Controlled release, blind test of DNAPL remediation by ethanol flushing

A dense nonaqueous phase liquid (DNAPL) source zone was established within a sheet-pile isolated cell through a controlled release of perchloroethylene (PCE) to evaluate DNAPL remediation by in-situ cosolvent flushing. Ethanol was used as the cosolvent, and the main remedial mechanism was enhanced dissolution based on the phase behavior of the water-ethanol-PCE system. Based on the knowledge of the actual PCE volume introduced into the cell, it was estimated that 83 L of PCE were present at the start of the test. Over a 40-day period, 64% of the PCE was removed by flushing the cell with an alcohol solution of approximately 70% ethanol and 30% water. High removal efficiencies at the end of the test indicated that more PCE could have been removed had it been possible to continue the demonstration. The ethanol solution extracted from the cell was recycled during the test using activated carbon and air stripping treatment. Both of these treatment processes were successful in removing PCE for recycling purposes, with minimal impact on the ethanol content in the treated fluids. Results from pre- and post-flushing partitioning tracer tests overestimated the treatment performance. However, both of these tracer tests missed significant amounts of the PCE present, likely due to inaccessibility of the PCE. The tracer results suggest that some PCE was inaccessible to the ethanol solution which led to the inefficient PCE removal rates observed. The flux-averaged aqueous PCE concentrations measured in the post-flushing tracer test were reduced by a factor of 3 to 4 in the extraction wells that showed the highest PCE removal compared to those concentrations in the pre-flushing tracer test.     

Manipulation of density and viscosity for the optimization of DNAPL recovery by alcohol flooding

Laboratory experiments demonstrate that in situ recovery of pooled tetrachloroethene (PCE) from porous media may be accomplished more efficiently using multiple-step alcohol floods than with single alcohol floods. To optimize flooding efficiency while maintaining a low risk of downward DNAPL mobilization, a three-step flooding process is developed employing an isobutanol preflood, a composite alcohol mainflood, and a polymer solution postflood. The density and viscosity of these solutions are manipulated to prevent the onset and propagation of viscous and gravitational fingers, while maintaining phase behavior critical for efficient miscible NAPL displacement. An aqueous partitioning preflood solution of 10% by volume (10% v) isobutanol reduces the NAPL density in situ to approximately 1.00 g/ml by swelling the NAPL prior to miscible displacement induced by the mainflood. The composite alcohol mainflood, containing 65% v ethylene glycol and 35% v 1-propanol maintains miscibility while achieving neutral buoyancy and near stable displacement of the NAPL. Aqueous solutions of xanthan gum polymer efficiently displace the mainflood, reducing viscous fingering associated with waterfloods. Two-dimensional experiments using the multiple-step technique achieve 99.8% DNAPL mass recovery using a total of 0.45 pore volumes of alcohol, illustrating greater recovery efficiency than previous alcohol flooding formulations under comparable conditions.     

DNAPL distribution in the source zone: effect of soil structure and uncertainty reduction with increased sampling density

This paper focuses on parameters describing the distribution of dense nonaqueous phase liquid (DNAPL) contaminants and investigates the variability of these parameters that results from soil heterogeneity. In addition, it quantifies the uncertainty reduction that can be achieved with increased density of soil sampling. Numerical simulations of DNAPL releases were performed using stochastic realizations of hydraulic conductivity fields generated with the same geostatistical parameters and conditioning data at two sampling densities, thus generating two simulation ensembles of low and high density (three-fold increase) of soil sampling. The results showed that DNAPL plumes in aquifers identical in a statistical sense exhibit qualitatively different patterns, ranging from compact to finger-like. The corresponding quantitative differences were expressed by defining several alternative measures that describe the DNAPL plume and computing these measures for each simulation of the two ensembles. The uncertainty in the plume features under study was affected to different degrees by the variability of the soil, with coefficients of variation ranging from about 20% to 90%, for the low-density sampling. Meanwhile, the increased soil sampling frequency resulted in reductions of uncertainty varying from 7% to 69%, for low- and high-uncertainty variables, respectively. In view of the varying uncertainty in the characteristics of a DNAPL plume, remedial designs that require estimates of the less uncertain features of the plume may be preferred over others that need a more detailed characterization of the source zone architecture.     

Infiltration and redistribution of LNAPL into unsaturated layered porous media

Enhanced understanding of light non-aqueous phase liquid (LNAPL) infiltration into heterogeneous porous media is important for the effective design of remediation strategies. We used a 2-D experimental facility that allows for visual observation of LNAPL contours in order to study LNAPL redistribution in a layered porous medium. The layers are situated in the unsaturated zone near the watertable and they are inclined to be able to observe the effect of discontinuities in capillary forces and relative permeabilities. Two experiments were performed. The first experiment consisted of LNAPL infiltration into a fine sand matrix with a coarse sand layer, and the second experiment consisted of a coarse sand matrix and a fine sand layer. The numerical multi-phase flow model STOMP was validated with regard to the experimental results. This model is able to adequately reproduce the experimental LNAPL contours. Numerical sensitivity analysis was also performed. The capillarity contrast between sands was found to be the main controlling factor determining the final LNAPL distribution.     

The velocity of DNAPL fingering in water-saturated porous media: laboratory experiments and a mobile–immobile–zone model

Dense nonaqueous phase liquids (DNAPLs) are immiscible with water and can give rise to highly fingered fluid distributions when infiltrating through water-saturated porous media. In this paper, a conceptual mobile–immobile–zone (MIZ) model is presented to describe the structure of a DNAPL finger in water-saturated porous media and the velocity of finger propagation. A finger is composed of a finger body and a tip. The finger body has a mobile core and an immobile sheath. All the DNAPL within the tip of a finger is mobile. Lab experiments utilizing image analyses of a DNAPL (PCE) penetrating into water-saturated homogeneous glass beads were carried out in a two-dimensional transparent chamber. The results show that the fingers elongated almost linearly with time. The fingers did not grow laterally after the tip of the finger had passed. The average finger diameters were between 3.9 and 5.4 mm for PCE propagation in water-saturated glass bead porous media with mean particle diameters from 0.32 to 1.36 mm. The estimated mobile core diameters were 51–60% of the average finger diameters.     

含油废水异质结微通道分离机理及实验

石油炼制废水等石化行业含油废水普遍存在油分与悬浮物高度复合、油分乳化且水质剧烈波动等特征,其达标处理成为关乎企业绿色发展与产能拓展的关键因素。针对含油废水分离资源化需求,采用聚二甲基硅氧烷(PDMS)、四氢呋喃(THF)、聚甲基丙烯酸甲酯(PMMA)、固化剂等配制涂敷剂,通过喷涂石英砂制备了改性颗粒,并混合常规石英砂构建了异质结颗粒群,由此开发出异质结微通道沸腾床分离实验装置,考察了其对复合污染乳化废水中污染物的分离效果。结果表明：涂覆改性颗粒的接触角明显增加,且改性颗粒与油滴接触的微界面动态识别过程表明其较原始石英砂的疏油性显著增加;异质结颗粒群经过撕裂、剥离和聚并过程,将乳化液中10 μm以下的细小油滴有效聚结并确保废水油分去除率超过92%。针对油分和悬浮物质量浓度不超过50 000 mg·L⁻¹的实际石化废水,现场10 m³·h⁻¹规模的异质结微通道沸腾床侧线实验结果表明,在常规工况和波动工况条件下,其出水平均油分质量浓度分别为11.4 mg·L⁻¹和18.2 mg·L⁻¹,悬浮物质量浓度则分别降至21.3 mg·L⁻¹和29.1 mg·L⁻¹,且经过20 min反洗后沸腾床分离器满足长期稳定运行要求。     

Ecotoxicological risk assessment linked to the discharge by hospitals of bio-accumulative pharmaceuticals into aquatic media: The case of mitotane

The release of hospital wastewater into the urban sewer networks contributes to the general contamination of aquatic media by pharmaceutical residues. These residues include bio-accumulative pharmaceuticals that lead to increased risk for ecosystems because they can concentrate in organisms and food chains, and therefore reach toxic levels. In order to assess the ecotoxicological risks linked to this particular category of residues, we have developed a specific method, by combining a theoretical calculation of pollutant concentrations in organisms to estimate Body Residue (BR), and ecotoxicity biomarkers in fish cell lines, enabling the calculation of a Critical Body Residue (CBR). This method finally results in the calculation of a specific risk quotient (Qb = BR/CBR), characterizing the risk linked to this type of pollutant. This method was applied to mitotane, a bio-accumulative pharmaceutical typically found in hospital wastewater, in the framework of an exposure scenario corresponding to the discharge of all the hospital wastewaters into the Rhone River which flows through the city of Lyon, France. This approach leads to risk quotients (Qb and Qbg) much higher than those found with the classical approach, i.e. Q = PEC/PNEC (Predictive Environmental Concentration/Predictive Non Effect Concentration) = 0.0006. This difference in the appreciation of risk is important when using cytotoxicity as the criterion for measuring the toxicity of mitotane (Qb = 0.056) and it is even greater when the criterion used is genotoxicity (Qbg = 6.8). This study must be now consolidated by taking the biomagnification of the pharmaceuticals into consideration.     

Removal of NAPLs from the unsaturated zone using steam: prevention of downward migration by injecting mixtures of steam and air

Steam injection for remediation of porous media contaminated by nonaqueous phase liquids has been shown to be a potentially efficient technology. There is, however, concern that the technique may lead to downward migration of separate phase contaminant. In this work, a modification of the steam injection technology is presented, where a mixture of steam and air was injected. In two-dimensional experiments with unsaturated porous medium contaminated with nonaqueous phase liquids, it was demonstrated how injection of pure steam lead to severe downward migration. Similar experiments, where steam and air were injected simultaneously, resulted in practically no downward migration and still rapid cleanup was achieved. The processes responsible for the prevention of downward migration when injecting steam-air mixtures were analyzed using a nonisothermal multiphase flow and transport model. Hereby, three mechanisms were identified and it was demonstrated how the effectiveness of these mechanisms depended on the air-to-steam mixing ratio.     

Adsorptive removal of an acid dye by lignocellulosic waste biomass activated carbon: equilibrium and kinetic studies

Chemically prepared activated carbon material derived from palm flower was used as adsorbent for removal of Amido Black dye in aqueous solution. Batch adsorption studies were performed for the removal of Amido Black 10B (AB10B), a di-azo acid dye from aqueous solutions by varying the parameters like initial solution pH, adsorbent dosage, initial dye concentration and temperature with three different particle sizes such as 100 μm, 600 μm and 1000 μm. The zero point charge was pH 2.5 and the maximum adsorption occurred at the pH 2.3. Experimental data were analyzed by model equations such as Langmuir, Freundlich and Temkin isotherms and it was found that the Freundlich isotherm model best fitted the adsorption data and the Freundlich constants varied from (K_F) 1.214, 1.077 and 0.884 for the three mesh sizes. Thermodynamic parameters such as ΔG, ΔH and ΔS were also calculated for the adsorption processes and found that the adsorption process is feasible and it was the endothermic reaction. Adsorption kinetics was determined using pseudo first-order, pseudo second-order rate equations and also Elovich model and intraparticle diffusion models. The results clearly showed that the adsorption of AB10B onto lignocellulosic waste biomass from palm flower (LCBPF) followed pseudo second-order model, and the pseudo second-order rate constants varied from 0.059 to 0.006 (g mg⁻¹ min) by varying initial adsorbate concentration from 25 mg L⁻¹ to 100 mg L⁻¹. Analysis of the adsorption data confirmed that the adsorption process not only followed intraparticle diffusion but also by the film diffusion mechanism.     

Insights into the structure of urea-like compounds as inhibitors of the juvenile hormone epoxide hydrolase (JHEH) of the tobacco hornworm Manduca sexta: analysis of the binding modes and structure-activity relationships of the inhibitors by docking and CoMFA calculations

Substituted urea compounds are well-known as potent inhibitors of juvenile hormone epoxide hydrolase (JHEH) of the tobacco hornworm Manduca sexta. Docking simulations of 47 derivatives inside JHEH were performed to gain insight into the structural characteristics of these complexes. The obtained orientations show a strong similitude with the observed in the known X-ray crystal structures of human soluble epoxide hydrolase (sEH) complexed with dialkylurea inhibitors. In addition, the predicted inhibitor concentration (IC₅₀) of the above-mentioned compounds as JHEH inhibitors were obtained by a quantitative structure-activity relationship (QSAR) method by using comparative molecular field analysis (CoMFA) applied to aligned dataset. The best models included steric and electrostatic fields and had adequate predictive abilities. In addition, these models were used to predict the activity of an external test set of compounds that was not used for building the model. Furthermore, plots of the CoMFA fields allowed conclusions to be drawn for the choice of suitable inhibitors.