Effects of hydrodynamic chromatography on colloid-facilitated migration of radionuclides in the fractured rock

The performance assessment of high level radioactive waste disposal has emphasized the role of colloids in the migration of radionuclides in the geosphere. Previous literature [Nagasaki S, Tanaka S, Suzuki A. Fast transport of colloidal particles through quartz-packed columns. J. Nucl. Sci. Technol. 1975;30(11):1136] indicates that owing to hydrodynamic chromatography the colloid velocity may not be equal to that of groundwater. Using hydrodynamic chromatography, this work investigates the effects of the size of colloidal particles on the radionuclide migration facilitated by colloids in a single fractured porous rock. Also, a methodology is proposed to develop a predictive model to assess transport within the fracture rock as well as various other phenomenological coefficients, particularly the size of colloidal particles. In addition, a fully developed concentration profile for non-reactive colloids in the fracture is developed to elucidate hydrodynamic chromatography of colloids in geological media. The external forces acting on colloidal particles hypothesized in the model proposed herein include inertial force, van der Waals attractive force, double layer force as well as gravitational force. The dispersion coefficient of colloids and the distribution coefficient for radionuclides with colloids are also considered as they pertain to the size of the colloid. In addition, the size distributions of colloids are utilized to investigate the effects of polydispersed colloids.     

A dynamic study of the sorption and the transport processes of cadmium in calcareous sandy soils

The interactions of Cd2+ with silica and calcite were observed through laboratory dynamic experiments. Cd2+ sorption processes were characterised as a function of reaction kinetics in aqueous solutions saturated or not with respect to calcite. Chromatographic column experiments show that Cd2+ sorption on silica can be considered as a reversible equilibrate reaction which depends on water composition and pH. For a porous medium composed by a mixture of silica and calcite, the Cd2+ migration behaviours are predominantly controlled by calcite. The amount and the reversibility of sorbed Cd on calcite are strongly affected by kinetic limitations. Stirred flow through reactor experiments provide an original method to separate and characterise the 'fast' and 'slow' Cd sorption on calcite processes. The 'fast' Cd reversible adsorption isotherms and the rate of Cd subsequent uptake by 'slow' reactions are determined. In addition, the inhibition of calcite dissolution is observed as a function of sorbed Cd in order to provide a complete mechanistic database for coupled transport-geochemistry models.     

Numerical modelling of multiphase flow and transport processes in landfills.

Waste material in municipal landfills can be described as heterogeneous porous media, where flow and transport processes of gases and liquids are combined with local material degradation. This paper deals with the basic formulation of a multiphase flow and transport model applicable to the numerical analysis of coupled transport and reaction processes inside landfills. The transport model treats landfills within the framework of continuum mechanics, where flow and transport processes are described on a macroscopic level. The composition of organic and inorganic matter in the solid phase and its degradation are modelled on a microscopic scale. The degradation model captures the different reaction schemes of various microbial activities. Subsequently, transport and reaction processes have to be coupled, since emissions at the surface and from the drainage layer depend on the flow of leachate and gas, the transport of various substances and heat, and the biodegradation of organic matter. The theoretical considerations presented here are fundamental to the development of numerical models for the simulation of multiphase flow and transport processes inside landfills coupled with biochemical reactions and heat generation. The implicit modelling of leachate and gas flows including growth and decay of micro-organisms are innovative contributions to landfill modelling     

Modeling of mercury sorption by activated carbon in a confined,a semi-fluidized,and a fluidized bed

A process model was developed to simulate elemental mercury sorption by activated carbon in three distinct beds, namely a confined, a semi-fluidized, and a fluidized bed. The model involved the coupling of a kinetic model based on the mechanisms of surface equilibrium and external mass transfer, and a material balance model based on the tank-in-series approach. For surface equilibrium, three different equilibrium laws were used in the model, namely the Henry's Law, the Langmuir isotherm and the Freundlich isotherm. Literature mercury sorption data were used to determine the best-fit values of parameters for these equilibrium expressions. The parameter-fitted model was then used to simulate mercury sorption processes in the three distinct beds. The simulation parameters were mercury concentration, gas flow rate, adsorption temperature and the degree of semi-fluidization. The simulation results have indicated that the model is capable of describing the literature available mercury sorption data. All the three surface equilibrium laws appear to simulate the adsorption profiles equally well mainly because the sorption process occurs in an extremely low concentration range. The simulation results for the three distinct beds have suggested that the confined bed has the best mercury control performance; however, it generates the highest pressure-drop across the bed. A fluidized bed creates the least pressure drop; however, its sorption performance is poor. A semi-fluidized bed offers acceptable performance with affordable pressure-drops and can be a practical candidate for the process.     

多孔黏土异构材料对气态萘的吸附

以膨润土为基质,添加表面活性剂和助表面活性剂,制备了多孔黏土异构材料(PCHs),采用SEM和BET技术进行了表征,并将其用于气态萘的吸附。考察了吸附效果的影响因素,并探讨了吸附机理。表征结果显示,PCHs具有较大的比表面积,孔径分布均匀,兼具微孔和中孔结构。实验结果表明:当吸附温度为30℃、初始萘质量浓度为560 mg/m3、相对湿度为0时,PCHs对萘的平衡吸附量达370 mg/g,远高于膨润土和有机膨润土;吸附为放热过程,温度越高平衡吸附量越低;平衡吸附量随初始萘质量浓度的增加呈非线性增长;水蒸气的存在导致萘的平衡吸附量减小;萘在PCHs上的吸附机理主要为表面物理吸附和有机质的分配作用。     

Fate and transport of phenol in a packed bed reactor containing simulated solid waste

An assessment of the risk to human health and the environment associated with the presence of organic contaminants (OCs) in landfills necessitates reliable predictive models. The overall objectives of this study were to (1) conduct column experiments to measure the fate and transport of an OC in a simulated solid waste mixture, (2) compare the results of column experiments to model predictions using HYDRUS-1D (version 4.13), a contaminant fate and transport model that can be parameterized to simulate the laboratory experimental system, and (3) determine model input parameters from independently conducted batch experiments. Experiments were conducted in which sorption only and sorption plus biodegradation influenced OC transport. HYDRUS-1D can reasonably simulate the fate and transport of phenol in an anaerobic and fully saturated waste column in which biodegradation and sorption are the prevailing fate processes. The agreement between model predictions and column data was imperfect (i.e., within a factor of two) for the sorption plus biodegradation test and the error almost certainly lies in the difficulty of measuring a biodegradation rate that is applicable to the column conditions. Nevertheless, a biodegradation rate estimate that is within a factor of two or even five may be adequate in the context of a landfill, given the extended retention time and the fact that leachate release will be controlled by the infiltration rate which can be minimized by engineering controls.     

Investigation of the Thermosensitive Nanosphere Polymer in Removing Organophosphorus Pesticides from Water and Its Isotherm Study (Case Study: Diazinon)

In this research, a novel thermosensitive nanosphere polymer (TNP) was synthesized by copolymerization of N-isopropylacrylamide with 3-allyloxy-1,2-propanediol for the removal of diazinon from water. The characterization of the synthesized adsorbent has been performed by Fourier transform infrared spectrometer, scanning electron microscopy and elemental analysis. Batch adsorption method was performed to investigate the influences of various parameters like pH, temperature and contact time on the adsorption of diazinon. The equilibrium adsorption data of diazinon by TNP was studied by Langmuir, Freundlich, Temkin and Redlich–Peterson model. According to equilibrium adsorption results, the Langmuir, Freundlich and Temkin constants were evaluated to be 0.912 (L/mg), 7.916 (mg/g) (L/mg)^1/n and 2.494 respectively at pH 7 and room temperature. Based on Redlich–Peterson model analysis, the equilibrium data for the adsorption of diazinon was conformed well to the Langmuir isotherm model. This method was successfully applied for removal of diazinon from environmental samples. Moreover, in reusing of TNP, the sorption capacity was maintained without any significant change after 10 cycles of sorption–desorption process.     

Quantifying the availability and the stability of trace cationic elements in fly ash

For adsorption-desorption controlled leaching processes, the total leachable mass and the adsorption constant are parameters representing the availability and the stability of trace elements in solid media. With these parameters, one can predict the leaching behavior of trace elements from solids under various pH and solid-to-liquid ratio conditions. An approach was developed in this paper to determine these parameters for model elements Cu(II), Cd(II), and Ni(II) in fly ash. This approach consists of a batch equilibrium titration, a batch equilibrium leaching with and without target element addition, and mathematical modeling. Results indicated that the adsorption constant of a trace element can be determined by modeling the adsorption ratio of the added element to the system as a function of pH. Results also indicated that the trace element originally present in fly ash had similar adsorption-desorption behavior as that added externally. By modeling the batch leaching data with and without external element addition, the total leachable mass and adsorption constant of the target element can be determined simultaneously. The total leachable mass is in agreement with experimental data from 50mM EDTA extraction.     

超细粉煤灰对模拟废水中孔雀石绿的吸附性能

以球磨制得的超细粉煤灰为吸附材料,采用振荡吸附法研究了其对模拟废水中孔雀石绿的吸附性能.实验结果表明:在超细粉煤灰加入量为10g/L、吸附温度为298K、初始孔雀石绿质量浓度为500mg/L、振荡时间为120min、孔雀石绿废水自然酸碱度条件下,达到吸附平衡时的吸附量为49.97 mg/g,孔雀石绿几乎全部被超细粉煤灰所吸附;该吸附反应很好地符合二级吸附动力学方程,Ea为3.95kJ/mol,吸附反应速率较快,吸附过程由孔雀石绿在超细粉煤灰颗粒内部的扩散控制;该吸附符合Langmuir吸附等温方程,随吸附温度升高,饱和吸附量下降,298K下的饱和吸附量可达526.32mg/g,是自发进行的放热反应过程.     

The neutralization behavior of MSWI bottom ash on different time scales and in different reaction systems

The neutralization behavior of municipal solid waste incineration (MSWI) bottom ash is characterized according to reaction time and reaction system. Batch and flow-through pH titrations are used to determine the acid neutralizing capacity of the MSWI bottom ash in different reaction systems. A reaction path model and a reactive transport model evaluate the detailed mechanisms and titration kinetics of the experiments. The results indicate that both the neutralization kinetics and titration kinetics of the test methods are important. They determine the relation between the time scale of the experiments and that of an actual leaching environment. Current pH titration experiments account mainly for the relatively fast neutralization reactions, so that they cannot assess the long-term neutralization processes of MSWI bottom ash. It is also found that the neutralization characteristics of MSWI bottom ash in a flow-through system are very different from those in a batch system. The movement of a pH front and the washing-out of soluble buffering components have large influences on the neutralization ability of MSWI bottom ash in a reaction system with flow-through of leachant.     

Model-based prediction of long-term leaching of contaminants from secondary materials in road constructions and noise protection dams

In this study, contaminant leaching from three different secondary materials (demolition waste, municipal solid waste incineration ash, and blast furnace slag) to groundwater is assessed by numerical modeling. Reactive transport simulations for a noise protection dam and a road dam (a typical German autobahn), in which secondary materials are reused as base layers, were performed to predict the breakthrough of a conservative tracer (i.e., a salt) and sorbing contaminants (e.g., PAHs like naphthalene and phenanthrene or heavy metals) at the groundwater table. The dam constructions have a composite architecture with soil covers in inclined layers and distinct contrasts in the unsaturated hydraulic properties of the used materials. Capillary barrier effects result in strong spatial variabilities of flow and transport velocities. Contaminant breakthrough curves at the groundwater table show significant tailing due to slow sorption kinetics and a wide distribution of travel times. While conservative tracer breakthrough depends primarily on subsoil hydraulic properties, equilibrium distribution coefficients and sorption kinetics represent additional controlling factors for contaminant spreading. Hence, the three secondary materials show pronounced differences in the temporal development of leached contaminant concentrations with consequences for breakthrough times and peak concentrations at the groundwater table. Significant concentration reductions due to dispersion occur only if the source concentrations decrease significantly prior to the arrival of the contaminant at the groundwater table. Biodegradation causes significant reduction of breakthrough concentrations only if flow velocities are low.     

Root Exudates Impact on Phenanthrene Availability

In order to improve and optimize phytoremediation of PAH we propose to focus on the rhizospheric processes controlling PAH degradation. In this paper the effect of root exudates on PAH availability is studied. Model organic compounds (malic acid, malonic acid and EDTA) representing root exudates have been tested for their effect on phenanthrene sorption on a reference non polluted agricultural soil material. Phenanthrene adsorption isotherms were first obtained with batch experiments. Results showed linear isotherms and phenanthrene sorption was enhanced as the concentration of organic compounds in the solution increased. Column leaching experiments were then used to simulate the effect of root exudation following the soil pollution. Inlet solutions containing the different organic acids used were flowed through the column containing the artificially polluted soil material. Elution curves showed that the phenanthrene was less easily eluted when the solution injected contained the organic acids. However, magnitude of the phenomena did not fit with adsorption constants obtained in batch experiments. Phenanthrene desorption appeared limited by sequestration but organic acids seemed able to partially disturb the soil material structure to limit the sequestration effect.     

Improving the adsorption capacity and solid structure of natural volcanic soil using a foaming-sintering process based on recycled polyethylene terephthalate (PET).

The volcanic soils of southern Chile have demonstrated a high capacity to adsorb environmental pollutants, but for an industrial application, a stable solid material is necessary. The objective of this work was to produce a stable ceramic material through a process involving volcanic soil-polyurethane foam produced with recycled polyethylene terephthalate (PET)-polyols, and further thermal treatment. The selected foam formulation with 35.4% volcanic soil (< 63 microm) seems to be the most suitable for thermal treatment, with temperature steps at 700, 850, 1000 and 1200 degrees C. The porous ceramic material obtained has a stable solid form and an improved chlorophenols adsorption capacity (comparable to natural zeolites) that makes it suitable for advanced wastewater treatment and landfill leachate depuration.     

Colloids in the mortar backfill of a cementitious repository for radioactive waste

Colloids are present in groundwater aquifers and water-permeable engineered barrier systems and may facilitate the migration of radionuclides. A highly permeable mortar is foreseen to be used as backfill for the engineered barrier of the Swiss repository for low- and intermediate-level waste. The backfill is considered to be a chemical environment with some potential for colloid generation and, due to its high porosity, for colloid mobility. Colloid concentration measurements were carried out using an in-situ liquid particle counting system. The in-house developed counting system with three commercially available sensors allowed the detection of single particles and colloids at low concentrations in the size range 50-5000 nm. The counting system was tested using suspensions prepared from certified size standards. The concentrations of colloids with size range 50-1000 nm were measured in cement pore water, which was collected from a column filled with a highly permeable backfill mortar. The chemical composition of the pore water corresponded to a Ca(OH)2-controlled cement system. Colloid concentrations in the backfill pore water were found to be typically lower than approximately 0.1 ppm. The specific (geometric) surface areas of the colloid populations were in the range 240 m2 g(-1) to 770 m2 g(-1). The low colloid inventories observed in this study can be explained by the high ionic strength and Ca concentrations of the cement pore water. These conditions are favourable for colloid-colloid and colloid-backfill interactions and unfavourable for colloid-enhanced nuclide transport.     

A comparative adsorption/biosorption study of mono-chlorinated phenols onto various sorbents

The potential use of dried activated sludge and fly ash as a substitute for granular activated carbon for removing mono-chlorinated phenols (o-chlorophenol and p-chlorophenol) was examined. The pollutant binding capacity of the adsorbent/biosorbent was shown to be a function of substituted group, initial pH and initial mono-chlorinated phenol concentration. The working sorption pH value was determined as 1.0 and the equilibrium uptake increased with increasing initial mono-chlorinated phenol concentration up to 500 mg dm(-3) for all the mono-chlorinated phenol-sorbent systems. The suitability of the Freundlich, Langmuir and Redlich-Peterson adsorption models to the equilibrium data were investigated for each mono-chlorinated phenol-sorbent system. The results showed that the equilibrium data for all the mono-chlorinated phenol-sorbent systems fitted the Redlich-Peterson model best within the concentration range studied.     

Waste form corrosion modeling: comparison with experimental results

Results of leaching experiments using active and inactively simulated HLW glass in concentrated NaCl solution are described. Measured solution concentrations of glass components, fission products and actinides are compared with computed data. The computed pH value corresponds with the findings from experiments with inactively simulated glass samples. Moreover, the concentrations of silica and strontium can be described adequately by reaction path modelling. The computed U concentration is explained by the precipitation of schoepite or Na2U2O7. The computed Am concentration significantly exceeds the measured data. This may be attributed to sorption processes on corrosion products of the glass, which are relevant also for lanthanide elements under the conditions of the experiments. This hypothesis is tested by solid solution approaches and by computing sorption of Am onto SiO2 precipitates.     

Combined MODFLOW‐FRACTRAN Application to Assess Chlorinated Solvent Transport and Remediation in Fractured Sedimentary Rock

Detailed field investigations and numerical modeling were conducted to evaluate transport and fate of chlorinated solvent contamination in a fractured sedimentary bedrock aquifer (sandstone/siltstone/mudstone) at a Superfund site in central New Jersey. Field investigations provided information on the fractured rock system hydrogeology, including hydraulic gradients, bulk hydraulic conductivity, fracture network, and rock matrix, and on depth discrete contaminant distribution in fractures (via groundwater sampling) and matrix (via detailed subsampling of continuous cores). The numerical modeling endeavor involved application of both an equivalent porous media (EPM) model for flow and a discrete fracture network (DFN) model for transport. This combination of complementary models, informed by appropriate field data, allowed a quantitative representation of the conceptual site model (CSM) to assess relative importance of various processes, and to examine efficacy of remedial alternatives. Modeling progressed in two stages: first a large‐scale (20 km x 25 km domain) 3‐D EPM flow model (MODFLOW) was used to evaluate the bulk groundwater flow system and contaminant transport pathways under historic and current aquifer stress conditions and current stresses. Then, results of the flow model informed a 2‐D DFN transport model (FRACTRAN) to evaluate transport along a 1,000‐m flowpath from the source represented as a 2‐D vertical cross‐section. The combined model results were used to interpret and estimate the current and potential future extent of rock matrix and aqueous‐phase contaminant conditions and evaluate remedial strategies. Results of this study show strong effects of matrix diffusion and other processes on attenuating the plume such that future impacts on downgradient well fields under the hydraulic stresses modeled should be negligible. Results also showed futility of source remediation efforts in the fractured rock, and supported a technical impracticability (TI) waiver for the site. © 2013 Wiley Periodicals, Inc.     

NUMERICAL MODELLING OF GENERATION AND TRANSPORT OF GAS AND HEAT IN LANDFILLS I. MODEL FORMULATION

A mathematical model for the generation and transport of gas and heat in a sanitary landfill was developed based on earlier work on the Mountain View Controlled Landfill Project (MVCLP) in California, U.S.A. The present model incorporates biokinetic model equations describing the dynamics of the microbial landfill ecosystem into multi-layer, time-dependent transport and generation of gas and heat models. It is based on the fundamental principles governing the physical, chemical and microbiological processes in a porous media context such as a sanitary landfill. The model includes biochemical and temperature feedback loops to simulate the effects of their corresponding parameters on microbiological processes. The resulting integrated biokinetic, gas and heat generation and transport model was used to simulate field data from the MVCLP and to assess the sensitivity of model results to biological parameters. The model can be used to predict the rate and total production of methane in a landfill. The present work is presented in a series of three papers: (I) model formulation; (II) model application; and (III) sensitivity analysis.