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1.
This work is focused on measuring the concentration distribution of a conservative tracer in a homogeneous synthetic porous material and in heterogeneous natural sandstone using MRI techniques, and on the use of spatially resolved porosity data to define spatially variable diffusion coefficients in heterogeneous media. The measurements are made by employing SPRITE, a fast MRI method that yields quantitative, spatially-resolved tracer concentrations in porous media. Diffusion experiments involving the migration of H(2)O into D(2)O-saturated porous media are conducted. One-dimensional spatial distributions of H(2)O-tracer concentrations acquired from experiments with the homogeneous synthetic calcium silicate are fitted with the one-dimensional analytical solution of Fick's second law to confirm that the experimental method provides results that are consistent with expectations for Fickian diffusion in porous media. The MRI-measured concentration profiles match well with the solution for Fick's second law and provide a pore-water diffusion coefficient of 1.75×10(-9)m(2)s(-1). The experimental approach was then extended to evaluate diffusion in a heterogeneous natural sandstone in three dimensions. The relatively high hydraulic conductivity of the sandstone, and the contrast in fluid density between the H(2)O tracer and the D(2)O pore fluid, lead to solute transport by a combination of diffusion and density-driven advection. The MRI measurements of spatially distributed tracer concentration, combined with numerical simulations allow for the identification of the respective influences of advection and diffusion. The experimental data are interpreted with the aid of MIN3P-D - a multicomponent reactive transport code that includes the coupled processes of diffusion and density-driven advection. The model defines local diffusion coefficients as a function of spatially resolved porosity measurements. The D(e) values calculated for the heterogeneous sandstone and used to simulate diffusive and advective transport range from 5.4×10(-12) to 1.0×10(-10)m(2)s(-1). These methods have broad applicability to studies of contaminant migration in geological materials.  相似文献   

2.
Matrix diffusion is an important transport process in geologic materials of low hydraulic conductivity. For predicting the fate and transport of contaminants, a detailed understanding of the diffusion processes in natural porous media is essential. In this study, diffusive tracer transport (iodide) was investigated in a variety of geologically different limestone and sandstone rocks. Porosity, structural and mineralogical composition, hydraulic conductivity, and other rock properties were determined. The effective diffusion coefficients were measured using the time-lag method. The results of the diffusion experiments indicate that there is a close relationship between total porosity and the effective diffusion coefficient of a rock (analogous to Archie's Law). Consequently, the tortousity factor can be expressed as a function of total porosity. The relationship fits best for thicker samples (> 1.0 cm) with high porosities (> 20%), because of the reduced influence of heterogeneity in larger samples. In general, these correlations appear to be a simple way to determine tortuosity and the effective diffusion coefficient from easy to determine rock porosity values.  相似文献   

3.
Medical X-ray computed tomography (CT) was applied to the measurement of the diffusion coefficients of heavy ions in an artificial barrier material for the disposal of nuclear wastes. Cs(+), Sr(2+), I(-), and Br(-) are the heavy ions measured and the barrier used is the water-rich gel of Wyoming montmorillonite (86.5-100 wt.% H(2)O). X-ray CT yields an inevitable artifact (beam-hardening) in the obtained images. Before the diffusion experiments, the polychromatic primary X-ray spectrum of the CT scanner was measured by a CdZnTe detector, and the effects of the artifact were examined for an aqueous CsCl solution sample. The results show that the beam-hardening artifact derived from the polychromatic photon energy distribution can be suppressed by applying a special image reconstruction method assuming the chemical composition of samples. The transient one-dimensional diffusion of heavy ions in a plastic container filled with the gel was imaged nondestructively by the X-ray CT scanner with an in-plane resolution of 0.31 mm and slice thickness of 2 mm. The results show that diffusivities decrease with increasing clay weight fraction. The degree of the diffusivity decrease was high for cations (Cs(+) and Sr(2+)) and low for anions (I(-) and Br(-)). The quantitative decomposition of the contribution of the geometrical tortuosity and of the sorption to the diffusivity was performed by subtracting the diffusivity of nonsorbing I(-) from the measured diffusivities. The results show that the contribution of the sorption is large for Cs(+), Sr(2+) and small for Br(-). Because X-ray CT allows nondestructive and quick measurements of diffusivities, the technique would be useful particularly for measuring the diffusive migration of harmful radioactive elements.  相似文献   

4.
The composition of fuels, mixed-solvent wastes and other contaminants that find their way into the subsurface are frequently chemically complex. The dispersion and diffusion characteristics of multicomponent solutions in soil have rarely been compared to equivalent single-solute systems. The purpose of this work was to examine the diffusive and dispersive transport of single- and multi-component solutions in homogeneous porous media. The miscible displacement technique was used to investigate the transport behavior of 14C-labelled 2,4-dichlorophenoxyacetic acid (2,4-D) in two materials for which sorption of 2,4-D was minimal. Comparison of breakthrough curves collected for 2,4-D in single- and multi-component solutions shows that there is little, if any, difference in transport behavior over a wide range of pore-water velocities (70, 7, 0.66 and 0.06 cm h−1). Thus, dispersivities measured with a non-sorbing single-solute solution should be applicable to multicomponent systems.  相似文献   

5.
Transport and retardation of non-sorbing tritiated water and chloride and slightly sorbing sodium was studied in Syyry area SY-KR7 mica gneiss, in altered porous tonalite and in fresh tonalite. Experiments were performed using dynamic fracture and crushed rock column methods. Static batch method for sodium was introduced to compare retardation values from static and dynamic experiments. The 14C-PMMA method was used to study the pore structure of matrices. The pore aperture distribution was evaluated from Hg-porosimetry determinations and the surface areas were determined using the B.E.T. method. The flow characteristics and transport behavior of tracers were interpreted using a numerical compartment model for dispersion. The effect of matrix diffusion was calculated using an analytical solution to the advection-matrix diffusion problem in which surface retardation was taken into account. Radionuclide transport behavior in rock fractures was explained on the basis of rock structure.  相似文献   

6.
Pore-scale processes govern fundamental behavior in multiphase porous media systems. A high-resolution, three-dimensional image of the interior of a multiphase porous media system was obtained using synchrotron X-ray tomography. The system was imaged at a resolution of 12.46 mum following entrapment of the nonwetting phase at residual saturation. First, the physically representative network structure of the porous media system is extracted from the void space. This provides a direct mapping of the pore bodies and throats and enables pore-level calculations of coordination numbers, aspect ratios, and pore body and throat correlations. Next, algorithms developed to calculate properties of the entrapped nonwetting phase, such as volume, sphericity, interfacial area, and orientation, are applied to the residual nonwetting phase blobs. Finally, correlations between the pore network structure and nonwetting phase characteristics are examined. As expected, it was found that the nonwetting phase was trapped primarily in the largest pore spaces, the pore bodies with the highest aspect ratios, and the pore bodies with the highest coordination numbers. This work shows that, while there may be limitations related to the ability to capture REV-sized domains for some of the multiphase flow properties and phenomena, high-resolution X-ray tomography is able to provide the high quality datasets needed to observe and quantify the pore-scale phenomena and processes that govern multiphase flow in unconsolidated porous media systems.  相似文献   

7.
Transverse dispersion is the most relevant process in mass transfer of contaminants across the capillary fringe (both directions), dilution of contaminants, and mixing of electron acceptors and electron donors in biodegrading groundwater plumes. This paper gives an overview on literature values of transverse vertical dispersivities alpha(tv) measured at different flow velocities and compares them to results from well-controlled laboratory-tank experiments on mass transfer of trichloroethene (TCE) across the capillary fringe. The measured values of transverse vertical dispersion in the capillary fringe region were larger than in fully saturated media, which is credited to enhanced tortuosity of the flow paths due to entrapped air within the capillary fringe. In all cases, the values observed for alpha(tv) were < 1 mm. The new measurements and the literature values indicate that alpha(tv) apparently declines with increasing flow velocity. The latter is attributed to incomplete diffusive mixing at the pore scale (pore throats). A simple conceptual model, based on the mean square displacement and the pore size accounting for only partial diffusive mixing at increasing flow velocities, shows very good agreement with measured and published data.  相似文献   

8.
Measurements have been made of diffusion coefficients (D(i)=-mass flux/concentration gradient) using a double reservoir, steady-state method with two tracers, CaBr(2) and amino-G-acid, on intact samples of Triassic red-bed sandstone from northwest England. Diffusibility (D'=D(i)/diffusion coefficient in water) averages 0.124, ranging between 0.075 and 0.215 (porosity 0.1 to 0.24), very similar for the two tracers. Implied tortuosities (actual path length/straight line length) average 1.21 (range 1.06 to 1.47), with constrictivities close to 1. In comparison with limited red-bed sandstone data from elsewhere, these D' values are up to 4 times greater, and tortuosity correspondingly lower. Re-interpretation of formation factor data from previous studies on shallow sandstone samples also from northwest England confirms that diffusibility is significantly higher in these sandstones than others from similar palaeoenvironment/stratigraphic units. The lower tortuosities appear to result from the relatively high permeability, open fabric of the rock, properties likely to be present in shallow sandstone systems used for water supply. It is concluded that diffusion rates may, in some shallow freshwater-containing continental sandstone systems, be significantly greater than is implied by estimates of sandstone diffusibility current in the literature.  相似文献   

9.
Transport experiments with colloids and radionuclides in a shear zone were conducted during the Colloid and Radionuclide Retardation experiment (CRR) at Nagra's Grimsel Test Site. Breakthrough curves of bentonite colloids and uranine, a non-sorbing solute, were measured in an asymmetric dipole flow field. The colloid breakthrough is earlier than that of uranine. Both breakthrough curves show anomalously long late time tails and the slope of the late time tails for the colloids is slightly higher. Anomalous late time tails are commonly associated with matrix diffusion processes; the diffusive interaction of solutes transported in open channels with the adjacent porous rock matrix or zones of stagnant water. The breakthrough curves for different colloid size classes are very similar and show no signs of fractionation due to their (size-dependent) diffusivity. It is proposed that tailing of the colloids is mainly caused by the structure of the flow field and that for the colloid transport, matrix diffusion is of minor importance. This has consequences for the interpretation of the uranine breakthrough. Comparisons of experimental results with numerical studies and with the evaluation of the colloid breakthrough with continuous time random theory imply that the tailing in the conservative solute breakthrough in this shear zone is not only caused by matrix diffusion. Part of the tailing can be attributed to advective transport in fracture networks and advection in low velocity regions. Models based on the advection-dispersion equation and matrix diffusion do not properly describe the temporal and spatial evolution of colloid and solute transport in such systems with a consistent set of parameters.  相似文献   

10.
Abstract

The wood charcoal treated by 1N HNO3 (WCT) was used to remove toxic chlorinated pesticide lindane (y‐HCH) residue from water by the sorption process. Using a simple first order reversible kinetics constants and half time equations, the film and pore diffusion coefficients were determined. Film diffusion was found to be rate limiting step in sorbing lindane by WCT. This was further authenticated by kinetics studies at different initial sorbate concentrations, different sorbent sizes, and different agitation speeds besides interruption test. A pore diffusion model was used to fit the data of kinetics in continuously mixed batch reactors (CMBR), and the tortuosity, external resistance, and surface diffusion effects on lindane sorption by WCT were noticed. The tortuosity values of 15 to 28 were obtained for WCT‐lindane system.  相似文献   

11.
Abstract

Activated carbons are well-known porous materials as an effective adsorbent used for the removal of emerging contaminants, such as herbicides, which are increasingly present in water bodies. Most water treatment plants, specially in Brazil, are unable to completely remove such contaminants by the conventional process and advanced treatment using activated carbons is required. The aim of this paper was to verify the influence of the activated carbons granulometry and specific surface area on the 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide removal efficiency using distilled-deionized water and filtered water collected from a conventional Water Treatment Plant. Commercial activated carbons samples used in this work were obtained from two different manufacturers. Activated carbons were analyzed by the specific surface area, pore size and volume distribution, nuclear magnetic resonance, infrared and x-ray spectroscopy, moisture, volatile matter and ash contents. Batch adsorption isotherms experiments were used and performed by Langmuir and Freundlich models. Granular and powdered activated carbons removed over 99% of 2,4-D in distilled water and near to 99% using filtered water. The activated carbons evaluated in this work presented high performance and played a key role in water treatment by removing 2,4-D herbicide, ensuring the protection of human health and the ecosystem.  相似文献   

12.
The spreading of concentration fronts in dynamic column experiments conducted with a porous, aggregated soil is analyzed by means of a previously documented transport model (DFPSDM) that accounts for longitudinal dispersion, external mass transfer in the boundary layer surrounding the aggregate particles, and diffusion in the intra-aggregate pores. The data are drawn from a previous report on the transport of tritiated water, chloride, and calcium ion in a column filled with Ione soil having an average aggregate particle diameter of 0.34 cm, at pore water velocities from 3 to 143 cm/h. The parameters for dispersion, external mass transfer, and internal diffusion were predicted for the experimental conditions by means of generalized correlations, independent of the column data. The predicted degree of solute front-spreading agreed well with the experimental observations. Consistent with the aggregate porosity of 45%, the tortuosity factor for internal pore diffusion was approximately equal to 2. Quantitative criteria for the spreading influence of the three mechanisms are evaluated with respect to the column data. Hydrodynamic dispersion is thought to have governed the front shape in the experiments at low velocity, and internal pore diffusion is believed to have dominated at high velocity; the external mass transfer resistance played a minor role under all conditions. A transport model such as DFPSDM is useful for interpreting column data with regard to the mechanisms controlling concentration front dynamics, but care must be exercised to avoid confounding the effects of the relevant processes.  相似文献   

13.
In a previous study, column experiments were carried out with Toyoura sand (permeability 2.05×10(-11)m(2)) and Toyoura sand mixed with bentonite (permeability 9.96×10(-13)m(2)) to obtain the molecular diffusion coefficient, the Knudsen diffusion coefficient, the tortuosity for the molecular diffusion coefficient, and the mechanical dispersion coefficient of soil-gas systems. In this study, we conducted column experiments with field soil (permeability 2.0×10(-13)m(2)) and showed that the above parameters can be obtained for both less-permeable and more-permeable soils by using the proposed method for obtaining the parameters and performing column experiments. We then estimated dispersivity from the mechanical dispersion coefficients obtained by the column experiments. We found that the dispersivity depended on the mole fraction of the tracer gas and could be represented by a quadratic equation.  相似文献   

14.
ABSTRACT

A major route for transport of volatile organic compounds within porous media is vapor phase diffusion. The diffusion rate through a porous medium is less than that through free-air due to the decreased cross-sectional area available for gas movement and the increased path length due to pore tortuosity. Numerous empirical expressions have been published that relate the diffusion coefficient in porous media to the diffusion coefficient in free-air (unobstructed gas phase). Published measurements of relative diffusivity and air-filled porosity were combined into a database. Empirical expressions available in the literature, including the popular Millington-Quirk equation, were evaluated along with a fourth-degree polynomial expression developed by the authors to determine the best type of equation to predict relative diffusivity as a function of air-filled porosity over the domain of values for porosity ranging from 0.071 to 1 for different types of materials. Mean square deviations were used as the statistical test to compare equations. The polynomial expression developed in this project produced a significantly different effective diffusion coefficient (1.3 x 10-6 m2/sec) compared to values of 9.2 x 10-6 m2/sec and 3.1 x 10-6 m2/ sec predicted by forms of the Millington-Quirk equation for a specific case.  相似文献   

15.
The fumigant 1,3-dichloropropene (1,3-D) is considered to be a potential replacement for methyl bromide when methyl bromide is phased out in 2005. This study on surface emissions and subsurface diffusion of 1,3-D in a Florida sandy soil was conducted in field beds with or without plastic covers. After injection of the commercial fumigant Telone II by conventional chisels to field beds at 30cm depth which were covered with polyethylene film (PE), virtually impermeable film, or no cover (bare), (Z)- and (E)-1,3-D rapidly diffused upward. Twenty hours after injection, majority of (Z)- and (E)-1,3-D had moved upward from 30 cm depth to the layer of 5-20 cm depth. Downward movement of the two isomers in the beds with or without a plastic cover was not significant. (Z)-1,3-D diffused more rapidly than (E)-1,3-D. Virtually impermeable films (VIF) had a good capacity to retain (Z)- and (E)-1,3-D in soil pore air space. Vapor concentrations of the two isomers in the shallow subsurface of the field bed covered with VIF were greater than that in the two beds covered with polyethylene film (PE) or no cover (bare). In addition, VIF cover provided more uniform distribution of (Z)- and (E)-1,3-D in shallow subsurface than PE cover or no cover. Virtually impermeable film also had a better capability to retard surface emissions of the two isomers from soil in field beds than PE cover or no cover.  相似文献   

16.
This paper investigates the dissolution characteristics of ternary nonaqueous phase liquid (NAPL) mixtures with the goal of comparing the relative contributions of multicomponent (intra-NAPL) diffusion, film transfer and thermodynamic nonideality. These contributions are compared at the pore scale and intermediate scale (several centimeters downstream from the source). Trichloroethene (TCE), tetrachloroethene (PCE) and 1,1,1-trichloroethane (TCA) were selected to model a reasonably ideal mixture; TCE, PCE and octanol were selected as a relevant nonideal mixture. A multicomponent diffusion-based dissolution model incorporating hydrodynamic theory was formulated to estimate intra-NAPL concentration gradients and associated aqueous interfacial concentrations for ideally shaped (spherical) NAPL blobs. Pore scale dissolution times for this model were compared to those generated using the conventional well-mixed NAPL dissolution model, applying the same film transfer boundary condition in both cases. Activity coefficients (spatially and temporally variable for the diffusion model, temporally variable for the well-mixed model) were estimated using UNIFAC. NAPL interfacial concentration histories generated using the pore scale models were used as input in a three-dimensional groundwater transport model (MT3DMS) to compare downstream concentration distributions. For the relatively large NAPL bodies simulated (r=0.6 cm), intra-NAPL diffusion effects were found to be significant at the pore scale and were strongly impacted by the mixture's thermodynamic ideality. At the intermediate scale, and for the conditions tested, modest differences in the simulations suggested that intra-NAPL diffusion effects would be negligible compared to those associated with mixture composition uncertainty, dissolution rate processes related to NAPL-induced permeability effects and hydrodynamic issues associated with flow field heterogeneity.  相似文献   

17.
The measurement of diffusive properties of low-permeability rocks is of interest to the nuclear power industry, which is considering the option of deep geologic repositories for management of radioactive waste. We present a simple, non-destructive, constant source in-diffusion method for estimating one-dimensional pore diffusion coefficients (D(p)) in geologic materials based on X-ray radiography. Changes in X-ray absorption coefficient (Deltamicro) are used to quantify changes in relative concentration (C/C(0)) of an X-ray attenuating iodide tracer as the tracer solution diffuses through the rock pores. Estimated values of D(p) are then obtained by fitting an analytical solution to the measured concentration profiles over time. Measurements on samples before and after saturation with iodide can also be used to determine iodide-accessible porosity (phi(I)). To evaluate the radiography method, results were compared with traditional steady-state through-diffusion measurements on two rock types: shale and limestone. Values of D(p) of (4.8+/-2.5)x10(-11) m(2).s(-1) (mean+/-standard deviation) were measured for samples of Queenston Formation shale and (2.6+/-1.0)x10(-11) m(2).s(-1) for samples of Cobourg Formation limestone using the radiography method. The range of results for each rock type agree well with D(p) values of (4.6+/-2.0)x10(-11) m(2).s(-1) for shale and (3.5+/-1.8)x10(-11) m(2).s(-1) for limestone, calculated from through-diffusion experiments on adjacent rock samples. Low porosity (0.01 to 0.03) and heterogeneous distribution of porosity in the Cobourg Formation may be responsible for the slightly poorer agreement between radiography and through-diffusion results for limestones. Mean values of phi(I) for shales (0.060) and limestones (0.028) were close to mean porosity measurements made on bulk samples by the independent water loss technique (0.062 and 0.020 for shales and limestones, respectively). Radiography measurements offer the advantage of time-saving for diffusion experiments because the experiment does not require steady-state conditions and also allows for visualization of the small-scale heterogeneities in diffusive properties within rocks at the mm to cm scale.  相似文献   

18.
This work focuses on the phenomenon of the immiscible two-phase flow of water and oil in saturated heterogeneous soil columns. The goal is to develop a fast and reliable method for quantifying soil heterogeneities for incorporation into the relevant capillary pressure and relative permeability functions. Such data are commonly used as input data in simulators of contaminant transport in the subsurface. Rate-controlled drainage experiments are performed on undisturbed soil columns and the transient response of the axial distribution of water saturation is determined from electrical measurements. The transient responses of the axial distribution of water saturation and total pressure drop are fitted with the multi-flowpath model (MFPM) where the pore space is regarded as a system of parallel paths of different permeability. The MFPM enables us to quantify soil heterogeneity at two scales: the micro-scale parameters describe on average the effects of pore network heterogeneities on the two-phase flow pattern; the macro-scale parameters indicate the variability of permeability at the scale of interconnected pore networks. The capillary pressure curve is consistent with that measured with mercury intrusion porosimetry over the low pressure range. The oil relative permeability increases sharply at a very low oil saturation (< 10− 3) and tends to a high end value. The water relative permeability decreases abruptly at a low oil saturation (~ 0.1), whereas the irreducible wetting phase saturation is quite high. The foregoing characteristics of the two-phase flow properties are associated with critical (preferential) flowpaths that comprise a very small percentage of the total pore volume, control the overall hydraulic conductivity, and are consistent with the very broad range of pore-length scales usually probed in soil porous matrix.  相似文献   

19.
The measurement of diffusive gels in thin films (DGT) has recently been developed to assess metal bioavailability in soils. The DGT-method is based on diffusion in a porous matrix. To test the predictive capabilities of the method with regard to metal bioavailability, a study was set up with 28 soils having a variety of textures and amounts of zinc salts added. Correlation and regression analyses were performed to compare DGT-extracted zinc levels to zinc concentrations obtained by extraction with 0.01 M CaCl(2) and 0.43 M HNO(3), digestion with aqua regia and the zinc concentration in pore water. The amount of zinc extracted with CaCl(2) correlated well with DGT-extracted zinc levels in all soils spiked with different amounts of ZnCl(2). A similar correlation was not found for zinc concentrations in soil samples collected in the field. Experiments were performed to compare zinc content in organisms and in soils. The organisms tested were plants (grass, lettuce and lupine) and the hard bodied soil dwelling isopod Oniscus asellus. Good correlations were found between zinc accumulation in grass and lettuce and the C(E) (effective concentration) measured by a DGT-device, CaCl(2) extracted zinc and the zinc content in the pore water of all soils. The correlation with C(E) was not significant for lupine, neither for spiked soils, nor for field soils (p< or =0.001). Zinc levels in the isopods were not significantly related to any set of zinc measurements. From a synthesis of all results obtained it is concluded that the DGT-methodology does not have an additional value in predicting bioavailability of zinc in terrestrial ecosystems as compared to conventional extraction methods.  相似文献   

20.
Abstract

The fumigant 1,3-dichloropropene (1,3-D) is considered to be a potential replacement for methyl bromide when methyl bromide is phased out in 2005. This study on surface emissions and subsurface diffusion of 1,3-D in a Florida sandy soil was conducted in field beds with or without plastic covers. After injection of the commercial fumigant Telone II by conventional chisels to field beds at 30 cm depth which were covered with polyethylene film (PE), virtually impermeable film, or no cover (bare), (Z)- and (E)-1,3-D rapidly diffused upward. Twenty hours after injection, majority of (Z)- and (E)-1,3-D had moved upward from 30 cm depth to the layer of 5–20 cm depth. Downward movement of the two isomers in the beds with or without a plastic cover was not significant. (Z)-1,3-D diffused more rapidly than (E)-1,3-D. Virtually impermeable films (VIF) had a good capacity to retain (Z)- and (E)-1,3-D in soil pore air space. Vapor concentrations of the two isomers in the shallow subsurface of the field bed covered with VIF were greater than that in the two beds covered with polyethylene film (PE) or no cover (bare). In addition, VIF cover provided more uniform distribution of (Z)- and (E)-1,3-D in shallow subsurface than PE cover or no cover. Virtually impermeable film also had a better capability to retard surface emissions of the two isomers from soil in field beds than PE cover or no cover.  相似文献   

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