活化过硫酸钠原位修复石油类污染土壤研究进展

过硫酸钠作为原位化学氧化技术常用的氧化剂在国外已经被广泛用于实际石油类污染土壤的修复,国内则应用较少.过硫酸钠通过活化能产生SO4-·和·OH,这些具有强氧化性的基团可以降解大部分的石油类污染物.本文在关注过硫酸钠活化技术与反应机理的基础上,分析过硫酸钠原位修复后土壤环境的生物地球化学变化以及多种修复技术联合的工程应用,对过硫酸钠自活化试剂的制备、过硫酸钠原位修复与其它土壤修复技术联合和当前应用中存在的问题等进行了展望.     

Stabilization of potassium permanganate particles with manganese dioxide

A new potassium permanganate reagent with slow-release properties was designed and tested for possible application in in situ chemical oxidation. For this purpose, MnO₂-coated KMnO₄ particles (MCP) were prepared by partial reduction of solid KMnO₄ using the acid-catalyzed reaction with n-propanol or the comproportionation of Mn(VII) and Mn(II) in n-propanol as reaction medium. Column tests showed that, for MCP with a residual KMnO₄ fraction of 70 wt%, the duration of permanganate release under flow-through conditions was prolonged by a factor of 10 compared to untreated KMnO₄. While KMnO₄ is too soluble to be used in reactive barriers, MCP could be introduced into the aquifer by filling of trenches or boreholes; this would allow a prolonged passive dosing of permanganate into the flowing groundwater. In addition, experiments were conducted in order to determine the oxidation capability of native KMnO₄ particles and MCP in CH₂Cl₂, a representative non-polar non-aqueous phase liquid (NAPL). It may be possible to utilize the significantly higher reactivity of MCP under these conditions for the design of slow-release permanganate particles for NAPL source treatment.     

Is it possible to remediate a BTEX contaminated chalky aquifer by in situ chemical oxidation?

An industrial coating site in activity located on a chalky plateau, contaminated by BTEX (mainly xylenes, no benzene), is currently remediated by in situ chemical oxidation (ISCO). We present the bench scale study that was conducted to select the most appropriate oxidant. Ozone and catalyzed hydrogen peroxide (Fenton’s reaction) were discarded since they were incompatible with plant activity. Permanganate, activated percarbonate and activated persulfate were tested. Batch experiments were run with groundwater and groundwater-chalk slurries with these three oxidants. Total BTEX degradation in groundwater was reached with all the oxidants. The molar ratios [oxidant]:[Fe²⁺]:[BTEX] were 100:0:1 with permanganate, 100:100:1 with persulfate and 25:100:1 with percarbonate. Precipitation of either manganese dioxide or iron carbonate (siderite) occurred. The best results with chalk slurries were obtained with permanganate at the molar ratio 110:0:1 and activated persulfate at the molar ratio 110:110:1. To avoid precipitation, persulfate was also used without activation at the molar ratio 140:1. Natural Oxidant Demand measured with both oxidants was lower than 5% of initial oxidant contents. Activated percarbonate was not appropriate because of radical scavenging by carbonated media. Permanganate and persulfate were both effective at oxidant concentrations of ca 1 g kg⁻¹ with permanganate and 1.8 g kg⁻¹ with persulfate and adapted to site conditions. Activation of persulfate was not mandatory. This bench scale study proved that ISCO remediation of a chalky aquifer contaminated by mainly xylenes was possible with permanganate and activated or unactivated persulfate.     

缓释型化学氧化剂在地下水DNAPLs污染修复中的应用研究进展

重质非水相有机污染物具有高密度、高毒性、低水溶性和高界面张力的特性,在自然条件下难以降解.缓释型化学氧化剂可以控制反应性化合物的释放,减少氧化剂的非选择性消耗,在地下水低渗透含水层DNAPLs(重非水相液体,dense nonaqueous-phase liquids)污染修复中有巨大的发展潜力.本文通过大量的文献调研...     

纳米CaO2氧化修复苯并噻唑类污染地下水的效果

为了探究纳米过氧化钙(nCaO₂)原位氧化降解地下水中苯并噻唑及其类似物(BTs)的可行性,采用静态批实验与动态柱实验相结合的方法开展了一系列研究,考察了不同条件下的处理效果,明确了修复试剂投加量、地下水pH、背景离子等因素的影响;同时研究了nCaO₂在含水层中的迁移分布规律以及Fe²⁺活化nCaO₂对BTs污染含水层的连续动态修复性能。批实验结果表明,在最佳氧化剂/活化剂配比下,3种难降解BTs在1 h后均有明显的降解;在强酸性(pH=3)和中性(pH=7)条件下BTs具有较好的去除效果;水中Cl⁻和HCO₃⁻离子对BTs降解的影响取决于pH和污染物自身的化学性质。柱实验结果表明,nCaO₂在含水层中具有一定的迁移能力,对3种BTs的累计去除率均在70%~80%。模拟含水层地球化学参数(pH、氧化还原电位、溶解氧和Fe²⁺等)在修复过程中也会发生相应的变化,表明nCaO₂能够持续有效地释放O₂。     

多相抽提和原位化学氧化联合修复技术应用——某有机复合污染场地地下水修复工程案例

某电子机械厂搬迁后原址约1 500 m区域地下水受到了多种类型的有机物复合污染,包括石油烃、苯系物和多环芳烃,并且部分区域发现有明显轻质非水溶相流体(LNAPL)。该案例首先应用多相抽提技术强化回收地下水中的LNAPL,并去除土壤气体和地下水中溶解态的污染物。当地下水中不存在明显LNAPL且污染物浓度不再明显降低后,继续应用原位化学氧化技术进行修复,所使用氧化剂为"过硫酸钠+Na OH"。经过45 d的多相抽提以及4t过硫酸盐氧化剂注射之后,验收监测表明污染区域地下水污染物浓度均达到了修复目标。该案例表明,多种修复技术的联合应用能够明显加快修复进度、提高修复效率、节约修复成本。对于存在LNAPL,且修复目标较严格的有机复合污染场地,多相抽提结合原位化学氧化联合修复是一种较好的修复技术选择。