腐殖酸分别代表水体中的多糖、氨基酸和腐殖质,考察了这些有机物对含溴水经臭氧氧化后的水质综合毒性效应的影响。研究发现溴离子浓度、溶解性有机碳浓度、臭氧浓度以及是否氯化都会影响含溴水经臭氧氧化后的水质毒性。当水中无溴离子时,单独臭氧氧化对水质毒性无明显影响。随溴离子浓度升高水质毒性增强,当溴离子达到4 mg/L时,水质毒性达到最大,继续增加溴离子浓度水质毒性不再增强,甚至有所降低。臭氧氧化后再进行氯化氧化,水质毒性会进一步增强。最佳臭氧浓度因溶解性有机碳浓度的不同而不同,增加或降低臭氧浓度都会引起水质毒性增加。在试验所考察的3种有机物中,腐殖酸对臭氧氧化后水质毒性的影响最大,牛血清白蛋白次之,淀粉最小。大型蚤Ca~(2+)/Mg~(2+)-ATP酶活性对水质毒性非常敏感,能较好地反映水质毒性,是评价水质安全的重要指标。
[Abstract]:The ozone oxidation process has been widely used in the process of water treatment. However, if bromine ions are contained in the water, bromine can be produced by ozone oxidation, which can induce renal cell tumor in rats. Therefore, it has a great threat to the safety of water quality. A systematic study of sexual risk was carried out to detect the acute biological toxicity of bromate and the regularity and characteristics of the toxic effect of bromate through several typical toxicology of different trophic levels, to find out the detection organisms and detection indexes sensitive to the toxic effect of bromate, and to explore the toxic mechanism of bromate to sensitive detection organisms. The comprehensive toxicity of bromine water after ozone oxidation was evaluated. The results of this paper provide theoretical support for the study of the toxicity and mechanism of bromate, and provide an important reference for the establishment of biotoxicology standard system for the safety of water. There may be differences between the toxic effects of bioassay, so it is necessary to make comprehensive evaluation of the toxic effects of bromate and to find a sensitive detection organism for the toxicity of bromate. It is necessary to use a variety of biological and multiple indicators to make a comprehensive evaluation. The study found that bromate (with potassium bromate) 96 h EC_ (50) is 738.18 mg/L, 96 h EC_ (50) is 195.39 mg/L to Microcystis, 48 h EC_ (50) and LC_ (50) of large fleas are 154.01 mg/L and 198.52 mg/L respectively. 6 h LC_ (50) was 931.4mg/L, and 215 mg/kg and 464 mg/kg. for Wistar rats and ICR mice were 215 mg/kg and 464 mg/kg., respectively. The sensitivity of different detection organisms to bromate toxicity was different, among which large fleas, Daphnia and Microcystis were very sensitive, and the other species were zebrafish, and Chlorella and luminescent bacteria were used for bromate. The toxic effects were not sensitive. Bromate did not have obvious accumulative toxicity and genotoxicity. It had no significant effect on the growth, development, morphology and liver function of rats, but bromate could significantly reduce the white cell count in experimental rats, and to test the renal function, sugar metabolism and lipid metabolism in experimental rats. The effects of Bromate on the toxic effects of Bromate on the toxic effects of Bromate on microcysta and large fleas were investigated. The study found that the cause of inhibition or death of the growth of the algae cells and the movement of the large fleas was the result of the comprehensive toxicity of bromate. Bromate caused algae to cause algae. The excessive active oxygen in the cells causes oxidative damage to the algae cells, the abnormal physiological function and the damage of the cell structure are its important toxic mechanism to the algal cells. The abnormality of bromate caused the antioxidant system of the fleas, the nervous system and the energy metabolism is an important toxic mechanism for the fleas. The effect of Bromate on the activity of Ca~ (2+) /Mg~ (2+) -ATP enzyme in the flea is significant. It can be used as an important indicator to evaluate the toxicity of bromate. It is not only a by-product of bromate in the process of bromine water ozonation, so only the toxicity effect of bromate can not reflect the true toxicity of water. The combined toxicity of bromate and di brooacetic acid on the large fleas was investigated by using Di bromo acetic acid as another by-product of the ozonation of bromine water. The results showed that there were two combined toxic effects of synergistic and partial additive effects, which indicated that the combined effect of the by-products had the risk of increasing the toxic effect of water quality, and the water quality was necessary. In this paper, the effects of Bromate on the activity of Ca~ (2+) /Mg~ (2+) -ATP enzyme were significantly affected. In this paper, the survival rate and Ca~ (2+) /Mg~ (2+) -ATP enzyme activity of Ca~ (2+) /Mg~ (2+) -ATP were used as indexes, and starch, bovine serum albumin and humic acid were used to substitute the polysaccharides, amino acids and humus in the water body. The study found that bromine ion concentration, concentration of dissolved organic carbon, ozone concentration and whether or not chlorination will affect the water toxicity of bromine water after ozonation. When no bromine ion in water, the ozone oxidation has no obvious effect on the toxicity of water. The toxicity of water quality increased. When bromine ion reached 4 mg/L, the toxicity of water quality reached the maximum. The toxicity of water quality was no longer enhanced or even decreased. The toxicity of water quality would be further enhanced after the oxidation of ozone. The best ozone concentration was different from the concentration of dissolved organic carbon, increasing or reducing odor. Of the 3 organic compounds examined in the experiment, humic acid has the greatest effect on the toxicity of water quality after ozonation, the second of the bovine serum albumin and the smallest starch. The activity of Ca~ (2+) /Mg~ (2+) -ATP enzyme of the large flea is very sensitive to the toxicity of water quality, and it can better reflect the toxicity of water quality, and it is important to evaluate the safety of water quality. Indicators.

【学位授予单位】：哈尔滨工业大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：X171.5
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本文编号：1802821