Harmfulness of fluorine−bearing groundwater and its current situation and progress of treatment technology
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摘要:
研究目的 地下水氟污染在世界范围内都被认为是一项重大公共卫生危害。据统计，全球有约2亿多人正面临氟中毒风险，至少有28个国家出现过饮用高氟水造成的氟中毒事件。高氟地下水主要分布于干旱缺水的欠发达地区，普遍缺乏可替代的饮用水源，使地方性氟中毒问题长期得不到有效解决。因此，研发经济可行的氟化物去除技术成为解决高氟地下水问题的关键。
研究方法 基于文献调研结果，以现阶段全球含氟地下水的污染现状为基础，综合考虑研究深度、理论和应用可行性、去除效率、可再生性等多种因素，对国内外含氟地下水研究和应用案例进行总结分析。
研究结果 介绍了世界范围内含氟地下水的成因和分布，系统总结了现有主流含氟地下水处理技术的优劣、除氟机理和应用进展，并对存在问题和未来发展趋势进行了分析和展望。
结论 每种技术都有各自的处理优势和一定的局限性，在选择和应用时需要综合考虑含氟地下水的水质情况和目标需求。同时，当前的地下水除氟技术在研发过程中也存在服务目标针对性不强、综合处理效率不佳以及吸附容量应用与理论值偏差较大等问题。多种处理工艺的耦合应用可以更好地发挥不同处理技术的优势，取得取长补短的效果，正受到人们日益关注。此外，多污染物的联合去除以及结构可人工调控的新型吸附材料的设计研发也是未来重要发展方向。
Abstract:This paper is the result of hydrogeological survey engineering.
Objective Fluorine contaminated groundwater is considered a major public health hazard worldwide. According to statistics, over 200 million people worldwide are at risk of fluorosis, and at least 28 countries have experienced fluorosis incidents caused by drinking high fluoride water. High fluoride groundwater is mainly distributed in underdeveloped areas with drought and water scarcity, and there is a general lack of alternative drinking water sources, making the problem of endemic fluorosis difficult to effectively solve for a long time. Therefore, developing economically feasible fluoride removal technologies has become the key to solving the problem of high fluoride groundwater.
Methods Based on the results of literature research and the current global pollution status of fluorinated groundwater, This article summarized and analyzed the research and application cases of fluorinated groundwater both domestically and internationally, taking into account various factors such as research depth, theoretical and application feasibility, removal efficiency, and renewability comprehensively.
Results This article systematically introduced the causes and distribution of fluorinated groundwater worldwide, summarized the advantages and disadvantages of existing mainstream fluorinated groundwater treatment technologies, fluoride removal mechanisms and application progress, and analyzed and prospected the existing problems and future development trends.
Conclusions Each technology had its own processing advantages and certain limitations, and when selecting and applying specific technologies, it was necessary to comprehensively consider the water quality and target requirements of fluorine contaminated groundwater. At the same time, there were also problems in the current research and development process of groundwater fluoride removal technology, such as lack of targeted service objectives, poor comprehensive treatment efficiency, and significant deviation between the application of adsorption capacity and theoretical values. The coupling application of multiple treatment processes could better leverage the advantages of different treatment technologies and achieved the effect of complementing each other's strengths, which was receiving increasing attention from people. In addition, the joint removal of multiple pollutants and the design and development of new adsorption materials with manually adjustable structures are also important development directions in the future.
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图 1 地下水中氟离子的来源（据Vithanage and Bhattacharya, 2015修改）
Figure 1.
图 2 常规沉淀法简易装置图（a）及流化床反应器的实验装置原理图（b）（据Lacson et al., 2021修改）
Figure 2.
图 3 离子交换树脂除氟原理图（据Yu et al., 2021修改）
Figure 3.
图 4 （a）电絮凝技术原理图（修改自Castaneda et al., 2021）；（b）电絮凝除氟装置示意图（据Haldar and Gupta, 2020修改）
Figure 4.
图 5 氧化石墨烯/氧化铝材料吸附氟离子机理图（据Xu et al., 2020修改）
Figure 5.
图 6 La−UiO−66−（COOH）2吸附剂的制备流程（a）及除氟机制（b）（据Zhao et al., 2022）
Figure 6.
图 7 氟化物在生物炭基材料上的吸附机理（据Kumar et al., 2022修改）
Figure 7.
图 8 MgO−MgFe2O4/GO 除氟机理示意图（据Sahoo and Hota, 2018修改）
Figure 8.
图 9 氟在LC−Ce材料吸附机制（据Nehra et al., 2020修改）
Figure 9.
图 10 电渗析原理图（据Aliaskari and Schäfer, 2021修改）
Figure 10.
图 11 反渗透工作原理图（据Hailemariam et al., 2020修改）
Figure 11.
图 12 纳滤工作组件示意图（据Xu et al., 2015修改）
Figure 12.
表 1 氟去除技术对比
Table 1. Comparison of fluorine removal technologies
去除技术 优势 局限性 部分去除案例 初始浓度/
（mg/L）去除率/% 参考文献 沉淀法 原理和装置简单，运行成本低，操作便捷，工艺技术成熟，可同步去除多种污染物 去除效率低，可能生成大量溶解性铝及有毒氟铝复合物污泥，占地面积大，主要应用于工业废水 4~16 77~90 Kumar et al.,
2022离子交换法 有毒污泥产量有限（回收率高），选择性去除离子，去除率高 离子交换树脂价格昂贵，易受干扰离子（硫酸盐，磷酸盐，氯化物，碳酸氢盐等）干扰，使用的介质产生有毒固体废物，效率依赖pH值 10 69~97 Castel et al.,
2000电絮凝法 适用污染物范围广，运行稳定，无二次污染，高去除率，可同步去除微生物 释放铝离子及其水解产物，电极易钝化，高能耗 2~125 68.9~96 Castaneda et al.,
2021吸附法 吸附剂易获取成本低，操作简单，吸附剂可用范围广，灵活性和去除效果好，选择性离子去除，通常不需要后处理 需要重新调整pH值，易受常见离子干扰，吸附剂耗尽后需要更换，人员素质要求高 5~100 35~97.4 Takmil et al.,
2020膜技术 去除率高，自动化程度高，无需添加药剂，不影响水体颜色和味道，可同时去除其他污染物 投资、能耗、运维成本高，污垢和结垢会降低效率，需前置预处理，浓水处理困难 0.8~50 42~99 Jadhav et al.,
2015
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