Impact of Reaction Conditions on MnO2 Genesis during Permanganate Oxidation

To enhance the understanding of the behavior and effects of the precipitation of MnO2 particles in the subsurface generated during in situ chemical oxidation (ISCO) using permanganate, laboratory batch experiments were completed to examine the influence that varied reaction matrix conditions have on the generation and properties of manganese oxides. The conditions examined include organic material type and concentration, permanganate concentration, pH, and the presence of calcium (as a representative divalent cation) in solution. Experimental studies included: (1) spectrophotometric examination of permanganate depletion and manganese oxides generation over time during reactions with trichloroethene; (2) scanning electron microscopy analyses of manganese particle morphology; (3) particle size distribution (filtration) characterization studies; and (4) optical particle sizing and numeration studies. Bench-scale, batch experiments were conducted to focus on fundamental chemical properties affecting particle development under varied potential environmental conditions. The amount of manganese oxides particles that develop, grow, and potentially settle as a result of permanganate ISCO of organic contaminants is a function of the particle size and concentration, the time allowed for particle development, and the impact of matrix conditions on the ability of particles to agglomerate.     

Modeling Tetrachloroethylene Decomposition in Photosonolysis Reactor

A mathematical model was developed for the decomposition of halogenated compounds in water and applied for tetrachloroethylene (PCE) in a flow-through photosonolysis reactor. To develop the model, a series of differential equations were formulated based on the principles of conservation of mass and mass action for hypothetical parent and daughter species, which were then solved analytically. The model sensitivity analysis was performed to determine if the model gives intuitive results. In support of the modeling effort, experiments were conducted. In a flow-through bench-scale reactor, simulated groundwater contaminated with PCE was irradiated with ultraviolet light and ultrasound concurrently in the presence of titanium dioxide (TiO2). The model was calibrated against the concentrations of PCE, trichloroethylene, methylene chloride, and chloride ion, obtained from the experiments. The proposition for the rate constants is based on fitting the model result to the experimental data. The model was further verified by comparing the model results against a different set of experimental data. The model results against available data indicated good agreement within experimental variations. The modeling suggests that PCE is more susceptible to the C-C double bond cleavage than the C-Cl bond cleavage. The results also support the assumptions that chlorinated methane compounds can be degraded at higher rates than chlorinated ethylene and that the values of the degradation rate constants increase with a decreasing number of chlorine atoms attached to the hydrocarbon compound.     

地下水污染修复的活性渗滤墙技术

活性渗滤墙是一种现场修复受污染地下水的新型技术，具有原理简单，施工方便，运行费用低廉等特点，活性渗滤墙垂直于地下水流动方向设置，当地下水流通过活性渗滤墙时，污染物与墙体材料发生化学反应，从而达到环境修复的目的。文中综述了活性渗滤墙技术的修复机理和实际应用，大量研究表明，应用金属铁作为活性渗滤墙材料，可以去除地下水中的重金属以及有机污染物，目前活性渗滤墙已经在世界各地应用，是一种非常有发展前景的环境污染修复技术。     

风险度量与风险管理的新工具ES

采用资产组合损失变量描述风险,并基于损失分布的α-(上)分位数给出"期望巨额损失值"ES(expected shortfall)和"条件风险价值"CVaR(conditional value at risk)的定义。在一般损失分布下,通过直接计算说明了任一资产组合损失变量的"期望巨额损失值"ES的定义与α-(上)分位数的选取无关;而且也通过直接计算证明了ES与CVaR两者的等价关系;进而通过构造出ES的概率测度族表示证明了ES是一致性风险度量方法。此外,还就相关问题,例如分位数、一致性风险度量、尾部条件期望TCE等,给出了一些有价值的注记。     

最大似然估计ROC凸包曲线算法

采用列联表表示特定阈值下入侵检测系统(IDS)的性能,使用ROC曲线对不同阈值下IDS的总体性能进行评估。在实际应用中,基于样本数据集,通过计算几何的方式得到ROC凸包曲线(ROCCH)。为降低ROCCH的计算复杂度,在曲线下面积(AUC)最大似然估计的条件下,通过保序回归得到最大似然估计ROC曲线(MLE-ROC)算法。实验表明,MLE-ROC算法在降低计算复杂度的同时提高了AUC的近似程度。     

Competitive Effects of Trichloroethylene on Cr(VI) Removal by Zero-Valent Iron

Eleven columns were set up under various groundwater geochemistry conditions to investigate the competitive effect of trichloroethylene (TCE) on hexavalent chromium [Cr(VI)] removal by zero-valent iron (Fe0). They were found to be electron competitors in the redox reactions. In the presence of TCE, the Cr(VI) removal capacities of Fe0 were decreased by about 40% when compared with their respective Cr(VI) removal capacities with identical groundwater geochemistry but without TCE. The specific reaction rate constant (kSA) of TCE was decreased by about 50% when Cr(VI) was singly applied. The kSA of TCE was further decreased by 75% in the presence of both Cr(VI) and carbonate. However, there was no apparent effect on the kSA of TCE when Cr(VI), hardness and carbonate were all present. It revealed that TCE was a stronger electron competitor of Cr(VI) and the degradation of TCE became more favorable when both hardness and carbonate were present. This suggests that the passivated precipitates formed on the Fe0 surface in the presence of both hardness and carbonate may significantly affect the Cr(VI) removal by Fe0 but has insignificant effect on the TCE removal.     

Physical Properties of Vegetable Oil and Chlorinated Ethene Mixtures

Laboratory experiments were conducted to investigate the abiotic interactions of soybean oil (SoyOil) and chlorinated ethene (CE) nonaqueous phase liquids (NAPLs). The mixed NAPL density and interfacial tension behaved ideally, as predicted by the volume ratio. The mixed NAPL viscosity increased exponentially from that of the pure CE to that of pure SoyOil as the volume fraction increased. The measured contact angle was highly variable and was unpredictable as a function of the volume composition of the mixed NAPL. The physical property effects indicate that the mobilization of residual CE NAPLs because of SoyOil injection is unlikely. Equilibrium dissolution of CEs from the NAPL mixtures behaved linearly as a function of the mole fraction. Dissolved SoyOil in simulated groundwater enhanced the dissolution of trichloroethene (TCE) during flow tests, increasing the effluent TCE concentration from 141?to?202?mg/L. The ready intermingling of the CE dense nonaqueous phase liquids (DNAPLs) and SoyOil indicate that such interactions may be significant at sites where vegetable oil is injected into DNAPL source areas to enhance in situ anaerobic bioremediation.     

原位厌氧修复化工园区地下水有机污染物的研究进展

综述了化工园区的发展带来的地下水污染现状、地下水主要有机污染物和地下水原位生物修复的研究进展,重点探讨了厌氧修复技术相关的有机污染物厌氧降解,并对地下水厌氧修复技术研究前景进行了简要分析。     

Degradation of soil-sorbed trichloroethylene by stabilized zero valent iron nanoparticles: effects of sorption, surfactants, and natural organic matter

Zero valent iron (ZVI) nanoparticles have been studied extensively for degradation of chlorinated solvents in the aqueous phase, and have been tested for in-situ remediation of contaminated soil and groundwater. However, little is known about its effectiveness for degrading soil-sorbed contaminants. This work studied reductive dechlorination of trichloroethylene (TCE) sorbed in two model soils (a potting soil and Smith Farm soil) using carboxymethyl cellulose (CMC) stabilized Fe-Pd bimetallic nanoparticles. Effects of sorption, surfactants and dissolved organic matter (DOC) were determined through batch kinetic experiments. While the nanoparticles can effectively degrade soil-sorbed TCE, the TCE degradation rate was strongly limited by desorption kinetics, especially for the potting soil which has a higher organic matter content of 8.2%. Under otherwise identical conditions, ∼44% of TCE sorbed in the potting soil was degraded in 30 h, compared to ∼82% for Smith Farm soil (organic matter content = 0.7%). DOC from the potting soil was found to inhibit TCE degradation. The presence of the extracted SOM at 40 ppm and 350 ppm as TOC reduced the degradation rate by 34% and 67%, respectively. Four prototype surfactants were tested for their effects on TCE desorption and degradation rates, including two anionic surfactants known as SDS (sodium dodecyl sulfate) and SDBS (sodium dodecyl benzene sulfonate), a cationic surfactant hexadecyltrimethylammonium (HDTMA) bromide, and a non-ionic surfactant Tween 80. All four surfactants were observed to enhance TCE desorption at concentrations below or above the critical micelle concentration (cmc), with the anionic surfactant SDS being most effective. Based on the pseudo-first-order reaction rate law, the presence of 1×cmc SDS increased the reaction rate by a factor of 2.5 when the nanoparticles were used for degrading TCE in a water solution. SDS was effective for enhancing degradation of TCE sorbed in Smith Farm soil, the presence of SDS at sub-cmc increased TCE degraded by ∼10%. However, effect of SDS on degradation of TCE in the potting soil was more complex. The presence of SDS at sub-cmc decreased TCE degradation by 5%, but increased degradation by 5% when SDS dosage was raised to 5×cmc. The opposing effects were attributed to combined effects of SDS on TCE desorption and degradation, release of soil organic matter and nanoparticle aggregation. The findings strongly suggest that effect of soil sorption on the effectiveness of Fe-Pd nanoparticles must be taken into account in process design, and soil organic content plays an important role in the overall degradation rate and in the effectiveness of surfactant uses.     

Activated carbon adsorption of trichloroethylene (TCE) vapor stripped from TCE-contaminated water

Ground water contaminated with trichloroethylene (TCE) used in electronic, electric, dry cleaning and the like industries is often treated by air-stripping. In this treatment process, TCE in its vapor form is stripped from ground water by air stream and sometimes emitted into the atmosphere without any additional treatments. Activated carbon adsorption is one of the practical and useful processes for recovering the TCE vapor from the exhaust air stream. However, adsorption of the TCE vapor from the stripping air stream onto activated carbons is not so simple as that from dry air, since in the exhaust air stream the TCE vapor coexists with water vapor with relatively high concentrations. The understanding of the adsorption characteristics of the TCE vapor to be adsorbed on activated carbon in the water vapor-coexisting system is essential for successfully designing and operating the TCE recovery process. In this work, the adsorption equilibrium relations of the TCE vapor adsorption on activated carbons were elucidated as a function of various relative humidity. Activated carbon fibers (ACFs) were used as model activated carbon. The adsorption equilibrium relations were studied by the column adsorption method. The adsorption isotherms of TCE vapor adsorbed on sample ACFs were successfully correlated by the Dubinin-Radushkevich equation for both cases with and without coexistent water vapor. No effects of coexistent water vapor were found on the limiting adsorption volume. However, the adsorption characteristic energy was significantly reduced by the coexistence of water vapor and its reduction was successfully correlated with the equilibrium amount of water vapor adsorbed under the dynamic condition.