改性粘土矿物去除硝酸根离子的试验研究
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摘要
地下水是地质环境的重要组成部分,是我国北方地区主要的饮用水源。随着我国城市化、工业化进程加快,地下水环境质量恶化,环境污染问题日益突出,处理地下水中硝酸根离子污染问题已经迫在眉睫。目前,我国处理地下水污染尤其是硝酸根离子污染主要的方式包括PRB技术、抽取-处理方法等,这些处理方法在一定程度上缓解了硝酸根离子的污染,在某些特定的区域具有较好的应用。但是,随着我国地下水污染加重,这些方法已经无法承担如此繁重的处理任务,经济方面亦不可行。粘土矿物在地质环境中是广泛存在的,几乎所有的粘土矿物含有结构铁,并且其结构铁可以通过自然环境微生物或者化学还原剂还原为结构二价亚铁,此结构二价亚铁又可氧化为结构三价铁。在结构铁的氧化还原过程中,粘土矿物的结构不会改变,结构铁的空间位置也不会改变,因此可以作为可再生资源加以利用。本文通过对这种潜在的可再生资源进行系列合适的处理措施,探讨了其在处理地下水硝酸根离子方面所具有的潜能。
土壤中的无机矿化氮可以通过淋洗进入地下水,造成地下水硝酸根离子污染。本文利用加速扩散法测定土壤中的无机矿化氮,对比了KCl提取法与CaCl2淋洗法在测定矿化氮时的效率,发现KCl提取法要明显优于CaCl2淋洗法,为更加准确地测定土壤无机矿化氮提供了依据,为后续研究提供了技术基础。本文详细介绍了粘土矿物结构三价铁的还原方法,结构三价铁在还原后其结构二价亚铁十分容易发生再氧化,如何保持还原态结构二价亚铁的含量,成为研究难题,本文采用CALE洗涤系统可以在无氧环境下洗涤还原态粘土矿物,洗涤过程中,结构二价亚铁不会发生再氧化,同时还讨论了利用带有手套的气密箱可以很好的在较长时间内保存还原态粘土矿物,为试验研究提供了统一的试验初始条件,为长期研究提供了基础。天然氧化态粘土矿物和还原态粘土矿物与水体硝酸根离子几乎没有任何反应,本文研究发现天然粘土矿物与硝酸根离子之间存在的库伦斥力是阻碍结构铁还原硝酸根离子的一大障碍,本文利用聚合阳离子交换粘土矿物层间阳离子所得到的改性粘土矿物可以克服库伦斥力,对地下水中硝酸根离子具有很强的吸附效用,同时还可以降解硝酸根离子至具有较小危害的硝族产物,如氮气。利用改性后的粘土矿物去除硝酸根离子,为我国地下水污染尤其是硝酸根离子污染的处理技术提供了新的研究方向。同时还讨论了在自然环境中,微生物还原粘土矿物结构铁的现象是普遍存在的,对其反应机理进行了探讨,并对反应条件进行了归纳研究,明确了利用还原态粘土矿物还原降解硝酸根离子在实际环境中发生的可能性。最后,对本文进行了归纳总结,以及为以后的研究方向与研究要点进行了展望。
Groundwater is an important part of geo-environment and major source of drinking water in north China. With the rapid urbanization and industrialization in China, the environmental quality of groundwater is exacerbated, and environmental pollution has become an increasingly striking issue. Therefore, treatment of nitrate pollution to groundwater has become extremely imminent. Currently in China, The major remediation methods of groundwater pollution, especially nitrate pollution include Permeable Reactive Barriers, Extraction and Processing method, etc. These methods can relieve the nitrate pollution to some extent, and has been applied effectively in some certain areas. However, as the pollution of groundwater aggravates, these above-mentioned methods turn out to be not enough capable and economic. Clays minerals widely exist in geo-environment, and almost all clay minerals contain structural iron, which can be reduced to ferrous iron by microorganism and chemical methods. During the iron reduction, the structure of clay minerals stays unchanged, so does the spatial position of the structural iron in clay minerals. The structural iron can thus be utilized as a renewable resource. In this paper this potential renewable resource was treated properbly. its potential ability to remediate groundwater nitrate pollution was investigated.
Soil mineralized nitrogen could get into the groundwater through leaching, causing groundwater nitrate pollution. This paper used accelerated diffusion methods to determine soil mineralized nitrogen, and compared the efficiency of KC1extraction method and CaCl2leaching method. Results showed that KC1extraction method has a better efficiency than CaCl2leaching method in leach soil mineralized nitrogen This result provides a basis to measure the soil mineralized nitrogen accurately, and also provides a foundation for the follow-up studies.In this paper, the method for reduction of the structural iron in clay minerals was fully introduced. The structural Fe(Ⅱ) can re-oxidize easily, how to prevent this re-oxidization and keep the content of the structural Fe(Ⅱ) came to be difficult. This paper used Controlled Atmosphere Liquid Exchange (CALE) system to wash the reduced clay minerals under anoxic environment. During the washing process, no structural Fe(II) was re-oxidized. A glove box, used for long-term storage of reduced clay minerals, was also discussed in this paper. These results provided a unified starting condition for clay minerals study, and offered a foundation for long-term studies. Oxidized and reduced natural clay minerals showed no reaction toward nitrate in water. The Coulomb repulsion between negative charged natural clay minerals and negative charged nitrate ion is an immense obstacle to the nitrate reduction. This research aimed at using polymer cations to intercalate into the interlayer of clay minerals and exchange with cations, so that the polymer-modified clay minerals can overcome the Coulomb repulsion, act strong adsorption to nitrate and degrade nitrate to other less hazardous nitrate group products, N2as an example. The polymer-modified clay minerals may inspire a new research trend in the field of groundwater pollution treatment, especially nitrate pollution treatment. The fact that microorganisms can reduce structural iron in clay minerals are ubiquitous in nature was also discussed. This paper also discussed the mechanism of microbial reduction of structural iron, and summarized the reaction conditions, which make it clear that this microbial reduced clay minerals reduce nitrate in nature can be occurred. At last, some important conclusions were summarized, and also give out fews outlooks about research direction and key points for the future studies.
土壤中的无机矿化氮可以通过淋洗进入地下水,造成地下水硝酸根离子污染。本文利用加速扩散法测定土壤中的无机矿化氮,对比了KCl提取法与CaCl2淋洗法在测定矿化氮时的效率,发现KCl提取法要明显优于CaCl2淋洗法,为更加准确地测定土壤无机矿化氮提供了依据,为后续研究提供了技术基础。本文详细介绍了粘土矿物结构三价铁的还原方法,结构三价铁在还原后其结构二价亚铁十分容易发生再氧化,如何保持还原态结构二价亚铁的含量,成为研究难题,本文采用CALE洗涤系统可以在无氧环境下洗涤还原态粘土矿物,洗涤过程中,结构二价亚铁不会发生再氧化,同时还讨论了利用带有手套的气密箱可以很好的在较长时间内保存还原态粘土矿物,为试验研究提供了统一的试验初始条件,为长期研究提供了基础。天然氧化态粘土矿物和还原态粘土矿物与水体硝酸根离子几乎没有任何反应,本文研究发现天然粘土矿物与硝酸根离子之间存在的库伦斥力是阻碍结构铁还原硝酸根离子的一大障碍,本文利用聚合阳离子交换粘土矿物层间阳离子所得到的改性粘土矿物可以克服库伦斥力,对地下水中硝酸根离子具有很强的吸附效用,同时还可以降解硝酸根离子至具有较小危害的硝族产物,如氮气。利用改性后的粘土矿物去除硝酸根离子,为我国地下水污染尤其是硝酸根离子污染的处理技术提供了新的研究方向。同时还讨论了在自然环境中,微生物还原粘土矿物结构铁的现象是普遍存在的,对其反应机理进行了探讨,并对反应条件进行了归纳研究,明确了利用还原态粘土矿物还原降解硝酸根离子在实际环境中发生的可能性。最后,对本文进行了归纳总结,以及为以后的研究方向与研究要点进行了展望。
Groundwater is an important part of geo-environment and major source of drinking water in north China. With the rapid urbanization and industrialization in China, the environmental quality of groundwater is exacerbated, and environmental pollution has become an increasingly striking issue. Therefore, treatment of nitrate pollution to groundwater has become extremely imminent. Currently in China, The major remediation methods of groundwater pollution, especially nitrate pollution include Permeable Reactive Barriers, Extraction and Processing method, etc. These methods can relieve the nitrate pollution to some extent, and has been applied effectively in some certain areas. However, as the pollution of groundwater aggravates, these above-mentioned methods turn out to be not enough capable and economic. Clays minerals widely exist in geo-environment, and almost all clay minerals contain structural iron, which can be reduced to ferrous iron by microorganism and chemical methods. During the iron reduction, the structure of clay minerals stays unchanged, so does the spatial position of the structural iron in clay minerals. The structural iron can thus be utilized as a renewable resource. In this paper this potential renewable resource was treated properbly. its potential ability to remediate groundwater nitrate pollution was investigated.
Soil mineralized nitrogen could get into the groundwater through leaching, causing groundwater nitrate pollution. This paper used accelerated diffusion methods to determine soil mineralized nitrogen, and compared the efficiency of KC1extraction method and CaCl2leaching method. Results showed that KC1extraction method has a better efficiency than CaCl2leaching method in leach soil mineralized nitrogen This result provides a basis to measure the soil mineralized nitrogen accurately, and also provides a foundation for the follow-up studies.In this paper, the method for reduction of the structural iron in clay minerals was fully introduced. The structural Fe(Ⅱ) can re-oxidize easily, how to prevent this re-oxidization and keep the content of the structural Fe(Ⅱ) came to be difficult. This paper used Controlled Atmosphere Liquid Exchange (CALE) system to wash the reduced clay minerals under anoxic environment. During the washing process, no structural Fe(II) was re-oxidized. A glove box, used for long-term storage of reduced clay minerals, was also discussed in this paper. These results provided a unified starting condition for clay minerals study, and offered a foundation for long-term studies. Oxidized and reduced natural clay minerals showed no reaction toward nitrate in water. The Coulomb repulsion between negative charged natural clay minerals and negative charged nitrate ion is an immense obstacle to the nitrate reduction. This research aimed at using polymer cations to intercalate into the interlayer of clay minerals and exchange with cations, so that the polymer-modified clay minerals can overcome the Coulomb repulsion, act strong adsorption to nitrate and degrade nitrate to other less hazardous nitrate group products, N2as an example. The polymer-modified clay minerals may inspire a new research trend in the field of groundwater pollution treatment, especially nitrate pollution treatment. The fact that microorganisms can reduce structural iron in clay minerals are ubiquitous in nature was also discussed. This paper also discussed the mechanism of microbial reduction of structural iron, and summarized the reaction conditions, which make it clear that this microbial reduced clay minerals reduce nitrate in nature can be occurred. At last, some important conclusions were summarized, and also give out fews outlooks about research direction and key points for the future studies.
引文
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