本文選題：臭氧氧化 + 溴酸鹽��； 參考：《哈爾濱工業(yè)大學(xué)》2016年博士論文

【摘要】：由于臭氧氧化工藝在水處理過(guò)程中具有許多優(yōu)點(diǎn)而得到了廣泛應(yīng)用,但是如果水中含有溴離子,則經(jīng)臭氧氧化后會(huì)產(chǎn)生能夠誘導(dǎo)試驗(yàn)鼠發(fā)生腎臟細(xì)胞腫瘤的副產(chǎn)物-溴酸鹽,因此對(duì)水質(zhì)安全產(chǎn)生了較大的威脅。本文針對(duì)水中溴酸鹽的毒性風(fēng)險(xiǎn)開(kāi)展系統(tǒng)的研究,通過(guò)幾種不同營(yíng)養(yǎng)級(jí)的典型毒理學(xué)檢測(cè)生物,分析溴酸鹽的急性生物毒性以及毒性作用規(guī)律和特征,尋找對(duì)溴酸鹽毒性效應(yīng)較敏感的檢測(cè)生物和檢測(cè)指標(biāo),探討溴酸鹽對(duì)敏感檢測(cè)生物的致毒機(jī)理,利用較敏感的檢測(cè)指標(biāo)對(duì)含溴水經(jīng)臭氧氧化后的水質(zhì)綜合毒性效應(yīng)進(jìn)行評(píng)價(jià)。本文的研究結(jié)果對(duì)深入研究溴酸鹽的毒性作用規(guī)律及其致毒機(jī)理提供理論支持,為保障水質(zhì)安全的生物毒理學(xué)標(biāo)準(zhǔn)體系的建立提供重要參考依據(jù)。由于溴酸鹽對(duì)不同檢測(cè)生物的毒性效應(yīng)之間可能存在差異,因此為全面評(píng)價(jià)溴酸鹽的毒性效應(yīng),尋找對(duì)溴酸鹽毒性效應(yīng)較敏感的檢測(cè)生物,需要利用多種生物,多種指標(biāo)進(jìn)行綜合評(píng)價(jià)。本文分別以不同營(yíng)養(yǎng)級(jí)的幾種典型的毒性檢測(cè)生物作為研究對(duì)象進(jìn)行試驗(yàn)研究。研究發(fā)現(xiàn),溴酸鹽(以溴酸鉀為例)對(duì)斜生柵藻的96 h EC_(50)為738.18 mg/L,對(duì)微囊藻的96 h EC_(50)為195.39 mg/L,對(duì)大型蚤的48 h EC_(50)和LC_(50)分別為154.01 mg/L和198.52 mg/L,對(duì)裸腹蚤的48 h EC_(50)和LC_(50)分別為161.80 mg/L和175.68 mg/L,對(duì)斑馬魚(yú)的96 h LC_(50)為931.4mg/L,對(duì)Wistar大鼠和ICR小鼠的14天LD50分別為215 mg/kg和464 mg/kg。由此可見(jiàn),不同檢測(cè)生物對(duì)溴酸鹽毒性效應(yīng)的敏感性不同,其中大型蚤、裸腹蚤和微囊藻非常敏感,斜生柵藻次之,然后是斑馬魚(yú),而普通小球藻和發(fā)光菌對(duì)溴酸鹽的毒性效應(yīng)不敏感。溴酸鹽沒(méi)有明顯的蓄積毒性和遺傳毒性,對(duì)試驗(yàn)大鼠的生長(zhǎng)發(fā)育、臟器發(fā)育和組織形態(tài)以及肝臟功能均沒(méi)有顯著影響,但溴酸鹽會(huì)引起試驗(yàn)大鼠白細(xì)胞計(jì)數(shù)顯著降低,并且對(duì)試驗(yàn)大鼠的腎臟功能、糖代謝和脂代謝具有一定程度的影響。針對(duì)微囊藻和大型蚤對(duì)溴酸鹽毒性效應(yīng)較敏感的結(jié)果,本文考察了溴酸鹽對(duì)藻細(xì)胞和大型蚤的致毒機(jī)理。研究發(fā)現(xiàn)造成藻細(xì)胞生長(zhǎng)及大型蚤運(yùn)動(dòng)受到抑制或死亡的原因是溴酸鹽毒性綜合作用的結(jié)果。溴酸鹽引起藻細(xì)胞產(chǎn)生過(guò)多活性氧導(dǎo)致藻細(xì)胞發(fā)生過(guò)氧化損傷、生理功能異常和細(xì)胞結(jié)構(gòu)受損是其對(duì)藻細(xì)胞重要的致毒機(jī)理,溴酸鹽引起大型蚤抗氧化系統(tǒng)、神經(jīng)系統(tǒng)以及能量代謝的異常是其對(duì)大型蚤的重要致毒機(jī)理。在試驗(yàn)所考察的檢測(cè)生物和檢測(cè)指標(biāo)中,溴酸鹽對(duì)大型蚤Ca~(2+)/Mg~(2+)-ATP酶活性的影響顯著,它可以作為評(píng)價(jià)溴酸鹽毒性效應(yīng)的重要指標(biāo)。由于在含溴水臭氧氧化過(guò)程中,不只產(chǎn)生溴酸鹽這一種副產(chǎn)物,因此僅僅考察溴酸鹽的毒性效應(yīng)不能反映水質(zhì)真實(shí)的毒性效應(yīng)。本文以二溴乙酸作為臭氧氧化含溴水的另一種副產(chǎn)物,考察了溴酸鹽和二溴乙酸對(duì)大型蚤的聯(lián)合毒性,結(jié)果發(fā)現(xiàn)有協(xié)同作用和部分相加作用兩種聯(lián)合毒性作用,說(shuō)明副產(chǎn)物之間的聯(lián)合作用有增加水質(zhì)毒性效應(yīng)的風(fēng)險(xiǎn),有必要對(duì)水質(zhì)的綜合毒性效應(yīng)進(jìn)行研究。針對(duì)溴酸鹽對(duì)大型蚤Ca~(2+)/Mg~(2+)-ATP酶活性影響顯著的結(jié)果,本文利用大型蚤存活率和Ca~(2+)/Mg~(2+)-ATP酶活性為指標(biāo),以淀粉、牛血清白蛋白和腐殖酸分別代表水體中的多糖、氨基酸和腐殖質(zhì),考察了這些有機(jī)物對(duì)含溴水經(jīng)臭氧氧化后的水質(zhì)綜合毒性效應(yīng)的影響。研究發(fā)現(xiàn)溴離子濃度、溶解性有機(jī)碳濃度、臭氧濃度以及是否氯化都會(huì)影響含溴水經(jīng)臭氧氧化后的水質(zhì)毒性。當(dāng)水中無(wú)溴離子時(shí),單獨(dú)臭氧氧化對(duì)水質(zhì)毒性無(wú)明顯影響。隨溴離子濃度升高水質(zhì)毒性增強(qiáng),當(dāng)溴離子達(dá)到4 mg/L時(shí),水質(zhì)毒性達(dá)到最大,繼續(xù)增加溴離子濃度水質(zhì)毒性不再增強(qiáng),甚至有所降低。臭氧氧化后再進(jìn)行氯化氧化,水質(zhì)毒性會(huì)進(jìn)一步增強(qiáng)。最佳臭氧濃度因溶解性有機(jī)碳濃度的不同而不同,增加或降低臭氧濃度都會(huì)引起水質(zhì)毒性增加。在試驗(yàn)所考察的3種有機(jī)物中,腐殖酸對(duì)臭氧氧化后水質(zhì)毒性的影響最大,牛血清白蛋白次之,淀粉最小。大型蚤Ca~(2+)/Mg~(2+)-ATP酶活性對(duì)水質(zhì)毒性非常敏感,能較好地反映水質(zhì)毒性,是評(píng)價(jià)水質(zhì)安全的重要指標(biāo)。
[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.

【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：X171.5
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本文編號(hào)：1802821