Development and modeling of a flat plate serpentine reactor for photocatalytic degradation of 17-ethinylestradiol

A flat plate serpentine reactor modified from ultraviolet disinfection pool in municipal wastewater treatment plants was developed for the removal of 17-ethinylestradiol (EE2) for the first time. The photocatalytic degradation performance of EE2 was investigated in this serpentine reactor under different conditions such as inlet concentrations, loaded catalyst concentrations, incident radiations fluxes, and flow velocities. More than 98 % of EE2 was removed under certain conditions within 120 min. An integrated model including a six-flux adsorption–scattering model and a modified flow diffusion model was established to investigate the effect of radiation field and flow velocities, respectively. A satisfactory agreement was observed between the model simulation and experimental results, showing a potential for design and scale-up of photocatalytic reactor for wastewater treatment.     

错流式生物滴滤床净化甲苯废气

采用焦化厂污泥为菌源驯化甲苯降解菌,接种错流式生物滴滤床,净化含甲苯废气。研究了生物滴滤床的挂膜启动和长期运行情况,填料和营养液对滴滤床去除能力的影响,并对长期运行的压降进行了观察分析。反应器挂膜启动需要6 d时间,稳定运行的平均去除效率为95％,单位体积最大去除负荷为251 g/(m³·h)。结果表明,采用错流式生物滴滤床可以有效去除甲苯废气;以比表面积大的生物陶粒作为填料以及定期适量更换营养液,均有助于提高生物滴滤床的去除能力;错流式生物滴滤床具有压降小、气液分布均匀的特点。     

Impact of nonaqueous phase liquid (NAPL) source zone architecture on mass removal mechanisms in strongly layered heterogeneous porous media during soil vapor extraction

An existing multiphase flow simulator was modified in order to determine the effects of four mechanisms on NAPL mass removal in a strongly layered heterogeneous vadose zone during soil vapor extraction (SVE): a) NAPL flow, b) diffusion and dispersion from low permeability zones, c) slow desorption from sediment grains, and d) rate-limited dissolution of trapped NAPL. The impacts of water and NAPL saturation distribution, NAPL-type (i.e., free, residual, or trapped) distribution, and spatial heterogeneity of the permeability field on these mechanisms were evaluated. Two different initial source zone architectures (one with and one without trapped NAPL) were considered and these architectures were used to evaluate seven different SVE scenarios. For all runs, slow diffusion from low permeability zones that gas flow bypassed was a dominant factor for diminished SVE effectiveness at later times. This effect was more significant at high water saturation due to the decrease of gas-phase relative permeability. Transverse dispersion contributed to fast NAPL mass removal from the low permeability layer in both source zone architectures, but longitudinal dispersion did not affect overall mass removal time. Both slow desorption from sediment grains and rate-limited mass transfer from trapped NAPL only marginally affected removal times. However, mass transfer from trapped NAPL did affect mass removal at later time, as well as the NAPL distribution. NAPL flow from low to high permeability zones contributed to faster mass removal from the low permeability layer, and this effect increased when water infiltration was eliminated. These simulations indicate that if trapped NAPL exists in heterogeneous porous media, mass transfer can be improved by delivering gas directly to zones with trapped NAPL and by lowering the water content, which increases the gas relative permeability and changes trapped NAPL to free NAPL.     

印染生化尾水反渗透深度处理工艺膜污染成因分析简

为阐明印染生化尾水反渗透膜处理时膜污染的成因,使用小试装置进行40 h膜污染实验,研究膜污染速率、污染程度以及可逆性,同时应用扫描电子显微镜-EDS能谱仪、傅里叶变换红外光谱仪、电感耦合等离子发射光谱仪、总有机碳测定仪等仪器对进水水质、膜表面污染物的形态和组成等进行表征。结果表明,膜表面主要是碳酸钙无机污染和钙与有机物络合污染,无机污染占主导,且可逆性差,有机污染物主要含有—OH和—CC官能团;单一去除废水中有机物污染物（TOC去除率达88%）对膜污染缓解不明显,但钙离子的去除可显著缓解膜污染,膜通量可增加72.6%;同时去除有机物和钙离子,膜通量可增加80.4%。     

印染生化尾水反渗透深度处理工艺膜污染成因分析

为阐明印染生化尾水反渗透膜处理时膜污染的成因,使用小试装置进行40h膜污染实验,研究膜污染速率、污染程度以及可逆性,同时应用扫描电子显微镜一EDS能谱仪、傅里叶变换红外光谱仪、电感耦合等离子发射光谱仪、总有机碳测定仪等仪器对进水水质、膜表面污染物的形态和组成等进行表征。结果表明,膜表面主要是碳酸钙无机污染和钙与有机物络合污染,无机污染占主导,且可逆性差,有机污染物主要含有--OH和～c-c官能团;单一去除废水中有机物污染物（TOC去除率达88％）对膜污染缓解不明显,但钙离子的去除可显著缓解膜污染,膜通量可增加72．6％;同时去除有机物和钙离子,膜通量可增加80．4％。     

The effects of matrix diffusion on radionuclide migration in rock column experiments

Rock column experiments were performed to examine the effects of matrix diffusion and hydrodynamic dispersion on the migration of radionuclides at the laboratory scale. Tritiated water and chloride transportation was studied in intact mica gneiss and in altered more porous tonalite columns with narrow flow channels. The column diffusion properties were estimated prior to water flow experiments using the gas diffusion method with helium as the tracer gas. The numerical compartment model for advection and dispersion, with and without matrix diffusion, was used to interpret the tracer transport in the columns. Matrix diffusion behavior was also distinguished from dominating hydrodynamic dispersion in rock column experiments at the slowest water flow rates.     

错流涡旋式高效固液分离器内固液两相流的数值模拟

介绍设计制作的一种新型错流涡旋式高效固液分离装备,利用离散相模型对其进行数值模拟,得到此分离装置的三维液相流场分布、离散相砂粒的运行轨迹以及砂粒的去除效率,明确了其沉淀特征。其结论对于优化错流涡旋式高效固液分离器的设计具有参考价值。     

Transverse dispersion of non-reactive tracers in porous media: a new nonlinear relationship to predict dispersion coefficients

Assessing the potential of natural attenuation in groundwater relies on the ability to predict and quantify the processes that occur in contaminant plumes. Transverse dispersion is a significant mass transfer mechanism for mixing of electron acceptors and donors and thus may control the lengths of steady state plumes. Laboratory experiments were carried out using a 2-dimensional acrylic glass tank filled with glass beads, quartz sand and field site material as porous media. Flow velocities and grain sizes were varied in order to cover a large range of Peclet numbers including typical field scenarios. The laboratory study was extended by a comprehensive literature search to compare the new results with earlier work. As a result we propose a new empirical relationship for prediction of transverse dispersion coefficients (Dt) which is based on the Peclet number (Pe). This new relationship indicates a nonlinear dependency on the flow velocity (nu a) and grain size (d), namely a relative decrease of the dispersion coefficient with increasing flow velocity in relatively fast flowing water: Dt/Daq=Dp/Daq+0.28(Pe)0.72 (with Pe=nu a d/Daq; Daq and Dp denote the aqueous and pore diffusion coefficients, resp.).     

Two-phase flow and transport in a single fracture-porous medium system

The prognosis for the remediation of contaminated fractured media is much worse than that for more homogeneous units. Fractures act as conduits for the flow of dense non-aqueous phase liquids (DNAPLs), while diffusion is responsible for the storage of dissolved mass in the surrounding matrix. A numerical model incorporating aqueous phase transport in a variable-aperture fracture and its surrounding matrix is developed and coupled with an existing two-phase flow model. The processes of transient two-phase flow, non-equilibrium dissolution, advective–dispersive transport in the fracture, and three-dimensional matrix diffusion are included in the model. Results from various investigations show that the DNAPL distribution is very sensitive to variations in aperture within a single fracture. Diffusion-controlled mass removal from both the matrix and from the hydraulically inaccessible zones within the fracture itself result in extremely large time frames for significant mass removal from these systems. Success in aqueous phase mass removal from the matrix is very sensitive to the effective fracture spacing. The hydraulic gradient in the fracture only affects the amount of water removed from the system, and does not greatly affect the amount of time required to remove the contaminant mass from the matrix. The ability to remove mass is somewhat sensitive to the porosity and effective matrix diffusion coefficient over the range of expected values.     

Modeling of air sparging of VOC-contaminated soil columns

Air sparging is a remediation technology currently being applied for the restoration of sites contaminated with volatile organic compounds (VOCs). Attempts have been made by various researchers to model the fate of VOCs in the gas and liquid phase during air sparging. In this study, a radial diffusion model with an air–water mass transfer boundary condition was developed and applied for the prediction of VOC volatilization from air sparging of contaminated soil columns. The approach taken was to use various parameters such as mass transfer coefficients and tortuosity factors determined previously in separate experiments using a single air channel apparatus and applying these parameters to a complex system with many air channels. Incorporated in the model, is the concept of mass transfer zone (MTZ) where diffusion of VOCs in this zone was impacted by the volatilization of VOCs at the air–water interface but with negligible impact outside the zone. The model predicted fairly well the change in the VOC concentrations in the exhaust air, the final average aqueous VOC concentration, and the total mass removed. The predicted mass removal was within 1% to 20% of the actual experimental mass removed. The results of the model seemed to suggest that air-sparged soil columns may be modeled as a composite of individual air channels surrounded by a MTZ. For a given air flow rate and air saturation, the VOC removal was found to be inversely proportional to the radius of the air channel. The approach taken provided conceptual insights on mass transfer processes during air sparging operations.     

Wind tunnel experiment of tracer gas diffusion within unstable boundary layer over coastal region

A wind tunnel experiment was carried out to simulate stack gas diffusion within an unstable atmospheric boundary layer over a coastal region. The wind tunnel floor, 4 m leeward of the entrance of the test section, was heated to 90°C over a length of 6 m in the streamwise direction, and wind tunnel experiments were performed under the flat plate condition with a prototype-to-model length scale ratio of 1200. Three similarity criteria of flow fields in the wind tunnel and in atmosphere, viz., bulk Richardson number, surface Reynolds number and the ratio of the Peclet number to the Richardson number, were considered in the wind tunnel experiment. Tracer gas was released along the coastline at a height of 10 cm, which corresponded to 120 m in height in atmosphere. The obtained wind tunnel experimental results of ground level concentration were compared with 30-min average values of the field experiments, viz., the data from the Tokai 82 field experiment. The maximum ground level concentration and its location were accurately simulated when there was close similarity between the wind tunnel and atmospheric flow conditions. The maximum concentration increased and occurred closer to the source when the level of convection was relatively stronger in atmosphere.     

Effects of reduced contaminant loading on downgradient water quality in an idealized two-layer granular porous media

The following explores the issue of how reductions in contaminant loading to plumes will effect downgradient water quality. An idealized scenario of two adjacent layers of uniform geologic media, one transmissive and the other low permeability, is considered. A high concentration source, similar to a thin DNAPL pool, is introduced in the transmissive layer immediately above the low permeability layer. While the source is active, dissolved constituents are driven along the contact by advection and into the low permeability layer by transverse diffusion. Removing the source reverses the concentration gradient between the layers, driving back diffusion of contaminants from the low permeability layer. Laboratory studies involving four contaminants demonstrate that 15 to 44% of the introduced contaminant moves into the low permeability zone (along a distance of 87 cm in a sand tank) over a period of 25 days. The greatest movement of contaminants into the low permeability zone is seen with the contaminants with the greatest sorption coefficients. A unique two-dimensional analytical solution is developed for the two-layer scenario. Processes addressed include advection; transverse dispersion; adsorption and degradation in the transmissive zones; and diffusion, adsorption, and degradation in the low permeability layer. Laboratory data agree favorably with the analytical solutions. Collectively, the laboratory results and analytical solutions provide a basis for testing other modeling approaches that can be applied to more complex problems. A set of field-scale scenarios are considered using the analytical solutions. Results indicate that improvement in water quality associated with source removal diminish with distance downgradient of the source. Furthermore, contaminant degradation and contaminant adsorption in the stagnant zone are shown to be critical factors governing the timing and magnitude of downgradient improvements in water quality. For five of six scenarios considered, observed improvements in water quality 100 m downgradient of the source fall in the range of 1 to 2 orders of magnitude 15 years after complete source removal. The sixth scenario, involving a contaminant half-life of three years and no adsorption, shows greater than three order of magnitude improvements in downgradient water quality within one year of source removal.     

Atrazine removal by ozonation processes in surface waters

Atrazine (6-chloro-N-ethyl-N'-isopropyl-1,3,5-triazinedyl-2,4-diamine) was treated with ozone alone and in combination with hydrogen peroxide or UV radiation in three surface waters. Experiments were carried out in two bubble reactors operated continuously. Variables investigated were the ozone partial pressure, temperature, pH, mass flow ratio of oxidants fed: hydrogen peroxide and ozone and the type of oxidation including UV radiation alone. Residence time for the aqueous phase was kept at 10 min. Concentrations of some intermediates, including deethylatrazine, deisopropylatrazine and deethyldeisopropylatrazine, were also followed. The nature of water, specifically the alkalinity and pH were found to be important variables that affected atrazine (ATZ) removal. Surface waters with low alkalinity and high pH allowed the highest removal of ATZ to be reached. There was an optimum hydrogen peroxide to ozone mass flow ratio that resulted in the highest ATZ removal in each surface water treated. This optimum was above the theoretical stoichiometry of the process. Therefore, to reach the maximum removal of ATZ in a O3/H2O2 process, more hydrogen peroxide was needed in the surface waters treated than in ultrapure water under similar experimental conditions. In some cases, UV radiation alone resulted in the removal of ATZ higher than ozonation alone. This was likely due to the alkalinity of the surface water. Ozonation and UV radiation processes yield different amounts of hydrogen peroxide. Combined ozonations (O3/H2O2 and O3/UV) lead to ATZ removals higher than single ozonation or UV radiation but the formation of intermediates was higher.     

Experimental study of cross-flow wet electrostatic precipitator

This paper reports development and testing of a novel cross-flow wet electrostatic precipitator (WESP), recently patented at Ohio University, that utilizes vertical columns of permeable material in the form of polypropylene ropes placed in a cross-flow configuration within a flue gas stream. The cross-flow design has large surface area, which provides scrubbing action; therefore, it has the potential for removing multiple pollutants, including particulates, gases, vapors, and mists. In this new method, the ropes are kept wet by the liquid (water) introduced from the top of the cells running downward on the ropes by capillary action, making the permeable materials act as the ground electrode for capturing particles from the flue gas. Preliminary testing has shown an efficiency of well above 80% using two cells and three sets of discharge electrodes. Since the material of construction is primarily corrosion-resistant polymeric material, both weight and cost reductions are expected from this new design.

Implications: The newly invented cross-flow WESP exhibit particulate collection efficiency of well above 80% when introduced in particulate-laden exhaust flow. This value was obtained using a two cells and three discharge electrodes configuration. The electric field strength has a substantial effect on the collection efficiency. Also, the pressure drop test results indicate that there is a potential to increase the collection area, which, in turn, will increase the collection efficiency further.     

Removal of emulsified fuel oils from brackish and pond water by dissolved air flotation with and without polyelectrolyte use: pilot-scale investigation for estuarine and near shore applications

In coastal areas, estuaries, and inland waters, dispersant use after oil spills is not allowed due to sensitivity of the ecosystems. The purpose of this study was to investigate the removal of emulsified fuel oils from brackish and pond water by dissolved air flotation (DAF) with and without use of coagulants. Experiments were conducted with a 60 L DAF system. Fuel oil-water emulsions were prepared with regular unleaded gasoline, jet fuel, and diesel fuel mixed at 1:1:1 (v/v/v) ratio. Batch and continuous runs were conducted at air pressurization of 354.6 kPa. During both batch and continuous modes, significant petroleum hydrocarbon (PHC) removal was achieved within 10 min. Coagulant addition initially increased the PHC removal by about 5-15%. However, effectiveness of the coagulant was not significant after 20 min due to breakage of the aggregates. In general, the pond water had higher PHC removal than the brackish water. With longer run times, PHC removal improved slightly and the effluent contained increasing fractions of higher molecular weight compounds indicating that PHC removal was due to both DAF and stripping processes. Results indicate that DAF process can be effective both with and without the use of coagulants for removing PHCs from brackish and pond waters.     

Modelling radionuclide transport for time varying flow in a channel network

Water flowrates and flow directions may change over time in the subsurface for a number of reasons. In fractured rocks flow takes place in channels within fractures. Solutes are carried by the advective flow. In addition, solutes may diffuse in and out of stagnant waters in the rock matrix and other stagnant water regions. Sorbing species may sorb on fracture surfaces and on the micropore surfaces in the rock matrix. We present a method by which solute particles can be traced in flowing water undergoing changes in flowrate and direction in a complex channel network where the solutes can also interact with the rock by diffusion in the rock matrix. The novelty of this paper is handling of diffusion in the rock matrix under transient flow conditions. The diffusive processes are stochastic and it is not possible to follow a particle deterministically. The method therefore utilises the properties of a probability distribution function for a tracer moving in a fracture where matrix diffusion is active. The method is incorporated in a three dimensional channel network model. Particle tracking is used to trace out a multitude of flowpaths, each of which consists of a large number of channels within fractures. Along each channel the aperture and velocity as well as the matrix sorption properties can vary. An efficient method is presented whereby a particle can be followed along the variable property flowpath. For stationary flow conditions and a network of channels with advective flow and matrix diffusion, a simple analytical solution for the residence time distribution along each pathway can be used. Only two parameter groups need to be integrated along each path. For transient flow conditions, a time stepping procedure that incorporates a stochastic Monte-Carlo like method to follow the particles along the paths when flow conditions change is used. The method is fast and an example is used for illustrative purposes. It is exemplified by a case where land rises due to glacial rebound. It is shown that the effects of changing flowrates and directions can be considerable and that the diffusive migration in the matrix can have a dominating effect on the results.     

Fate and transport of monoterpenes through soils. Part II: calculation of the effect of soil temperature, water saturation and organic carbon content

This theoretical study was performed to investigate the influence of soil temperature, soil water content and soil organic carbon fraction on the mobility of monoterpenes (C10HnOn') applied as pesticides to a top soil layer. This mobility was expressed as the amount volatilized and leached from the contaminated soil layer after a certain amount of time. For this, (slightly modified) published analytical solutions to a one dimensional, homogeneous medium, diffusion/advection/biodegradation mass balance equation were used. The required input-parameters were determined in a preceding study. Because the monoterpenes studied differ widely in the values for their physico-chemical properties, the relative importance of the various determinants also differed widely. Increasing soil water saturation reduced monoterpene vaporization and leaching losses although a modest increase was usually observed at high soil water contents. Organic matter served as the major retention domain, reducing volatilization and leaching losses. Increasing temperature resulted in higher volatilization and leaching losses. Monoterpene mobility was influenced by vertical water flow. Volatilization losses could be reduced by adding a clean soil layer on top of the contaminated soil. Detailed insight into the specific behaviour of different monoterpenes was obtained by discussing intermediate calculation results; the transport retardation factors and effective soil diffusion coefficients. One insight was that the air-water interface compartment is probably not an important partitioning domain for monoterpenes in most circumstances. The results further indicated that biodegradation is an important process for monoterpenes in soil.     

Evaluation of tritiated water diffusion through the Toarcian clayey formation of the Tournemire experimental site (France)

Through-diffusion experiments with tritiated water were performed on argillaceous samples from various zones of the Tournemire test site. It was intended to evaluate the homogeneity of the transport property of unfracturated samples and the influence of the orientation and the nature of the samples (presence of an opened fracture or a pre-existing tectonic fracture filled with calcite and pyrite). Homogeneous values of the tritiated water (HTO) effective diffusion coefficients were deduced from experiments carried out when diffusion occurred parallel to the stratigraphic bedding, with an apparent sensitivity to experimental conditions. Anisotropy was significant, De(HTO) perpendicular to the bedding being 1/3 lower than that parallel to the bedding. The observed fractures of the samples created by mechanical stress and partial dehydration during sawing and the presence of a pre-existing opened fracture did not affect the effective diffusion coefficients of tritiated water, which is probably due to the healing ability of the clayey medium during the re-saturation phases of the equilibrium steps performed prior to the diffusion experiments. On the contrary, a significant decrease of this transport parameter was induced by the occurrence of a pre-existing tectonic fracture, which was assigned to the dense structure of the filling phases.     

One-dimensional simulation of solute transfer in saturated-unsaturated porous media using the discontinuous finite elements method

A one-dimensional transport model for simulating water flow and solute transport in homogeneous-heterogeneous, saturated-unsaturated porous media is presented. The model is composed of a combination of accurate numerical algorithms for solving the nonlinear Richard's and advection-dispersion equations (ADE). The mixed form of Richard's equation is solved using a standard finite element method (FEM) with primary variable switching. The transport equation is solved using operator splitting, with the discontinuous finite element method (DFE) for discretization of the advective term. A slope limiting procedure for DFE avoids numerical instabilities but creates very limited numerical dispersion for high Peclet numbers. An implicit finite differences scheme (FD) is used for the dispersive term. The unsaturated flow and transport model (Wamos-T) is applied to a variety of rigorous problems including transient flow, heterogeneous medium and abrupt variations of velocity in magnitude and direction due to time-varying boundary conditions. It produces accurate and mass-conservative solutions for a very large range of grid Peclet numbers. The Wamos-T model is a good and robust alternative for the simulation of mass transport in unsaturated domain.     

Atrazine removal by ozonation processes in surface waters

Abstract

Atrazine (6‐chloro‐N‐ethyl‐N'‐isopropyl‐1,3,5‐triazinedyl‐2,4‐diamine) was treated with ozone alone and in combination with hydrogen peroxide or UV radiation in three surface waters. Experiments were carried out in two bubble reactors operated continously. Variables investigated were the ozone partial pressure, temperature, pH, mass flow ratio of oxidants fed: hydrogen peroxide and ozone and the type of oxidation including UV radiation alone. Residence time for the aqueous phase was kept at 10 min. Concentrations of some intermediates, including deethylatrazine, deisopropylatrazine and deethyldeisopropylatrazine, were also followed. The nature of water, specifically the alkalinity and pH were found to be important variables that affected atrazine (ATZ) removal. Surface waters with low alkalinity and high pH allowed the highest removal of ATZ to be reached. There was an optimum hydrogen peroxide to ozone mass flow ratio that resulted in the highest ATZ removal in each surface water treated. This optimum was above the theoretical stoichiometry of the process. Therefore, to reach the maximum removal of ATZ in a O₃/H₂O₂ process, more hydrogen peroxide was needed in the surface waters treated than in ultrapure water under similar experimental conditions. In some cases, UV radiation alone resulted in the removal of ATZ higher than ozonation alone. This was likely due to the alkalinity of the surface water. Ozonation and UV radiation processes yield different amounts of hydrogen peroxide. Combined ozonations (O₃/H₂O₂ and O₃/UV) lead to ATZ removals higher than single ozonation or UV radiation but the formation of intermediates was higher.