地下土壤、水中DNAPLs污染的修复技术研究进展

综述了国内外地下土壤、含水层DNAPLs污染的迁移机理及其修复技术研究进展,对该领域的研究前景做了展望.     

基于替代模型的地下水DNAPLs污染源反演识别

应用基于核极限学习机替代模型的模拟-优化理论和方法研究解决了地下水DNAPLs污染源及含水层参数的同步反演识别问题.结果表明：1）核极限学习机替代模型对模拟模型有较高的逼近精度,能够识别并模仿模拟模型的输入-输出关系,绝大部分相对误差小于5%,平均相对误差仅有2.98%;2）以替代模型代替模拟模型,大幅度地减小了模拟-优化过程的计算负荷,将反演识别时间由传统方法的83天减少到3小时,并能够保持较高的计算精度;3）应用基于模拟退火的粒子群优化算法求解优化模型,能够以较快的速度搜寻到全局最优,同时避免搜索过程陷于局部极小解.     

地下水DNAPLs污染的研究进展

地下水有机污染特别是DNAPLs污染是当前国际上地下水污染控制的热点问题。本文综述了DNAPLs的监测技术、DNAPL在含水层的迁移及DNAPb污染场地修复技术的研究进展。     

Effect of scale and dimensionality on the surfactant-enhanced solubilization of a residual DNAPL contamination

The mass transfer rate from residual dense non-aqueous phase liquids (DNAPLs) to the mobile aqueous phase is an important parameter for the efficiency of surfactant-enhanced remediation through solubilization of this type of contamination. The mass transfer kinetics are highly dependent on the dimensionality of the system. In this study, irregularly shaped residual TCE saturations in two-dimensional saturated flow fields were flushed with a 2% polyoxyethylene sorbitan (20) monooleate (POESMO) solution until complete removal had been achieved. A numerical model was developed and used for the simulation of the various surfactant-flushing experiments with different initial saturation patterns and flow rates. Through optimization against in situ concentration and saturation data, a phenomenological power-law model for the relationship between the mass transfer rate from the DNAPL to the mobile aqueous phase on the one hand and the residual DNAPL saturation and the flow velocity on the other hand was derived. The obtained mass transfer rate parameters provide a reasonable fit to the experimental data, predicting the cleanup time and the general saturation and concentration pattern quite well but failing to predict the concentration curves at every individual sampling port. The obtained mass transfer rate model gives smaller values for the predicted mass transfer rate but shows a comparable dependence on water flow and saturation as in earlier published one-dimensional column experiments with identical characteristics for porous medium, DNAPL and surfactant. Mass transfer rate predictions were about one order of magnitude lower in the 2-D flow cell experiment than in 1-D column experiments. These results give an indication for the importance of dimensionality during surfactant remediation.     

地下水中Tween80对DNAPL运移和分布的影响

选用地下环境中普遍存在的四氯乙烯（PCE）为典型DNAPLs污染物,建立二维砂箱模型,研究一种人为引入表面活性剂Tween 80对粗砂介质中DNAPLs迁移和分布的影响.测定了含不同浓度Tween 80水溶液/石英砂/PCE三相体系下的液/液界面张力及PCE在石英介质表面的接触角,结果表明PCE在石英砂表面的接触角随着Tween 80浓度的增大而增大,PCE/水的界面张力随着Tween 80浓度的增大而减小,Tween 80浓度在CMC值附近时变化急剧.随后的二维砂箱实验定量描述地下水中表面活性剂Tween 80对PCE的迁移和最终形态的影响.由于Tween 80可以使石英砂介质由水相润湿转变为中间润湿或油相润湿态,相应地在20~30目的粗砂均质介质中Tween 80对DNAPLs迁移存在明显影响.背景溶液中表面活性剂的存在使得DNAPL的垂直运移速度减小,垂向迁移距离减小,最终使得被截留在运移路径上的残留PCE增加.和纯水流情况下相比,地下水中含有表面活性物剂Tween 80时,使得DNPAL污染羽向水流方向偏移减弱,污染羽展布面积与纯水情形下相比,在垂向上均明显减小,并且以较大饱和度残留的DNAPL量增加.     

地下水DNAPLs污染修复多相流模拟的替代模型

应用克里格法、支持向量回归法、核极限学习机法建立多相流模拟模型的替代模型,并应用集对分析法建立组合替代模型,通过将多种替代模型进行对比,分析不同替代模型在地下水DNAPLs污染修复多相流模拟问题中的适用性.结果表明,3种单一替代模型中,克里格模型的精度最高,其次是核极限学习机模型,最后是支持向量回归模型;应用集对分析原理建立集对权组合替代模型,与单一替代模型相比,其模拟模型的逼近精度更高,且提升效果十分显著,平均残差和平均相对误差分别为0.4009%和0.5373%;集对权组合替代模型运行一次仅需1.5s,选择组合替代模型代替多相流模拟模型进行地下水DNAPLs污染的修复方案优选分析,能够大幅减小模拟-优化过程的计算负荷,并保持较高的计算精度.     

阴-非混合表面活性剂对DNAPLs的增溶作用

表面活性剂增溶修复是一种有效的土壤有机污染修复技术.采用静态平衡法比较研究了单一的阴离子表面活性剂十二烷基硫酸钠(SDS)和非离子表面活性剂聚氧乙烯失水山梨脂肪酸酯醇醚(TWSO)及其混合表面活性剂对3种氯代烃化合物氯苯(CB)、1,2-二氯苯(1,2-DCB)和三氯乙烯(TCE)的增溶作用.考察了无机盐离子Na 、M2 和Ca2 对增溶作用的影响,以期为土壤和地下水重非水相液体(DNAPLs)污染提供新的修复途径.结果表明,阴-非混合表面活性剂TW80-SDS对3种化合物的增溶效果明显强于单一的阴离子表面活性剂SDS,混合表面活性剂的临界胶束浓度(CMC)随着非离子表面活性剂质量分数的增加而降低,其增溶能力随着非离子表面活性剂质量分数的增加而增加,对污染物的增溶程度排序为:三氯乙烯＞氯苯＞1,2-二氯苯.表面活性剂在临界胶束浓度以上,对有机物的分配系数Kmc与有机物的辛醇-水分配系数Kow相当,而增溶比与有机物的水溶解度呈正相关,与Kow、kow、溶质的摩尔体积和表面活性剂的亲水-亲油平衡值HLB呈负相关.Na 、Mg2 和Ca2 能增大氯苯在表面活性剂中的表观溶解度,阴非离子表面活性剂SDS与TW80混合后能提高表面活性剂的抗硬水能力,提高增溶效率.     

Multiphase flow and transport through fractured heterogeneous porous media

The migration of Dense, Non-Aqueous Phase Liquid (DNAPL) and dissolved phase contamination through a fractured heterogeneous porous medium has been investigated through the use of a multiphase compositional model. The sensitivity of the timescales of migration and the distribution of contaminant in the subsurface to the mean permeability, the variance of the permeability, and the degree of fracturing of the domain were examined. It was found that increasing the mean permeability of the domain allowed the DNAPL to penetrate deeper into the subsurface, while decreasing the mean permeability caused the DNAPL to pool at shallower depths. The presence of fractures within the system was found to control the infiltration only in the most fractured domain. Moment analysis of the nonwetting phase showed that large-scale movement had ceased after approximately 9 years (maximum duration of the source-on condition was approximately 4.5 years). This tended to be due to a redistribution of the DNAPL towards a residual configuration, as was evidenced by the gradual trending of average nonwetting phase saturations within the domain to a static value. The dissolved phase plume was found to migrate at essentially the same rate as the nonwetting phase, due to the reduced relative permeability of lenses containing DNAPL, and due to diffusive losses of mass to the matrix of fractured clay and silty-clay lenses. Some exceptions to this were found when the DNAPL could not overcome the displacement pressure of a lens, and could not by-pass the lens due to the lack of available driving force after the source had been shut off.     

地球物理方法在地下水有机污染DNAPLs的调查与监测中的应用

地下水有机污染特别是重非水相液体(densenon-aqueousphaseliquids,缩写为DNAPLs)污染是当前国际上地下水污染控制的热点问题,而对DNAPLs的调查与监测也一直是近年来环境地球物理研究的热点。文章简述了DNAPLs的运移、分布规律和DNAPLs与周围土壤及岩石存在的物理性质差异,综述了地球物理方法在DNAPLs的调查与监测应用中的有效性,探讨了地球物理方法直接探测DNAPLs的可行性,并提出了展望。     

Mechanism for the destruction of carbon tetrachloride and chloroform DNAPLs by modified Fenton's reagent

The destruction of a carbon tetrachloride DNAPL and a chloroform DNAPL was investigated in reactions containing 0.5 mL of DNAPL and a solution of modified Fenton's reagent (2M H2O2 and 5mM iron(III)-chelate). Carbon tetrachloride and chloroform masses were followed in the DNAPLs, the aqueous phases, and the off gasses. In addition, the rate of DNAPL destruction was compared to the rate of gas-purge dissolution. Carbon tetrachloride DNAPLs were rapidly destroyed by modified Fenton's reagent at 6.5 times the rate of gas purge dissolution, with 74% of the DNAPL destroyed within 24h. Use of reactions in which a single reactive oxygen species (hydroxyl radical, hydroperoxide anion, or superoxide radical anion) was generated showed that superoxide is the reactive species in modified Fenton's reagent responsible for carbon tetrachloride DNAPL destruction. Chloroform DNAPLs were also destroyed by modified Fenton's reagent, but at a rate slower than the rate of gas purge dissolution. Reactions generating a single reactive oxygen species demonstrated that chloroform destruction was the result of both superoxide and hydroxyl radical activity. Such a mechanism of chloroform DNAPL destruction is in agreement with the slow but relatively equal reactivity of chloroform with both superoxide and hydroxyl radical. The results of this research demonstrate that modified Fenton's reagent can rapidly and effectively destroy DNAPLs of contaminants characterized by minimal reactivity with hydroxyl radical, and should receive more consideration as a DNAPL cleanup technology.