锰氧化菌的激活及生物氧化锰去除有机药物效果的研究

摘要
近年来,有机药物随着人类的生产和使用不断进入水体,使得有机药物不断在全球各地水体中被发现,持续威胁着人类及生态环境的安全。而传统的污水处理工艺对有机药物去除率较低,高级氧化、活性炭吸附、膜处理等工艺虽然对有机药物有不错的去除效果,但存在成本较高、产生毒害产物、反应废物处理困难等缺点,制约着其进一步应用。生物氧化锰是由锰氧化菌在好氧环境下产生的代谢产物,具有大比表面积、高氧化还原电位等优点,其对环境中的有机污染物有较好的去除潜力。因此,开展生物氧化锰降解环境中有机药物的研究,能够帮助理解环境中有机药物类污染物的迁移转化规律以及提供一种高性价比的含药物类污染物废水处理技术,具有一定的科学和实际意义。
以污水厂好氧污泥、稻田土、清水溪底泥、锰矿场地表土为菌源及常用锰氧化菌培养基Leptothrix培养基和K培养基为培养基对菌源进行初筛,选出最佳菌源和最适培养基。随后在不同pH及不同Mn2+投加量下对最佳菌源进行激活,优化激活条件,对最优激活条件下的菌源微生物落变化及产物进行分析。在此基础上,选取四种典型有机药物——双氯芬酸、萘普生、乙炔基雌二醇、卡马西平,以激活产生的生物氧化锰,探究pH和生物氧化锰投加量对激活产生的生物氧化锰去除四种有机药物的影响。实验主要结论如下:
遗传病论文①选择污水厂好氧污泥和Leptothrix培养基分别作为激活菌源和培养基。不同pH条件下,pH=7.0时锰氧
化菌激活效果最好,且锰氧化菌较为适应酸性条件,碱性条件对其生长产生较大抑制。不同Mn2+投加量下,1mM时锰氧化菌激活效果最佳,且当Mn2+投加量在5mM以上时会对锰氧化菌产生较强抑制作用。
②激活锰氧化菌产生的生物氧化锰价态复杂,主要含有Na3Mn(PO3)CO3、Mn3O4、MnO2等成分。在激活过程中,主要发现气单胞菌属、微杆菌属、黄杆菌属、不动杆菌属、鞘氨醇杆菌属、假单胞菌属、芽孢杆菌属七个菌属的锰氧化菌,在激活过程七种锰氧化菌属的相对丰度显著提高,最终总丰度可达18.25%。
儿童虚拟社区③生物氧化锰去除有机药物反应为受pH影响较大,随着反应pH的降低和生物氧化锰的投加量的提高,生物氧化锰对有机药物的去除效果及速率逐渐升高。当生物氧化锰投加量为20mg/L、反应pH=4时双氯芬酸、萘普生、乙炔基雌二醇取得最佳去除效果,48h后激活产物对三种药物的去除率分别为100%、65.5%、100%,其中生物氧化锰贡献的去除率分别为75.5%、35.7%、78.3%。当生物氧化锰投加量为20mg/L、反应pH=3时卡马西平取得最佳降解效果,48h后激活产物对卡马西平的去除率为29%,其中生物氧化锰贡献的去除率为21.2%。
关键词:锰氧化菌,生物氧化锰,有机药物,去除效果波导
ABSTRACT
In the recent decade, because of the production and use of human beings, pharmaceuticals have been found in water bodies around the world, and continuously endanger the safety of human and ecological environment. The regular sewage treatment process have poor biodegradation performance on pharmaceuticals. Although AOPs, active carbon adsorption, membrane can remove pharmaceuticals effectively, but the cost, toxic by-product, production waste make it difficult to be further applied. Biogenic manganese oxides are metabolites produced by manganese oxide bacteria in aerobic environment. Because of its high specific surface area, high redox potential, biogenic manganese oxides can remove organic contaminant. Therefore,it has great  scientific and practical significance to study the degradation of pharmaceuticals by biogenic manganese oxides which can reveal the migration and transformation rules of pharmaceuticals in the environment and provide a cost-effective treatement technology wastewater containing pharmaceuticals
In order to find the optimal bacteria source and medium, aerobic sludge from sewage plant, paddy soil, freshwater sediment from Qingshuixi and surface soil from manganese ore field were chosen as the inoculation bacteria using Letpothrix medium, K medium as medium. Afterwards, the best bacteria source was activated under difference pH and difference Mn2+ dosage, the activation condition was optimized and the changes of microbial communities and the products were also analy
zed. Four typical pharmaceuticals namely diclofenac, naproxen, 17α-ethinylestradiol, carbamazepine, were chosen as target pharmaceuticals. The removal efficiency of target pharmaceuticals degraded by biogenic manganese oxides produced after activation were investigated under different pH and biogenic manganese oxidesd dosage.The main conclusion were as follows:
①Aerobic sludge and Leptrothrix medium were chosen as the best bacteria source and medium. The manganese oxide bacteria were activated best at pH=7.0. Manganese oxide bacteria were more suitable for acidic conditions, and alkane conditions would inhibit their growth. The best activation result was obtained when the Mn2+ dosage was 1mM.When Mn2+ dosage was increased by 5mM, it would strongly inhibited the activity of manganese oxides bacteria.
②The biogenic manganese oxides produced by manganese oxide bacteria is
complex and mainly contained Na3Mn(PO3)CO3、Mn3O4、MnO2. Seven genus with manganese oxide bacteria,Areomonas,Exiguobacterium,Flavobacterium,Acinetobacter,Sphingobacterium,Pseudomonas,Bacillus were found. The relative frequency of the seven genus was significantly increased after activation, and the total relative frequency was 18.25%.
③The removal of pharmaceuticals by biogenic manganese oxide depends on pH. The removal efficiency and rate of pharmaceuticals gradually increased with the decrease of reaction pH and the increase of the dosage of biogenic manganese oxide. When the dosage of biogenic manganese oxides was 20mg/L and the reaction pH was 4, diclofenac, naproxen, 17α-ethinylestradiol had the best removal efficiency. After 48h reaction,the removal efficiency of the three pharmaceuticals was 100%,65.5%,100%, in which 75.5%,35.7%,78.3% was removed by biogenic manganese oxides. When the dosage of biogenic manganese oxide was 20mg/L and the reaction pH was 3, carbamazepine had the best removal efficiency. After 48h reaction,the removal efficiency of carbamazepine was 29%, in which 21.2% was removed by biogenic manganese oxides.
Keywords: Mnaganese oxide bacteria,Biogenic manganese oxides, Pharmaceuticals, Removl efficiency
目录
中文摘要.......................................................................................................................................... I 英文摘要....................................................................................................................................... III 1 绪论.. (1)
1.1 有机药物的研究现状 (1)
1.1.1 有机药物的种类及来源 (1)
1.1.2 水环境中有机药物的污染现状及毒害性 (2)
1.1.3 有机药物去除研究现状 (4)
1.2 锰氧化菌及生物氧化锰的研究现状 (7)
1.2.1 锰氧化菌的概述 (7)
1.2.2 锰氧化菌氧化Mn(II)的原因与生物氧化锰的形成机制 (8)
1.2.3 锰氧化菌氧化Mn(II)的影响因素 (9)
1.2.4 生物氧化锰的特征 (10)
1.2.5 生物氧化锰的环境意义 (11)
1.3 研究的目的、意义 (12)
1.4 研究的主要内容 (13)
1.5 研究的技术路线 (14)
被遗忘的稻草
2 实验材料及测试方法 (15)
2.1 实验材料 (15)
2.1.1 菌种来源 (15)
2.1.2 培养基的成分 (15)
2.1.3 有机药物 (16)
2.1.4 实验所用试剂及材料 (17)
2.2 测试方法 (20)
2.2.1 有机药物浓度测试方法 (20)
2.2.2 生物氧化锰浓度测试方法 (23)
2.2.3 Mn2+浓度测试方法 (24)
2.2.4 生物氧化锰的XRD表征 (25)
2.2.5 菌源微生物多样性分析 (25)
石诗龙
3 锰氧化菌的激活及生物氧化锰的表征 (27)
3.1 实验方案 (27)
复乐园
3.2 菌源及培养基的选择 (27)

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