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钙离子影响下磷酸铵镁微生物成矿机制研究

Exploration of the Mineralization Mechanism of Microbial Struvite under the Influence of Calcium Ions

作者:唐明阳
  • 学号
    2021******
  • 学位
    硕士
  • 电子邮箱
    Ttm******com
  • 答辩日期
    2024.05.14
  • 导师
    李兵
  • 学科名
    资源与环境
  • 页码
    106
  • 保密级别
    公开
  • 培养单位
    599 国际研究生院
  • 中文关键词
    微生物成矿;磷回收;磷酸铵镁;副炭疽芽孢杆菌;胞外聚合物
  • 英文关键词
    Microbial mineralization; Phosphorus recovery; Magnesium ammonium phosphate; Bacillus paraanthracis; Extracellular polymers

摘要

微生物诱导成矿技术是一种具有环境可持续性潜力的磷回收策略,不仅能有效地从废水中去除氮磷污染物,而且能合成具有二次利用价值的矿物磷酸铵镁(Magnesium Ammonium Phosphate,MAP)。在自然界中,钙的存在会对MAP合成的反应过程产生干扰作用。非生物成矿途径合成MAP是已被广泛研究的磷回收方式,钙被证实具有明显的负面效应。相较于非生物成矿途径,钙影响下微生物成矿方法显示出诸多优势,是一种具有潜力的水处理技术。首先,针对钙对微生物成矿途径的影响开展实验研究。结果表明,钙对微生物的生长没有负面效应,不同钙浓度下合成矿物均为晶态MAP,矿物品质不受影响。在微生物调节下,钙不会产生其他沉淀物,培养过程中产物特征不变。钙促进磷污染物去除,高钙含量对矿物产量有负面影响。其次,本文采用钙对微生物成矿及非生物成矿影响差异对比的方法,表明微生物成矿MAP具有更大的应用优势,主要表现在成矿经济性、矿物品质以及资源回收效率上。微生物通过降解代谢形成弱碱性环境,无需额外投加碱液,降低MAP合成成本;微生物成矿合成MAP粒径更大,有利于处理与运输,高纯度使产物更具功能性;微生物成矿途径对钙、氨氮、磷酸盐等具有优秀的去除能力,有效处理污水。同时,微生物成矿途径相较非生物成矿途径存在处理时间长、后续处理复杂等问题,需要综合考虑。最后,探究两种MAP合成途径结果差异形成原因,模拟作用机制,从分子层面探究钙对微生物成矿的影响机制。研究表明,副炭疽芽孢杆菌产生的胞外聚合物腐殖酸可能是导致差异的原因。腐殖酸的羧基是钙离子及其水合物的主要结合位点,腐殖酸和钙离子的结合机制以配位作用为主。钙浓度导致部分基因上调或下调,影响合成矿物产量与形貌等。钙基本不影响代谢物的生成。研究可揭示微生物成矿过程中的钙影响机制,钙离子与胞外聚合物中腐殖酸(HA)羧基配位形成HA-Ca复合物,降低钙对微生物及MAP成矿反应的干扰。MAP的形成以HA为成核位点,此后,各离子在细胞表面反应形成颗粒状MAP。一段时间后,溶液中各离子可自发反应生成MAP。随着反应进行,有机酸代谢减弱,有机酸积累,腐殖酸等有机酸与钙离子螯合沉降,避免了钙对MAP合成的干扰,提高产物纯度。研究结果有助于对污水磷回收中钙干扰问题的解决,推动微生物成矿方法在磷回收领域的运用与拓展,维护水生态环境,促进磷资源的循环可持续发展,为我国污水资源化利用提供支持,缓解全球磷匮乏局势。

Microbial induced mineralization technology is a phosphorus recovery strategy with environmental sustainability potential. It can not only effectively remove nitrogen and phosphorus pollutants from wastewater, but also synthesize the mineral magnesium ammonium phosphate (MAP) with secondary utilization value. In nature, the presence of calcium can interfere with the reaction process of MAP synthesis. The synthesis of MAP through non biological mineralization pathway has been widely studied as a phosphorus recovery method, and calcium has been proven to have significant negative effects. Compared to non biological mineralization pathway, microbial mineralization method under calcium influence has shown many advantages and is a potential water treatment technology.Firstly, experimental research will be conducted on the impact of calcium on microbial mineralization pathway. The results indicate that calcium has no negative effect on the growth of microorganisms, and the synthesized minerals at different calcium concentrations are all crystalline MAP, and the mineral quality is not affected. Under microbial regulation, calcium does not produce other precipitates, and the product characteristics remain unchanged during the cultivation process. Calcium promotes the removal of phosphorus pollutants, and high calcium content has a negative impact on mineral yield.Secondly, this article adopts the method of comparing the differences in the effects of calcium on microbial mineralization and abiotic mineralization, indicating that microbial mineralization MAP has greater application advantages, mainly manifested in mineralization economy, mineral quality, and resource recovery efficiency. Microorganisms form a weakly alkaline environment through degradation metabolism, without the need for additional alkaline solution, reducing the cost of MAP synthesis. Microbial mineralization synthesis of MAP has a larger particle size, which is beneficial for processing and transportation, and high purity makes the product more functional. The microbial mineralization pathway has excellent removal ability for calcium, ammonia nitrogen, phosphate, etc., effectively treating wastewater. Meanwhile, the microbial mineralization pathway has issues such as longer processing time and more complex subsequent processing compared to non biological mineralization pathways, which require comprehensive consideration.Finally, explore the reasons for the differences in the results of the two MAP synthesis pathways, simulate the mechanism of action, and explore the impact mechanism of calcium on microbial mineralization from a molecular level. Research has shown that the extracellular polymeric humic acid produced by Bacillus paraanthracis may be the reason for the differences. The carboxyl group of humic acid is the main binding site for calcium ions and their hydrates, and the binding mechanism between humic acid and calcium ions is mainly through coordination. Calcium concentration leads to upregulation or downregulation of some genes, affecting the production and morphology of synthesized minerals. Calcium does not significantly affect the generation of metabolites.Research can reveal the mechanism of calcium influence in microbial mineralization, where calcium ions coordinate with humic acid (HA) carboxyl groups in extracellular polymers to form HA-Ca complexes, reducing the interference of calcium on microbial and MAP mineralization reactions. The formation of MAP takes HA as the nucleation site, and thereafter, various ions react on the cell surface to form granular MAP. After a period of time, each ion in the solution can spontaneously react to generate MAP. As the reaction proceeds, organic acid metabolism weakens, organic acid accumulates, humic acids and other organic acids chelate and settle with calcium ions, avoiding calcium interference in MAP synthesis and improving product purity.The research results contribute to solving the calcium interference problem in wastewater phosphorus recovery, promoting the application and expansion of microbial mineralization methods in the field of phosphorus recovery, promoting the large-scale and market-oriented use of microbial treatment for phosphorus recovery, solving nitrogen and phosphorus pollution, maintaining the water ecological environment, promoting the sustainable development of phosphorus resources, providing support for the resource utilization of wastewater in China, and alleviating the global phosphorus shortage situation.