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1.
Huang HL  Lee WM 《Chemosphere》2001,44(5):963-972
Surfactants can increase the solubility of non-polar compounds, and have been applied in areas such as soil washing and treatment of non-aqueous phase liquids (NAPLs). This investigation explored the feasibility of removing vapor phase polycyclic aromatic hydrocarbon (PAH) from gases using an anionic surfactant. The solubility of vapor phase naphthalene was measured herein using gas chromatograph (GC) with a photon ionization detector (PID). The measurement results indicated that surfactant molecules were not favorable to micelle formation when temperatures increased from 25 degrees C to 50 degrees C. Regardless of whether solutions were quiescent or agitated, equilibrium naphthalene apparent solubility increased linearly with surfactant concentrations exceeding critical micelle concentration (CMC). The pH effects on naphthalene apparent solubility were small. Agitation increased naphthalene apparent solubility and lumped mass transfer coefficients. Furthermore, lumped mass transfer coefficients decreased with increasing surfactant concentration owing to increase in interfacial resistance and viscosity and decreased spherical micelle diffusion coefficients. Finally, the net absorption rate increased because the solubilization effects of micelles exceeded the reduction effects of mass transfer coefficient above the CMC. The enhanced naphthalene apparent solubility from the addition of surfactant can be expressed by an enrichment factor (EF). The EF value of naphthalene for the surfactant solution at 0.1 M with agitation at 270 rpm relative to quiescent water could reach 18.6. This work confirms that anionic surfactant can improve the removal efficiency of hydrophobic organic compound (HOC) from the gas phase.  相似文献   

2.
The presence of surface-active solutes such as organic acids and bases may have a profound influence on the transport of organic liquid contaminants through their impact on the constitutive relationship of capillary pressure vs. saturation. This relationship is a function of the interfacial tension and wettability of the system, which, in turn, depend on the pH and the concentration of organic acids and bases that are present. This study examines the impact of pH and the concentration on the interfacial tension, contact angle, and capillary pressure of systems consisting of tetrachloroethylene, water, and quartz containing either octanoic acid or dodecylamine. In general, the ionic form of the solute tended to remain in the aqueous phase and reduced the capillary pressure through its impact on the interfacial tension and contact angle; on the other hand, the neutral form of the solute partitioned into the organic liquid phase and had a lesser impact on the capillary pressure for the same total mass of solute. A comparison of these data with data generated in previous research in similar systems where o-xylene was the organic liquid showed that the trends are analogous. Thus, the behavior of these two solvent systems seems to be driven primarily by the aqueous phase speciation of the solute, and the differences between the capillary pressure relationships for the two systems could be attributed to the pure system interfacial tension.  相似文献   

3.
The mass transfer of naphthalene vapor to water droplets in air was studied in the presence of ozone (O3) in the gas phase. A falling droplet reactor with water droplets of diameters 55, 91, and 182 microm was used for the study. O3 reacted with naphthalene at the air-water interface, thereby decreasing the mass transfer resistance and increasing the rate of uptake of naphthalene into the droplet. A Langmuir-Hinshelwood reaction mechanism at the air-water interface satisfactorily described the surface reaction. The first-order surface reaction rate constant, ks, increased with decreasing droplet size. Three organic intermediates were identified in the aqueous phase as a result of ozonation of naphthalene at the surface of the droplet indicating both peroxidic and nonperoxidic routes for ozonation. The presence of an organic carbon surrogate (fulvic acid) increased both the partition constant of naphthalene and the surface reaction rate of O3. The heterogeneous oxidation of naphthalene by O3 on the droplet was 15 times faster than the homogeneous oxidation by O3 in the bulk air phase, whereas it was only 0.08 times the homogeneous gas-phase oxidation by hydroxyl radicals under atmospheric conditions.  相似文献   

4.
《Chemosphere》1987,16(4):745-757
The phenomena of hydrophobic organic chemical sorption to particulate organic matter in aqueous systems are reviewed. It is speculated that the primary process is “loose sorption” in which an organic chemical reduces the total organic-water interfacial area and hence free energy by associating loosely with the natural organic surface, displacing the water from the surface and from part of the chemical. This process is easily reversible as a result of particle collisions, thus the apparent sorption partition coefficient decreases as the particle concentration and collision rate rise. Quantifying this speculated phenomenon using a mass transfer approach yields an expression for a variable partition coefficient which is in agreement with observations that a maximum of approximately half the sorbate present can be sorbed to particles. Some implications are discussed.  相似文献   

5.
Abstract

The mass transfer of naphthalene vapor to water droplets in air was studied in the presence of ozone (O3) in the gas phase. A falling droplet reactor with water droplets of diameters 55, 91, and 182 μm was used for the study. O3 reacted with naphthalene at the air-water interface, thereby decreasing the mass transfer resistance and increasing the rate of uptake of naphthalene into the droplet. A Langmuir-Hinshelwood reaction mechanism at the air-water interface satisfactorily described the surface reaction. The first-order surface reaction rate constant, ks, increased with decreasing droplet size. Three organic intermediates were identified in the aqueous phase as a result of ozonation of naphthalene at the surface of the droplet indicating both peroxidic and nonperoxidic routes for ozonation. The presence of an organic carbon surrogate (fulvic acid) increased both the partition constant of naphthalene and the surface reaction rate of O3. The heterogeneous oxidation of naphthalene by O3 on the droplet was 15 times faster than the homogeneous oxidation by O3 in the bulk air phase, whereas it was only 0.08 times the homogeneous gas-phase oxidation by hydroxyl radicals under atmospheric conditions.  相似文献   

6.
Prak DJ 《Chemosphere》2008,72(2):133-140
A key component to predicting the success of utilizing surfactants to enhance the removal of organic liquids from soil system is quantifying micellar solubilization kinetics. In this study, a flow reactor was employed to investigate the influence of surfactant ethoxylate chain length on the rates of solubilization of octane, decane, and dodecane in micellar solutions of a homologous series of purified dodecyl alcohol ethoxylates. Effluent concentration data were fit using a finite element model utilizing a linear-driving-force model to represent mass transfer at the interface. For flow rates between 0.1 and 2 ml min(-1), mass transfer coefficients ranged from 5 x 10(-8) to 7 x 10(-7)m s(-1) and did not vary in a systematic way with either solute structure or surfactant ethoxylate chain length and were lower than those found in pure water. Correlations developed for the Sherwood number based on diffusion coefficients of surfactant micelles containing organic material (organic-laden micelle) exhibit a velocity dependence similar to that found for systems based on aqueous diffusion. These results suggest that under gentle flowing conditions, the mass transfer is limited by diffusion of the organic-laden micelle. Although these trends are specific for this experimental system, the results demonstrate the importance of selecting the proper diffusion coefficient when modeling surfactant solubilization processes.  相似文献   

7.
Sorption equilibria and rates were characterized for a matrix of four aquifer sands and two slightly to moderately hydrophobic organic solutes (nitrobenzene and lindane), and the effects of sorption on the behavior of these solutes in saturated systems of the soils were determined. Experimental data were used to test and evaluate a variety of mathematical models for predicting contaminant fate and transport in groundwater systems.Observed equilibrium relationships between soil and solution phase solute concentrations were found to be described best by the nonlinear Freundlich isotherm model. It was further determined that the sorption process in the systems tested is rate controlled, requiring several days to approach equilibrium in completely mixed batch reactors. Subsequent modeling of solute transport in continuous flow soil column reactors was found to be most successful when rate-controlled models were used, the best results were obtained with a dual-resistance model incorporating the coupled mass transport steps of boundary-layer and intraparticle diffusion.  相似文献   

8.
A solute transport model that describes nonequilibrium adsorption in soil/groundwater systems by mass transfer equations for film and intraparticle diffusion is presented. The model is useful in cases where breakthrough curve spreading cannot be explained by dispersion only. To evaluate its validity, the model was applied to several data sets from column experiments. The validity was also proved by a comparison with an analytical solution for the limiting case of predominating dispersion. Furthermore, a sensitivity analysis was performed to illustrate the influence of different process and sorption parameters (pore water velocity, intraparticle mass transfer coefficient, isotherm nonlinearity) on the shape of the calculated breakthrough curves. The application of the proposed model is discussed in comparison to the widely used dispersed flow/local equilibrium model, and a relationship between both models, which is based on a lumped parameter approach, is shown.  相似文献   

9.
Soil macropore networks establish a dual-domain transport scenario in which water and solutes are preferentially channeled through soil macropores while slowly diffusing into and out of the bulk soil matrix. The influence of macropore networks on intra-ped solute diffusion and preferential transport in a soil typical of subsurface-drained croplands in the Midwestern United States was studied in batch- and column-scale experiments. In the batch diffusion studies with soil aggregates, the estimated diffusion radius (length) of the soil aggregates corresponded to the half-spacing of the aggregate fissures, suggesting that the intra-ped fissures reduced the diffusion impedance and preferentially allowed solutes to diffuse into the soil matrix. In the column-scale solute transport experiments, the average diffusion radius (estimated from HYDRUS-2D simulations and a first-order diffusive transfer term) was nearly double that of the batch-scale study. This increase may be attributed to a loss of pore continuity and a compounding of the small diffusion impedance through macropores at the larger scale. The column-scale solute transport experiments also suggest that two preferential networks exist in the soil. At and near soil saturation, a primary network of large macropores (possibly root channels and earthworm burrows) dominate advective transport, causing a high degree of physical and sorption nonequilibrium and simultaneous breakthrough of a nonreactive (bromide) and a reactive (alachlor) solute. As the saturation level decreases, the primary network drains, while transport through smaller macropores (possibly intra-ped features) continues, resulting in a reduced degree of nonequilibrium and separation in the breakthrough curves of bromide and alachlor.  相似文献   

10.
The effect of water content on the volatilization of nonaqueous phase liquid (NAPL) in unsaturated soils was characterized by one-dimensional venting experiments conducted to evaluate the lumped mass transfer coefficient. An empirical correlation based upon the modified Sherwood number, Peclet number, and normalized mean grain size was used to estimate initial lumped mass transfer coefficients over a range of water content. The effects of water content on the soil vapor extraction SVE process have been investigated through experimentation and mathematical modeling. The experimental results indicated that a rate-limited NAPL-gas mass transfer occurred in water-wet soils. A severe mass transfer limitation was observed at 61.0% water saturation where the normalized effluent gas concentrations fell below 1.0 almost immediately, declined exponentially from the initiation of venting, and showed long tailing. This result was attributed to the reduction of interfacial area between the NAPL and mobile gas phases due to the increased water content. A transient mathematical model describing the change of the lumped mass transfer coefficient was used. Simulations showed that the nonequilibrium mass transfer process could be characterized by the exponent beta, a parameter which described the reduction of the specific area available for NAPL volatilization. The nonequilibrium mass transfer limitations were controlled by the soil mean grain size and pore gas velocity, were well described by beta values below 1.0 at low water saturation, and were well predicted with beta values greater than 1.0 at high water saturation.  相似文献   

11.
Diffusion cell experiments were conducted to measure nonsorbing solute matrix diffusion coefficients in forty-seven different volcanic rock matrix samples from eight different locations (with multiple depth intervals represented at several locations) at the Nevada Test Site. The solutes used in the experiments included bromide, iodide, pentafluorobenzoate (PFBA), and tritiated water ((3)HHO). The porosity and saturated permeability of most of the diffusion cell samples were measured to evaluate the correlation of these two variables with tracer matrix diffusion coefficients divided by the free-water diffusion coefficient (D(m)/D*). To investigate the influence of fracture coating minerals on matrix diffusion, ten of the diffusion cells represented paired samples from the same depth interval in which one sample contained a fracture surface with mineral coatings and the other sample consisted of only pure matrix. The log of (D(m)/D*) was found to be positively correlated with both the matrix porosity and the log of matrix permeability. A multiple linear regression analysis indicated that both parameters contributed significantly to the regression at the 95% confidence level. However, the log of the matrix diffusion coefficient was more highly-correlated with the log of matrix permeability than with matrix porosity, which suggests that matrix diffusion coefficients, like matrix permeabilities, have a greater dependence on the interconnectedness of matrix porosity than on the matrix porosity itself. The regression equation for the volcanic rocks was found to provide satisfactory predictions of log(D(m)/D*) for other types of rocks with similar ranges of matrix porosity and permeability as the volcanic rocks, but it did a poorer job predicting log(D(m)/D*) for rocks with lower porosities and/or permeabilities. The presence of mineral coatings on fracture walls did not appear to have a significant effect on matrix diffusion in the ten paired diffusion cell experiments.  相似文献   

12.
Organic substrates in reactive barrier systems are often heterogeneous material mixtures with relatively large contrasts in hydraulic conductivity and porosity over short distances. These short-range variations in material properties imply that preferential flow paths and diffusion between regions of higher and lower hydraulic conductivity may be important for treatment efficiency. This paper presents the results of a laboratory column experiment where denitrification is investigated using a heterogeneous reactive substrate (sawdust mixed with sewage sludge). Displacement experiments with a non-reactive solute at three different flow rates are used to estimate transport parameters using a dual porosity non-equilibrium model. Parameter estimation from breakthrough curves produced relatively consistent values for the fraction of the porosity consisting of mobile water (β) and the mass transfer coefficient (α), with average values of 0.27 and 0.42 d(-1), respectively. The column system removes >95% of the influent nitrate at low and medium flow, but only 50-75% of the influent nitrate at high flow, suggesting that denitrification kinetics and diffusive mass transfer rates are limiting the degree of treatment at lower hydraulic residence times. Reactive barrier systems containing dual porosity media must therefore consider mass transfer times in their design; this is often most easily accommodated by adjusting flowpath length.  相似文献   

13.
Ruelle P 《Chemosphere》2000,40(5):457-512
The quantitative thermodynamic development of the mobile order and disorder theory in H-bonded liquids is extended in order to predict the partition coefficient. With respect to the classical predictive methods, the great advantage of the present approach resides in the possibility of predicting partition coefficient not only in the reference n-octanol/water partitioning system, but also in any mutually saturated two-phase system made up of two largely immiscible solvents. Constructed from the various free energy contributions encoded in the distribution process, the model furthermore provides a useful tool to understand both the origin and the factors, like the solute molar volume, that determine the partitioning of non-electrolytes between two immiscible liquid phases. From the comparison of the relative magnitude of the terms which contribute to the overall log P value, much information can also be gained concerning the variation of the partition coefficients of the same substances in different distribution systems. For example, the model has successfully been applied to the log P prediction of a number of environmentally important chemicals of varying structure, size and chemical nature in the n-octanol/water and n-hexane/water systems. Whatever the complexing or non-complexing substances studied, the hydrophobic effect always represent the driving force that rules distribution processes in the aqueous environments. As the dominant contribution to the partition coefficient in any organic/aqueous binary system, it is evidenced why hydrophobicity is usually considered to be a good measure of lipophilicity.  相似文献   

14.
At concentrations above the critical micelle concentration, surfactants can significantly enhance the solubilization of residual nonaqueous phase liquids (NAPL) and, for this reason, are the focus of research on surfactant-enhanced aquifer remediation (SEAR). As a consequence of their amphiphilic nature, surfactants may also partition to various extents between the organic and aqueous phases, thereby affecting SEAR performance. We report here on the observation and analysis of the effect of surfactant partitioning on the dissolution kinetics of residual perchloroethylene (PCE) by aqueous solutions (1000 mg/L) of the non-ionic surfactant Triton X-100 in a model porous medium. For this fluid system, batch equilibration experiments showed that the surfactant partitions strongly into the NAPL (NAPL-water partition coefficient equal to 12.5). Dynamic interfacial tension (IFT) measurements were employed to study surfactant diffusion and interfacial adsorption. The dynamic IFT measurements were consistent with partitioning of the surfactant between the two liquid phases. PCE dissolution experiments, conducted in a transparent glass micromodel using an aqueous surfactant solution, were contrasted to experiments using clean water. Surfactant partitioning was observed to delay significantly the onset of micellar solubilization of PCE, an observation reproduced by a numerical model. This effect is attributed to the reduction of surfactant concentration in the immediate vicinity of the NAPL-water interface, which accompanies transport of the surfactant into the NAPL. Accordingly, it is suggested that both the rate and the extent of diffusion of the surfactant into the NAPL affect the onset of and the driving force for micellar solubilization. While many surfactants do not readily partition in NAPL, this possibility must be considered when selecting non-ionic surfactants for the enhanced solubilization of residual chlorinated solvents in porous media.  相似文献   

15.
It is known that under unsaturated conditions, the transport of solutes can deviate from ideal advective-dispersive behaviour even for macroscopically homogeneous porous materials. Causes may include physical non-equilibrium, sorption kinetics, non-linear sorption, and the irregular distribution of sorption sites. We have performed laboratory experiments designed to identify the processes responsible for the non-ideality of radioactive Sr transport observed under unsaturated flow conditions in an Aeolian sandy deposit from the Chernobyl exclusion zone. Miscible displacement experiments were carried out at various water contents and corresponding flow rates in a laboratory model system. Results of our experiments have shown that breakthrough curves of a conservative tracer exhibit a higher degree of asymmetry when the water content decreases than at saturated water content and same Darcy velocity. It is possible that velocity variations caused by heterogeneities at the macroscopic scale are responsible for this situation. Another explanation is that molecular diffusion drives the solute mass transfer between mobile and immobile water regions, but the surface of contact between these water regions is small. At very low concentrations, representative of a radioactive Sr contamination of the pore water, sorption and physical disequilibrium dominate the radioactive Sr transport under unsaturated flow conditions. A sorption reaction is described by a cation exchange mechanism calibrated under fully saturated conditions. The sorption capacity, as well as the exchange coefficients are not affected by desaturation. The number of accessible exchange sites was calculated on the basis that the solid remained in contact with water and that the fraction of solid phase in contact with mobile water is numerically equal to the proportion of mobile water to total water content. That means that for this type of sandy soil, the nature of mineral phases is the same in advective and non-advective domains. So sorption reaction parameters can be estimated from more easily conducted saturated experiments, but hydrodynamic behaviour must be characterized by conservative tracer experiments under unsaturated flow conditions.  相似文献   

16.
The long-term management of dissolved plumes originating from a coal tar creosote source is a technical challenge. For some sites stabilization of the source may be the best practical solution to decrease the contaminant mass loading to the plume and associated off-site migration. At the bench-scale, the deposition of manganese oxides, a permanganate reaction byproduct, has been shown to cause pore plugging and the formation of a manganese oxide layer adjacent to the non-aqueous phase liquid creosote which reduces post-treatment mass transfer and hence mass loading from the source. The objective of this study was to investigate the potential of partial permanganate treatment to reduce the ability of a coal tar creosote source zone to generate a multi-component plume at the pilot-scale over both the short-term (weeks to months) and the long-term (years) at a site where there is >10 years of comprehensive synoptic plume baseline data available. A series of preliminary bench-scale experiments were conducted to support this pilot-scale investigation. The results from the bench-scale experiments indicated that if sufficient mass removal of the reactive compounds is achieved then the effective solubility, aqueous concentration and rate of mass removal of the more abundant non-reactive coal tar creosote compounds such as biphenyl and dibenzofuran can be increased. Manganese oxide formation and deposition caused an order-of-magnitude decrease in hydraulic conductivity. Approximately 125 kg of permanganate were delivered into the pilot-scale source zone over 35 days, and based on mass balance estimates <10% of the initial reactive coal tar creosote mass in the source zone was oxidized. Mass discharge estimated at a down-gradient fence line indicated >35% reduction for all monitored compounds except for biphenyl, dibenzofuran and fluoranthene 150 days after treatment, which is consistent with the bench-scale experimental results. Pre- and post-treatment soil core data indicated a highly variable and random spatial distribution of mass within the source zone and provided no insight into the mass removed of any of the monitored species. The down-gradient plume was monitored approximately 1, 2 and 4 years following treatment. The data collected at 1 and 2 years post-treatment showed a decrease in mass discharge (10 to 60%) and/or total plume mass (0 to 55%); however, by 4 years post-treatment there was a rebound in both mass discharge and total plume mass for all monitored compounds to pre-treatment values or higher. The variability of the data collected was too large to resolve subtle changes in plume morphology, particularly near the source zone, that would provide insight into the impact of the formation and deposition of manganese oxides that occurred during treatment on mass transfer and/or flow by-passing. Overall, the results from this pilot-scale investigation indicate that there was a significant but short-term (months) reduction of mass emanating from the source zone as a result of permanganate treatment but there was no long-term (years) impact on the ability of this coal tar creosote source zone to generate a multi-component plume.  相似文献   

17.
Matrix diffusion is an important process for solute transport in fractured rock, and the matrix diffusion coefficient is a key parameter for describing this process. Previous studies have indicated that the effective matrix diffusion coefficient values, obtained from a large number of field tracer tests, are enhanced in comparison with local values and may increase with test scale. In this study, we have performed numerical experiments to investigate potential mechanisms behind possible scale-dependent behavior. The focus of the experiments is on solute transport in flow paths having geometries consistent with percolation theories and characterized by multiple local flow loops formed mainly by small-scale fractures. The water velocity distribution through a flow path was determined using discrete fracture network flow simulations, and solute transport was calculated using a previously derived impulse-response function and a particle-tracking scheme. Values for effective (or up-scaled) transport parameters were obtained by matching breakthrough curves from numerical experiments with an analytical solution for solute transport along a single fracture. Results indicate that a combination of local flow loops and the associated matrix diffusion process, together with scaling properties in flow path geometry, seems to be an important mechanism causing the observed scale dependence of the effective matrix diffusion coefficient (at a range of scales).  相似文献   

18.
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   

19.
This paper introduces a new reversible-flow design for a continuously stirred reactor used to study sorption mass transfer in soil and solvent systems. The stirred reactor has potential advantages over conventional packed column or batch reactors because it isolates intraparticle sorption rate limitations from advective-dispersive transport, yet allows changes to flux through the reactor for analysis of sorption kinetics under dynamic conditions. Previously, stirred reactors have often failed due to clogging of sediment on the effluent frit. The reverse-flow backwashing design allows longer life and higher confidence in maintaining mixed conditions than previous designs. Mass transfer 'rate coefficients estimated from stirred and column experiments are compared; both techniques produced results consistent with a published correlation. The data also show that fitted sorption mass transfer coefficients can be strongly dependent on the choice of equilibrium partition coefficient (i.e. batch or first-moment derived values), and that the conventional two-site sorption kinetics model fails to accurately predict sorption mass transfer in the presence of changing solvent velocity through the reactor.  相似文献   

20.
Chao HP  Lee JF  Lee CK  Huang HC 《Chemosphere》2005,59(5):711-720
A method for predicting organic compound volatilization rates under turbulent liquid and gas conditions is developed. The reference compounds are classified according to their physico-chemical properties. The mass transfer coefficient (K(OL)) ratios for organic solutes to the reference compounds are constant for a wide range of environmental conditions, including liquid or air turbulence, or both at once. The obtained results indicate that when the environmental conditions are the same the determination of the volatilization rates is strongly dependent on the solute properties and the chemical structure. The presented method can more effectively estimate the volatilization rates of the solutes than the traditional one under various environmental conditions especially for low volatility solutes. The advantages and disadvantages of the traditional method are also discussed.  相似文献   

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