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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.
Prak DJ 《Chemosphere》2007,68(10):1961-1967
A key factor in selecting surfactants to enhance chemical or biological transformation or physical removal of an organic pollutant from contaminated soil is knowledge of the pollutant's solubility behavior in the surfactant solution. This study investigated the influence of nonionic surfactant structure on the solubility of 4-nitrotoluene (NT), 2,3-dinitrotoluene, 2,4-dinitrotoluene, 2,6-dinitrotoluene, and 2,4,6-trinitrotoluene (TNT) at room temperature. For a series of alkyl phenol ethoxylates (Tergitol NP-8 to NP-40), decreasing the ethoxylate chain length increased the solubility of these nitrotoluenes by a factor of two or less in 10 g l(-1) surfactant solutions, but did not significantly change their molar solubilization ratios (MSR, e.g. 0.02 for TNT) or their micelle-water partition coefficients (K(m), e.g. 3.4 for TNT). For Tergitol NP-8 solutions ranging from 1.0 to 12.4 g l(-1), no enhancement in NT solubility was found, suggesting that the cloud point was reached. The MSRs for Tween 80 were higher than those of Tween 20 and the MSRs of Brij-58 were higher than those for Brij-35. When comparing solutes, NT had the highest solubility and MSR (0.28-0.41), while TNT had the lowest solubility and MSR (0.02-0.03). A linear relationship between K(m) values and octanol-water partition coefficients based on Triton X-100 predicted the logK(m) values within 0.5 of their measured values. A linear solvation free energy correlation for K(m) suggested the importance of solute volume and effective hydrogen bond basicity in the partitioning process while implying that the nitrotoluenes are solubilized in a polar portion of the micelle.  相似文献   

3.
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   

4.
A matrix of batch, column and two-dimensional (2-D) box experiments was conducted to investigate the coupled effects of rate-limited solubilization and layering on the entrapment and subsequent recovery of a representative dense NAPL, tetrachloroethylene (PCE), during surfactant flushing. Batch experiments were performed to determine the equilibrium solubilization capacity of the surfactant, polyoxyethylene (20) sorbitan monooleate (Tween 80), and to measure fluid viscosity, density and interfacial tension. Results of one-dimensional column studies indicated that micellar solubilization of residual PCE was rate-limited at Darcy velocities ranging from 0.8 to 8.2 cm/h and during periods of flow interruption. Effluent concentration data were used to develop effective mass transfer coefficient (Ke) expressions that were dependent upon the Darcy velocity and duration of flow interruption. To simulate subsurface heterogeneity, 2-D boxes were packed with layers of F-70 Ottawa sand and Wurtsmith aquifer material within 20-30 mesh Ottawa sand. A 4% Tween 80 solution was then flushed through PCE-contaminated boxes at several flow velocities, with periods of flow interruption. Effluent concentration data and visual observations indicated that both rate-limited solubilization and pooling of PCE above the fine layers reduced PCE recovery to levels below those anticipated from batch and column measurements. These experimental results demonstrate the potential impact of both mass transfer limitations and subsurface layering on the recovery of PCE during surfactant enhanced aquifer remediation.  相似文献   

5.
A numerical model of surfactant enhanced solubilization was developed and applied to the simulation of nonaqueous phase liquid recovery in two-dimensional heterogeneous laboratory sand tank systems. Model parameters were derived from independent, small-scale, batch and column experiments. These parameters included viscosity, density, solubilization capacity, surfactant sorption, interfacial tension, permeability, capillary retention functions, and interphase mass transfer correlations. Model predictive capability was assessed for the evaluation of the micellar solubilization of tetrachloroethylene (PCE) in the two-dimensional systems. Predicted effluent concentrations and mass recovery agreed reasonably well with measured values. Accurate prediction of enhanced solubilization behavior in the sand tanks was found to require the incorporation of pore-scale, system-dependent, interphase mass transfer limitations, including an explicit representation of specific interfacial contact area. Predicted effluent concentrations and mass recovery were also found to depend strongly upon the initial NAPL entrapment configuration. Numerical results collectively indicate that enhanced solubilization processes in heterogeneous, laboratory sand tank systems can be successfully simulated using independently measured soil parameters and column-measured mass transfer coefficients, provided that permeability and NAPL distributions are accurately known. This implies that the accuracy of model predictions at the field scale will be constrained by our ability to quantify soil heterogeneity and NAPL distribution.  相似文献   

6.
Previous research has demonstrated that an anionic surfactant can increase the solubility of the vapor phases of both naphthalene and sulfur dioxide in water. This study examines the feasibility of removing polycyclic aromatic hydrocarbons (PAHs) during gas absorption by adding the polyoxyethylenated nonionic surfactants tetraethylene glycol monodecyl ether (C10E4), octaethylene glycol monodecyl ether (C10E8), and octaethylene glycol monotetradecyl ether (C14E8), to water. The apparent solubility and absorption rates of naphthalene in surfactant solution were slightly higher than in pure water at a concentration lower than the critical micelle concentration (CMC). However, the apparent equilibrium naphthalene solubility increased linearly in proportion to the concentrations of nonionic surfactants because of the solubilization effect of micelles at concentrations above the CMC. The solubilization effect exceeded that of the reduced mass transfer coefficient, increasing the rate of absorption of vaporous naphthalene. For the four surfactants, the capacity to solubilize naphthalene was in the order C10E4 > C14E8 > C10E8 > sodium dodecyl sulfate (SDS) and was related to the hydrophile-lipophile balance values of the surfactants. The enrichment factors, which can express the degree of naphthalene solubility in solution, were 6.09-14.2 at a surfactant concentration of 0.01 M for the three polyoxyethylenated nonionic surfactants. Empirical findings confirm that adding nonionic surfactants increases the absorption efficiency of hydrophobic organic compounds (HOCs) using spray or packed tower.  相似文献   

7.
Hong L  Luthy RG 《Chemosphere》2008,72(2):272-281
Polyoxymethylene (POM) is a polymeric material used increasingly in passive sampling of hydrophobic organic contaminants such as PAHs and PCBs in soils and sediments. In this study, we examined the sorption behavior of 12 PAH compounds to POM and observed linear isotherms spanning two orders of magnitude of aqueous concentrations. Uptake kinetic studies performed in batch systems for up to 54 d with two different volume ratios of POM-to-aqueous phase were evaluated with coupled diffusion and mass transfer models to simulate the movement of PAHs during the uptake process and to assess the physicochemical properties and experimental conditions that control uptake rates. Diffusion coefficients of PAHs in POM were estimated to be well correlated with diffusants' molecular weights as D(POM) proportional, variant(MW)(-3), descending from 2.3 x 10(-10) cm(2) s(-1) for naphthalene to 7.0 x 10(-11) cm(2) s(-1) for pyrene. The uptake rates for PAHs with log K(ow)<5.8 were controlled by the POM phase and the hydrophobicity of PAH compounds. For more hydrophobic PAH compounds, the aqueous boundary layer played an increasingly important role in determining the overall mass transfer rate. The POM partitioning technique was demonstrated to agree well with two other procedures for measuring PAH soil-water distribution coefficients in oil-soot (lampblack) containing soil samples.  相似文献   

8.
Surfactant-enhanced aquifer remediation (SEAR) involves the injection of surfactant solutions into aquifers contaminated with nonaqueous phase liquids (NAPL). Batch and column experiments were used to assess the effect of surfactant formulation on the rate of NAPL solubilization. The experimental variables were surfactant type, surfactant concentration, electrolyte concentration, and cosolvent concentration. Model equations were proposed and solved to describe solubilization under the conditions of each type of experiment. Using these models, a solubilization rate constant, kappa(b), and an overall mass transfer rate coefficient, kappa, were estimated from the batch and column experiments, respectively. The solubilization rate constant was consistently sensitive to surfactant type, surfactant concentration, and electrolyte concentration. The estimated solubilization rate constants varied over two orders of magnitude. The results of the column experiments also were sensitive to the surfactant formulation. Variations in the fitted mass transfer rate coefficient parameter, beta(0), were related to variations in the surfactant formulations. A comparison between the results of the batch and column experiments yields an apparent relationship between beta(0) and kappa(b). This relationship suggests that the mass transfer rate coefficient is directly related to the formulation of the surfactant solution.  相似文献   

9.
Alcohol addition has been suggested for use in combination with surfactant flushing to enhance solubilization kinetics and permit density control of dense non-aqueous phase liquid (DNAPL)-laden surfactant plumes. This study examined the effects of adding ethanol (EtOH) to a 4% Tween 80 (polyoxyethylene (20) sorbitan monooleate) solution used to flush tetrachloroethene (PCE)-contaminated porous media. The influence of EtOH concentration, subsurface layering and scale on flushing solution delivery and PCE recovery was investigated through a combination of experimental and mathematical modeling studies. Results of batch experiments demonstrated that the addition of 2.5%, 5% and 10% (wt.) EtOH incrementally increased the PCE solubilization capacity and viscosity of the surfactant solution, while reducing solution density from 1.002 to 0.986 g/cm3. Effluent concentration data obtained from one-dimensional (1-D) column experiments were used to characterize rate-limited micellar solubilization of residual PCE, which was strongly dependent upon flow velocity and weakly dependent upon EtOH concentration. Two-dimensional (2-D) box studies illustrated that minor differences (0.008 g/cm3) between flushing and resident solution density can strongly influence surfactant front propagation. A two-dimensional multiphase simulator, MISER, was used to model the influence of EtOH composition on the aqueous flow field and PCE mass recovery. The ability of the numerical simulator to predict effluent concentrations and front propagation was demonstrated for both 1-D columns and 2-D boxes flushed with EtOH-amended Tween 80 solutions. Results of this study quantify the potential influence of alcohol addition on surfactant solution properties and solubilization capacity, and demonstrate the importance of considering small density variations in remedial design.  相似文献   

10.
Zhu L  Feng S 《Chemosphere》2003,53(5):459-467
Water solubility enhancements of naphthalene (Naph), acenaphthylene (Acen), anthracene (An), phenanthrene (Phen) and pyrene (Py) by micellar solutions of single and mixed anionic-nonionic surfactants were measured and compared. Effects of typical inorganic ions, such as NH(4)(+), Na(+) and Mg(2+) coexisted with the organic pollutants (in soils) on water solubilities of polycyclic aromatic hydrocarbons (PAHs) in the presence of single and mixed surfactants were also investigated. Solubilities of PAHs in water are greatly enhanced in a linear fashion by each of Triton X-100 (TX100), Triton X-305 (TX305), Brij 35, and sodium dodecyl sulfate (SDS). Solubility enhancement efficiencies of surfactants above the critical micelle concentration (CMC) follow the order of TX100>Brij 35>TX305>SDS. PAHs are solubilized synergistically in mixed anionic-nonionic surfactant solutions, especially at low surfactant concentrations. The synergistic power of the mixed surfactants is SDS-TX305>SDS-Brij 35>SDS-TX100. Synergistic effect of a given mixed-surfactant solution on different PAHs also appears to be linearly related to the solute logK(ow). The noted synergism for the mixed surfactants is attributed to the formation of mixed micelles, the lower CMC of the mixed-surfactant solutions, and the increase of the solute's molar solubilization ratio or micellar partition coefficients (K(mc)) because of the lower polarity of the mixed micelles. Suitable quantity of inorganic cations can enhance the solubilization capacities of anionic-nonionic mixed surfactants, the effect being Mg(2+)>NH(4)(+)>Na(+). The water solubility of pyrene was slightly increased by anthracene and significantly increased by 1,2,3-TCB in the presence of SDS-Brij 35. Mixed surfactants may improve the performance of surfactant-enhanced remediation of soils and sediments by decreasing the applied surfactant level and thus the remediation cost.  相似文献   

11.
The mass transfer rate from residual dense non-aqueous phase liquids (DNAPLs) to the mobile aqueous phase is an important parameter for the efficiency of surfactant-enhanced remediation through solubilization of this type of contamination. The mass transfer kinetics are highly dependent on the dimensionality of the system. In this study, irregularly shaped residual TCE saturations in two-dimensional saturated flow fields were flushed with a 2% polyoxyethylene sorbitan (20) monooleate (POESMO) solution until complete removal had been achieved. A numerical model was developed and used for the simulation of the various surfactant-flushing experiments with different initial saturation patterns and flow rates. Through optimization against in situ concentration and saturation data, a phenomenological power-law model for the relationship between the mass transfer rate from the DNAPL to the mobile aqueous phase on the one hand and the residual DNAPL saturation and the flow velocity on the other hand was derived. The obtained mass transfer rate parameters provide a reasonable fit to the experimental data, predicting the cleanup time and the general saturation and concentration pattern quite well but failing to predict the concentration curves at every individual sampling port. The obtained mass transfer rate model gives smaller values for the predicted mass transfer rate but shows a comparable dependence on water flow and saturation as in earlier published one-dimensional column experiments with identical characteristics for porous medium, DNAPL and surfactant. Mass transfer rate predictions were about one order of magnitude lower in the 2-D flow cell experiment than in 1-D column experiments. These results give an indication for the importance of dimensionality during surfactant remediation.  相似文献   

12.
Brix R  Hvidt S  Carlsen L 《Chemosphere》2001,44(4):759-763
The water solubility of nonylphenol (NP) has been estimated to be 4.9 +/- 0.4 mg/l corresponding to (2.22 +/- 0.18) x 10(-5) mol/l at 25 degrees C using shake flask and surface tension techniques. The low solubility in combination with an observed rather slow dissolution process will limit the leachability of NP in the terrestrial environment. Based on indirect evidence, it is suggested that NP, in contrast to nonylphenol ethoxylate (NPEO) with, e.g., 12 ethoxylate moieties, is not subject to micelle formation, and as such does not constitute a potential vehicle for the transport of hydrophobic pollutants in the environment. For NPEOs with a very high number of ethoxy moieties, e.g., 100, the compounds appear water soluble without micelle formation.  相似文献   

13.
Biodegradation rates of PAHs are typically low at mesophilic conditions and it is believed that the kinetics of degradation is controlled by PAH solubility and mass transfer rates. Solubility tests were performed on phenanthrene, fluorene and fluoranthene at 20 degrees C, 40 degrees C and 60 degrees C and, as expected, a significant increase in the equilibrium solubility concentration and of the rate of dissolution of these polycyclic aromatic hydrocarbons (PAHs) was observed with increasing temperature. A first-order model was used to describe the PAH dissolution kinetics and the thermodynamic property changes associated with the dissolution process (enthalpy, entropy and Gibb's free energy of solution) were evaluated. Further, other relevant thermodynamic properties for these PAHs, including the activity coefficients at infinite dilution, Henry's law constants and octanol-water partition coefficients, were calculated in the temperature range 20-60 degrees C. In parallel with the dissolution studies, three thermophilic Geobacilli were isolated from compost that grew on phenanthrene at 60 degrees C and degraded the PAH more rapidly than other reported mesophiles. Our results show that while solubilization rates of PAHs are significantly enhanced at elevated temperatures, the biodegradation of PAHs under thermophilic conditions is likely mass transfer limited due to enhanced degradation rates.  相似文献   

14.
In this paper, comparison is made of terms describing solubilization of hydrophobic organic compounds (HOC) by dissolved humic substances (DHS) and commercial non-ionic surfactants. This paper examines the ability of a commercial humic acid (Aldrich humic acid) to solubilize and mobilize tetrachlorothene (PCE) residual in porous media. The constant for solubilization of PCE by Aldrich humic acid is shown to be a factor of two to thirty times less than that published for dodecyl alcohol ethoxylate surfactants, showing that Aldrich humic acid is less capable than some non-ionic surfactants at solubilizing residual PCE. The depression of PCE–water interfacial tension in the presence of DHS is shown to be significantly less than published values for a non-ionic surfactant, and surfactant mixtures, indicating that the DHS used in this study is less prone to cause mobilization of non-aqueous phase liquids relative to surfactants. Several possible advantages of DHS use in the remediation of subsurface media contaminated with HOC are described, including the ability of DHS to solubilize HOC irrespective of the DHS concentration, and potential lesser tendency of DHS to depress the interfacial tension between non-aqueous phases and water relative to surfactants (an advantage when mobilization is undesired).  相似文献   

15.
16.
Because of their low solubility, waste chemicals in the form of nonaqueous phase liquids (NAPLs) that are entrapped in subsurface formations act as long-term sources of groundwater contamination. In the design of remediation schemes that use surfactants, it is necessary to estimate the mass transfer rate coefficients under multi-dimensional flow fields that exit at field sites. In this study, we investigate mass transfer under a two-dimensional flow field to obtain an understanding of the basic mechanisms of surfactant-enhanced dissolution and to quantify the mass transfer rates. Enhanced dissolution experiments in a two-dimensional test cell were conducted to measure rates of mass depletion from entrapped NAPLs to a flowing aqueous phase containing a surfactant. In situ measurement of transient saturation changes using a gamma attenuation system revealed dissolution patterns that are affected by the dimensionality of the groundwater flow field. Numerical modeling of local flow fields that changed with time, due to depletion of NAPL sources, enabled the examination of the basic mechanisms of NAPL dissolution in complex groundwater systems. Through nonlinear regression analysis, mass transfer rates were correlated to porous media properties, NAPL saturation and aqueous phase velocity. Results from the experiments and numerical analyses were used to identify deficiencies in existing methods of analysis that uses assumptions of one-dimensional flow, homogeneity of aquifer properties, local equilibrium and idealized transient mass transfer.  相似文献   

17.
Zhou W  Zhu L 《Chemosphere》2005,60(9):1237-1245
The effect of a nonionic surfactant, Triton X-100 (TX100), on the distribution of four representative polycyclic aromatic hydrocarbons (PAHs), phenanthrene, fluorene, acenaphthene and naphthalene, in soil-water system was studied on a natural soil. The apparent soil-water distribution coefficient with surfactant (Kd*) for these compounds increased when TX100 equilibrium concentration from zero to around the critical micelle concentration (CMC), followed by a decrease in Kd* at TX100 equilibrium concentration greater than CMC. This is a direct result of surfactant sorption onto soil followed by PAHs partitioning to the sorbed surfactant. The values of carbon-normalized solute distribution coefficient (Kss) with the sorbed TX100 are greater than the corresponding partition coefficients with soil organic matter (Koc), which indicates the soil-sorbed nonionic surfactant is more effective per unit mass as a partitioning medium than the native soil organic matter for PAHs. When Kd* = Kd the corresponding initial concentration of surfactant was defined as critical washing concentration (CWC). Depending on the surfactant initial concentration below or above the CWC, the addition of nonionic surfactant can enhance the retardation of soil for PAHs or promote the removal of PAHs from soil, respectively. The values of Kd* and CWC can be predicted by a model, which correlates them with the compounds' octanol-water partition coefficients (Kow), soil property and the amount of soil-sorbed surfactant.  相似文献   

18.
The efficacy of a new rhamnolipid biosurfactants mixture to enhance the removal of pyrene from a soil artificially contaminated was investigated. The molar solubilization ratio (MSR) and the partition coefficient between the micelles and water (log K(m)) were found to be 7.5 x 10(-3) and 5.7, respectively. From soil column studies, the pyrene removal increased linearly with the concentration of the injected biosurfactants solution above the effective critical micellar concentration (0.4 g L(-1)). Flushing with a 5.0 g L(-1) biosurfactants solution increased the pyrene concentration in the effluent by 178 times. At high biosurfactants' concentrations (2.5 and 5.0 g L(-1)), the cumulative pyrene recovery reached 70%. This pyrene remobilization takes place independently of the soil organic carbon solubilization. This study provides a combination of batch and column experiments in order to find the conditions for effective soil remediation using a new rhamnolipids mixture.  相似文献   

19.
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   

20.
Eighteen fungal strains were tested in toxicity assays with surfactants in order to select surfactants and strains tolerant to surfactants for degradation assays. Two nonionic surfactants were used, an alkylphenol ethoxylate, Triton X-100, a sorbitan ester, Tween 80 and an anionic surfactant, sodium dodecyl sulfate. Solubilization and biodegradation tests were conducted in liquid medium batch; fluorene was quantified by HPLC. Results showed the enhancement of fluorene solubilization by the three surfactants, good tolerance of nonionic surfactants by the fungal strains and the enhancement of the biodegradation of fluorene by Doratomyces stemonitis (46-62%) and Penicillium chrysogenum (28-61%) in the presence of Tween 80 (0.324 mM) after 2 days.  相似文献   

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