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典型制药废水及其受纳水体的毒性研究

发布时间:2018-08-12 19:10
【摘要】:制药废水是我国工业废水重点处理处置目标。药物生产的全生命周期过程中,产生大量含有溶解性原材料、有机溶剂、有毒有害化学物质的废水。该废水具有难降解、组成复杂、COD值偏高的特点,并且废水中的有毒有害污染物质会导致严重的生态危害。我国以化学需氧量(COD)、生物需氧量(BOD5)、氨氮等理化指标作为制药行业废水排放管理标准,但是这些参数无法准确反映废水中残留的有毒有害物质对生态系统和人类的潜在毒害作用。生物毒性测试是监测水质安全的有效手段。利用水生生物进行水质毒性监测能够较好的反映综合废水中多种有毒物质复合暴露的实际毒性效应。本论文研究典型制药废水对水生生物的一般毒性和遗传毒性,以及水解酸化-好氧过程对该废水生物毒性的消减能力。比较研究制药废水受纳水体对国际标准模式生物-斑马鱼和本土物种-麦穗鱼的遗传毒性和氧化损伤作用,为控制制药废水的生态毒性和对人类健康的潜在危害提供科学依据。比较制药废水对4个营养级别5种不同水生生物的一般毒性和遗传毒性,受试生物包括细菌(明亮发光杆菌)、浮游植物(斜生栅藻)、浮游动物(草履虫、大型蚤)和鱼类(斑马鱼)为受试生物。一般毒性结果显示,该制药废水处理过程水及排放水对斑马鱼致死效应的毒性单位(TU,100/LC5o)在1.4~2.9,对大型蚤的活动抑制效应TU在1.0~2.7;草履虫致死效应TU在0-1.5;对斜生栅藻、发光细菌无明显生长抑制和发光抑制效应。4个营养级别生物对该制药废水毒性反应的灵敏性从高到低依次为,斑马鱼大型蚤草履虫明亮发光杆菌和斜生栅藻。提示该制药废水对高等生物毒性较强。斑马鱼肝细胞彗星实验结果显示,该制药废水在2%浓度下,即造成显著的DNA损伤作用。经过水解酸化-好氧法处理后,该制药废水水质达到《化学合成类制药工业水污染物排放标准》,但出水仍对草履虫、大型蚤和斑马鱼产生急性毒性作用,并对斑马鱼产生遗传毒性。细河、蒲河是辽河流域制药行业污水排放的主要受纳水体。以国际通用物种斑马鱼和辽河流域本地物种麦穗鱼为受试生物进行细河、蒲河及二者汇入浑河后河段的毒性评价。各采样点对斑马鱼和麦穗鱼无致死作用。与对照组相比,细河上游、蒲河中游采样点对两种受试鱼类无显著遗传毒性。细河汇入浑河后下游、蒲河下游水体对受试鱼类表现为极显著的遗传毒性效应和氧化损伤作用。与通用物种斑马鱼相比,辽河流域本地物种麦穗鱼在DNA损伤和氧化损伤评价过程中,具有较高的生物灵敏性和稳定性,可作为辽河流域水质安全性评价的本土受试生物。
[Abstract]:Pharmaceutical wastewater is the target of industrial wastewater treatment in China. During the whole life cycle of drug production, a large number of wastewater containing dissolved raw materials, organic solvents and toxic and harmful chemicals are produced. The wastewater is difficult to degrade and the COD value of complex components is high, and the toxic and harmful pollutants in the wastewater will cause serious ecological harm. In China, chemical oxygen demand (COD), biological oxygen demand (BOD5), ammonia nitrogen and other physical and chemical indexes are taken as the management standard of wastewater discharge. However, these parameters can not accurately reflect the potential toxic effects of residual toxic and harmful substances in wastewater on ecosystem and human beings. Biotoxicity test is an effective method to monitor the safety of water quality. Using aquatic organisms to monitor the toxicity of water quality can reflect the actual toxicity effect of the compound exposure of many toxic substances in the comprehensive wastewater. In this paper, the general toxicity and genetic toxicity of typical pharmaceutical wastewater to aquatic organisms and the ability of hydrolytic acidification-aerobic process to reduce the biological toxicity of the wastewater were studied. In order to control the ecological toxicity of pharmaceutical wastewater and its potential harm to human health, the genotoxicity and oxidative damage of pharmaceutical wastewater to the international standard organism zebrafish and native species, were studied comparatively in order to provide a scientific basis for controlling the ecological toxicity of pharmaceutical wastewater and its potential harm to human health. The general toxicity and genetic toxicity of pharmaceutical wastewater to 5 different aquatic organisms of four nutrient levels were compared. The tested organisms included bacteria (luminescent bacilli), phytoplankton (S. obliquus), zooplankton (paramecium), and phytoplankton (paramecium). Large fleas and fish (zebrafish) were tested. The general toxicity results showed that the toxic unit of lethal effect of water and discharged water on zebrafish (TUU / 100 / LC5o) was 1.4 / 2.9, the activity inhibitory effect on flea was 1.0 / 2.7, the lethal effect of paramecium was 0-1.5, and the activity inhibition effect of P.macrophylla was 0-1.5, respectively. There was no obvious growth inhibition and luminescence inhibition by luminescent bacteria. The sensitivity of the four nutrient-grade organisms to the toxic reaction of the pharmaceutical wastewater was in the order of high to low, the bioluminescent bacilli of Paramecia macrophylla and S. obliquus were in the order of high to low. The results suggest that the pharmaceutical wastewater is highly toxic to higher biological organisms. The results of comet assay of zebrafish hepatocytes showed that the DNA damage of the wastewater was significant at the concentration of 2%. After hydrolytic acidification-aerobic treatment, the wastewater reached the discharge standard of water pollutants in chemosynthetic pharmaceutical industry, but the effluent still had acute toxicity to paramecium, flea and zebrafish. And genotoxicity to zebrafish. Xianhe and Puhe are the main water bodies for wastewater discharge from pharmaceutical industry in Liaohe River Basin. Using zebrafish, an international common species, and wheat spike fish, a native species in the Liaohe River Basin, as experimental organisms, the toxicity evaluation of the small river, Puhe River and the hind reaches of the Hunhe River was carried out. There was no lethal effect on zebrafish and wheat spike fish at each sampling point. Compared with the control group, the sampling sites in the upper reaches of the river and the middle reaches of Puhe had no significant genotoxicity to the two species of fish. After the river flows into the lower reaches of the Hunhe River, the water in the lower reaches of the Puhe River shows very significant genotoxicity and oxidative damage to the tested fish. Compared with the common species zebrafish, the native species of wheat spikfish in Liaohe River Basin has higher biological sensitivity and stability in the process of DNA damage and oxidative damage evaluation, and can be used as the native tested organisms for water quality safety evaluation in Liaohe River Basin.
【学位授予单位】:大连理工大学
【学位级别】:硕士
【学位授予年份】:2015
【分类号】:X787;X171.5

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