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1.
Zhao B  Zhu L  Yang K 《Chemosphere》2006,62(5):772-779
Efforts to remediate the dense nonaqueous phase liquids (DNAPLs) by mobilizing them face with risks of driving the contaminants deeper into aquifer zones. This spurs research for modifying the approach for in situ remediation. In this paper, a novel solubilization of DNAPLs by mixed nonionic and anionic surfactant, Triton X-100 (TX100) and sodium dodecylbenzene sulfonate (SDBS), was presented and compared with those by single ones. Given 1:40 phase ratio of DNAPL:water (v/v) and the total surfactant concentration from 0.2 to 10gl(-1), mixed TX100-SDBS at the total mass ratios of 3:1, 1:1 and 1:3 exhibited significant solubilization for the DNAPLs, trichloroethene (TCE), chlorobenzene (CB) and 1,2-dichlorobenzene (1,2-DCB). The solubilization extent by mixed TX100-SDBS was much larger than by single TX100 and even larger than by single SDBS at the ratios of 1:1 and 1:3, respectively. TX100 partitioning into the organic phase dictated the solubilization extent. The TX100 losses into TCE, CB and 1,2-DCB phases were more than 99%, 97% and 97% when single TX100 was used. With SDBS alone, no SDBS partitioned into DNAPLs was observed and in mixed systems, SDBS decreased greatly the partition loss of TX100 into DNAPLs. The extent of TX100 partition decreased with increasing the amount of SDBS. The mechanism for reduction of TX100 partition was discussed. TX100 and SDBS formed mixed micelles in the solution phase. The inability of SDBS to partition into DNAPLs and the mutual affinity of SDBS and TX100 in the mixed micelle controlled the partitioning of TX100 into DNAPL phase. The work presented here demonstrates that mixed nonionic-anionic surfactants would be preferred over single surfactants for solubilization remediation of DNAPLs, which could avoid risks of driving the contaminants deeper into aquifers and decrease the surfactant loss and remediation cost.  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.
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   

4.
Little is known about the environmental fate of adjuvants after application on the agricultural land. Adjuvants constitute a broad range of substances, of which solvents and surfactants are the major types. Nonionic surfactants such as alcohol ethoxylates (AEOs) and alkylamine ethoxylates (ANEOs) are typically examples of pesticide adjuvants. In view of their chemical structure this paper outlines present knowledge on occurrence, fate and effect on the aquatic and terrestrial environment of the two adjuvants: AEOs and ANEOs.Both AEOs and ANEOs are used as technical mixtures. This implies that they are not one single compound but a whole range of compounds present in different ratios. Structurally both groups of substances have a mutual core with side chains of varying lengths. Each of these compounds besides having the overall ability to distribute between different phases also possesses some single compound behaviour. This is reflected in the parameters describing the fate e.g. distribution coefficient, leaching, run-off, adsorption to soil, degradation and effects of these substances. The adsorption behaviour of ANEOs in contrast to AEOs is particularly variable and matrix dependent due to the ability of the compound to ionise at environmentally relevant pH. Probably because the compounds exceeds high soil adsorption and are easily degradable which is reflected in the low environmental concentrations generally found in monitoring studies. The compounds generally possess low potency to both terrestrial and aquatic organisms. The major environmental problem related to these compounds is the ability to enhance the mobility of other pollutants in the soil column.  相似文献   

5.
6.
本实验的目的是研究非离子型表面活性剂吐温 80 (Tween 80 )对菲的溶解及生物降解过程的影响。结果表明 ,通过吐温 80促溶 ,菲在水中的溶解度有明显的提高。在与菲共同降解的过程中 ,吐温 80亦能作为碳源被降解微生物利用。但是 ,高浓度的吐温 80对菲的降解有一定的抑制作用 ,同时在菲的降解完成后造成较高的残留表面活性剂量和微生物量  相似文献   

7.
Brigante M  Zanini G  Avena M 《Chemosphere》2008,71(11):2076-2081
The dissolution kinetics of humic acid particles has been studied in batch experiments, and the effects of monocarboxylic (formic, acetic, and propionic) acids are reported. The dissolution rate of the particles is significantly affected by the presence of monocarboxylic acids in the pH range 4–10. At pH 7, for example, propionic acid increases 30 times this dissolution rate. The capacity of increasing the dissolution rate is in the order formic acid < acetic acid < propionic acid, and this dissolving capacity of carboxylics seems to be directly related to their affinity for HA molecules located at the surface of the solid particles. The results indicate that carboxylics and related compounds may affect markedly the mobility and transport of humic substances in the environment.  相似文献   

8.
This study investigates the influence of fluctuating toluene concentrations on aerobic toluene degradation in a sandy porous medium colonized with Ralstonia pickettii PKO1. Column effluent toluene concentrations were found to increase after a temporary decrease in influent toluene concentration. Subsequent examination of the spatial gradient of toluene degradative activity in the column suggested that the observed increase in effluent toluene concentrations was attributable to an adverse effect of toluene limitation on the biodegradative activity of attached cells. The traditional Michaelis-Menten-type biodegradation equation associated with batch-measured Vmax (2.26 mg toluene/mg living cell/day) and KS (1.20 mg toluene/1) of nonstarved cells was unable to predict the observed toluene breakthrough behavior when the column had been previously exposed to no-toluene conditions. An alternative modeling approach was developed based upon the assumptions that (i) degradative activity was completely deactivated within the no-toluene exposure period (53.5 h) and (ii) a lag-phase was present prior to the subsequent reactivation of degradative activity in previously toluene-starved cells. These assumptions were independently verified by batch microbial investigations, and the modified model provided a good fit to the same observed toluene breakthrough curve. Application of single lag-time and threshold concentration values, however, failed to predict observed toluene breakthrough under different toluene exposure conditions. Results of this experimental and modeling investigation suggested that substrate exposure history, including the length of the starvation period and the level of substrate concentration, affected the induction of biodegradation in the porous medium.  相似文献   

9.
Rao P  He M 《Chemosphere》2006,63(7):1214-1221
Adsorption of anionic surfactant (sodium dodecylbenzenesulfonate, SDBS) and nonionic surfactant (an alcohol ethoxylates with 12 carbons and 9 oxyethyl groups, A12E9) mixtures, widely used as the major constituents of synthetic detergents in China and become the most common pollutants in the environment, on soils was conducted to investigate the behavior of mixed surfactants in soils. The effects of addition order and mixing ratios of two surfactants, associated with pH and ion strength in solutions, on adsorptions were considered. The results show that saturated adsorption amount of SDBS and A12E9 on soils decreased respectively when A12E9 was added into soils firstly compared with that secondly, possibly resulting from the screening of A12E9 to part adsorption sites on soils and the hydrocarbon chain-chain interactions between SDBS and A12E9. The adsorption of SDBS and A12E9 on soils was enhanced each other at pre-plateau region of isotherms. At plateau region of isotherms, the adsorption of SDBS on soils decreased with the increase of molar fraction of A12E9 in mixed surfactant solutions, while that of A12E9 increased except the molar ratio of SDBS to A12E9 0.0:1.0. With the increase of pH in mixed surfactant solutions, adsorption amount of SDBS and A12E9 on soils decreased, respectively. The reduction of ion strength in soils resulted in the decrease of adsorption amount of SDBS and A12E9 on soils, respectively.  相似文献   

10.
Remediation schemes for contaminated sites are often evaluated to assess their potential for source zone reduction of mass, or treatment of the contaminant between the source and a control plane (CP) to achieve regulatory limits. In this study, we utilize a stochastic stream tube model to explain the behavior of breakthrough curves (BTCs) across a CP. At the local scale, mass dissolution at the source is combined with an advection model with first-order decay for the dissolved plume. Field-scale averaging is then employed to account for spatial variation in mass within the source zone, and variation in the velocity field. Under the assumption of instantaneous mass transfer from the source to the moving liquid, semi-analytical expressions for the BTC and temporal moments are developed, followed by derivation of expressions for effective velocity, dispersion, and degradation coefficients using the method of moments. It is found that degradation strongly influences the behavior of moments and the effective parameters. While increased heterogeneity in the velocity field results in increased dispersion, degradation causes the center of mass of the plume to shift to earlier times, and reduces the dispersion of the BTC by lowering the concentrations in the tail. Modified definitions of effective parameters are presented for degrading solutes to account for the normalization constant (zeroth moment) that keeps changing with time or distance to the CP. It is shown that anomalous dispersion can result for high degradation rates combined with wide variation in velocity fluctuations. Implications of model results on estimating cleanup times and fulfillment of regulatory limits are discussed. Relating mass removal at the source to flux reductions past a control plane is confounded by many factors. Increased heterogeneity in velocity fields causes mass fluxes past a control plane to persist, however, aggressive remediation between the source and CP can reduce these fluxes.  相似文献   

11.
Cheng KY  Wong JW 《Chemosphere》2006,62(11):1907-1916
Batch experiments were performed to examine the desorption behavior of phenanthrene and pyrene in soil–water system in the presence of nonionic surfactant Tween 80 and dissolved organic matter (DOM) derived from pig manure or pig manure compost. Addition of 150 mg l−1 Tween 80 desorbed 5.8% and 2.1% of phenanthrene and pyrene from soil into aqueous phase, respectively, while the addition of both Tween 80 and DOM derived from pig manure compost and pig manure could further enhance the desorption of phenanthrene to 15.8% and 16.2%, respectively, and 6.4% and 10.9%, respectively, for pyrene. In addition, our finding also suggested that subsequent addition of Tween 80 into the soil–water system could further enhance PAHs desorption. The enhancement effect of the co-existence of Tween 80 and DOM was more than the additive effect of the Tween 80 and DOM individually. It is likely that the formation of DOM–surfactant complex in the soil–water system may be a possible reason to explain such desorption enhancement phenomenon. Therefore, it is anticipated that the coexistence of both Tween 80 and DOM derived from pig manure or pig manure compost in soil environment will enhance the bioavailability of PAHs as well as other hydrophobic organic contaminants (HOCs) by enhancing the desorption during remediation process.  相似文献   

12.
The partitioning tracer technique is among the DNAPL source-zone characterization methods being evaluated, while surfactant in-situ flushing is receiving attention as an innovative technology for enhanced source-zone cleanup. Here, we examine in batch and column experiments the magnitude of artifacts introduced in estimating DNAPL content when residual surfactants are present. The batch equilibrium tests, using residual surfactants ranging from 0.05 to 0.5 wt.%, showed that as the surfactant concentrations increased, the tracer partition coefficients decreased linearly for sodium hexadecyl diphenyl oxide disulfonate (DowFax 8390), increased linearly for polyoxyethylene (10) oleyl ether (Brij 97), and decreased slightly or exhibited no observable trend for sodium dihexyl sulfosuccinate (AMA 80). Results from column tests using clean sand with residual DowFax 8390 and Tetrachloroethylene (PCE) were consistent with those of batch tests. In the presence of DowFax 8390 (less than 0.5 wt.%), the PCE saturations were underestimated by up to 20%. Adsorbed surfactants on a loamy sand with positively charged oxides showed false indications of PCE saturation based on partitioning tracers in the absence of PCE. Using no surfactant (background soil) gave a false PCE saturation of 0.0004, while soil contacted by AMA 80, Brij 97, and DowFax 8390 gave false PCE saturations of 0.0024, 0.043, and 0.23, respectively.  相似文献   

13.
在用粉煤灰合成沸石分子筛的过程中,粉煤灰在碱液中的溶解影响到合成反应的速率以及合成分子筛的性能。采用碱熔的方法处理粉煤灰,研究了粉煤灰在碱液中的溶解机理以及碱熔预处理对粉煤灰溶解规律的影响,并采用Noyes-Whitney方程分析其溶解动力学。结果表明,经过碱熔预处理的粉煤灰有36.11%的SiO2和16.33%的Al2O3转化为水溶性成分,剩余的非水溶性部分在碱液中的溶解速率也有大幅提高,硅铝离子达到平衡浓度的时间缩短,铝离子的平衡浓度有较大提升。Noyes-Whitney方程对粉煤灰在碱液中的溶解规律适用,相关系数都达到0.979以上。  相似文献   

14.
Two-dimensional multiphase flow and transport simulators were refined and used to numerically investigate the entrapment and dissolution behavior of tetrachloroethylene (PCE) in heterogeneous porous media containing spatial variations in wettability. Measured hydraulic properties, residual saturations, and dissolution parameters were employed in these simulations. Entrapment was quantified using experimentally verified hydraulic property and residual saturation models that account for hysteresis and wettability variations. The nonequilibrium dissolution of PCE was modeled using independent estimates of the film mass transfer coefficient and interfacial area for entrapped and continuous (PCE pools or films) saturations. Flow simulations demonstrate that the spatial distribution of PCE is highly dependent on subsurface wettability characteristics that create differences in PCE retention mechanisms and the presence of subsurface capillary barriers. For a given soil texture, the maximum and minimum PCE infiltration depth was obtained when the sand had intermediate (an organic-wet mass fraction of 25%) and strong (water- or organic-wet) wettability conditions, respectively. In heterogeneous systems, subsurface wettability variations were also found to enhance or diminish the performance of soil texture-induced capillary barriers. The dissolution behavior of PCE was found to depend on the soil wettability and the spatial PCE distribution. Shorter dissolution times tended to occur when PCE was distributed over large regions due to an increased access of flowing water to the PCE. In heterogeneous systems, capillary barriers that produced high PCE saturations tended to exhibit longer dissolution times.  相似文献   

15.
Gao Y  Shen Q  Ling W  Ren L 《Chemosphere》2008,72(4):636-643
A greenhouse study examined plant uptake of phenanthrene and pyrene, as representatives of polycyclic aromatic hydrocarbons (PAHs), from an aqueous solution containing a nonionic surfactant Tween 80. The uptake was conducted with 1.0 mg l(-1) phenanthrene and 0.12 mg l(-1) pyrene under a wide range of Tween 80 concentrations (0-105.6 mg l(-1)). Tween 80 at the test concentrations did not show any apparent phytotoxity toward the growth of red clover (Trifolium pretense L.). At concentrations generally lower than 13.2 mg l(-1), Tween 80 enhanced the plant uptake based on the concentrations and PCFs (plant concentration factors) of these two PAHs. When present at higher concentrations, Tween 80 inhibited the uptake of both PAH compounds by the tested plant. The maximal plant uptake was observed at 6.6 mg l(-1) Tween 80, in which PAH concentrations and PCFs were 18-115% higher than those in Tween 80-free controls. The total mass removal (off-take) of phenanthrene and pyrene by root or shoot increased initially and decreased thereafter with the increase in Tween 80 concentrations. Although shoot biomass was evidently larger than root, the off-take was much higher in root than shoot because of the larger root concentrations of these chemicals. Results from this study show promises for the potential efficacy of enhanced phytoremediation in PAH contaminated sites using surfactant amendment.  相似文献   

16.
Contamination has occurred many non-indurated and bedrock systems wherein the groundwater flows almost exclusively through a network of connected, open fractures. The matrix surrounding the fractures often possesses porosity which allows contaminant diffusion into the matrix. If the diffusion rates are fast relative to the fracture groundwater velocity, transport effects may be predicted by considering the system to be an equivalent porous medium (EPM). The rapidity with which fracture/immobile-matrix equilibrium is established will be determined in part by the: fracture aperture (2b); interfracture spacing (2B); porosity in the immobile matrix im); and the matrix diffusion coefficient (D′). Two systems which are characterized by very different values of the above parameters have been studied by our laboratories. At Alkali Lake, Oregon, the EPM approach describes contaminant transport well. At Bayview Park, Ontario, the EPM approach is not appropriate. Several features of the two sites are compared to illustrate the different nature of these two sites. These features include: (1) natural characteristics of the groundwater systems; (2) contaminant distributions; (3) observed transport; and (4) computed fracture/immobile-matrix diffusion times.  相似文献   

17.
Meunier L  Koch I  Reimer KJ 《Chemosphere》2011,84(10):1378-1385
Dissolution kinetics of arsenic from soils and tailings were studied under simulated gastrointestinal conditions to determine the effects of residence time, pH and soil composition on the bioaccessibility of arsenic. The samples were sieved to four particle size fractions from bulk to <45 μm, and included arsenic minerals, soils and tailings with total arsenic concentrations ranging from 19 to 420 00 mg kg−1. The bioaccessible arsenic concentrations varied from 2.8 to 10 000 mg kg−1, and the highest concentrations were associated with the smallest particle size fractions. Kinetic parameters were determined for each sample extracted under gastric conditions (pH = 1.8) followed by intestinal conditions (pH = 7.0). Under gastric pH conditions, dissolution appeared to be diffusion-controlled and followed an exponential curve, whereas a logarithmic or linear model was used to describe the mixed dissolution mechanisms observed under intestinal conditions. Nine of the 13 samples tested reached a steady state bioaccessible arsenic concentration within the 5-h physiologically-based extraction test (PBET). However the bioaccessible arsenic concentrations in four tailings samples increased significantly (= 0.034) between the 5-h and the extended 24-h extraction under intestinal conditions. Since arsenic absorption may occur along the entire digestive tract, assessments based on the standard 5-h PBET extraction may not adequately estimate the risks associated with arsenic absorption in such cases. The slow dissolution kinetics associated with secondary arsenic minerals in some tailings samples may require extending the PBET extractions to longer periods, or extrapolating using the proposed kinetic models, to reach steady state concentrations in simulated gastrointestinal fluids.  相似文献   

18.
Effect of a cationic surfactant on the volatilization of PAHs from soil   总被引:1,自引:0,他引:1  

Purpose

Cationic surfactants are common in soils because of their use in daily cosmetic and cleaning products, and their use as a soil amendment for the mitigation and remediation of organic contaminated soils has been proposed. Such surfactant may affect the transfer and fate of organic contaminants in the environment. This study investigated the effect of a cationic surfactant, dodecylpyridinium bromide (DDPB), on the volatilization of polycyclic aromatic hydrocarbons (PAHs) from a paddy soil.

Materials and methods

The volatilization of PAHs from moist soil amended with different concentrations of DDPB was tested in an open system. The specific effects of DDPB on the liquid?Cvapor and solid?Cvapor equilibriums of PAHs were separately investigated in closed systems by headspace analysis.

Results and discussion

DDPB affects both liquid?Cvapor and solid?Cvapor processes of PAHs in soil. At DDPB concentrations below the critical micelle concentration (CMC), movement of PAHs from the bulk solution to the gas?Cliquid interface appeared to be facilitated by interaction between PAHs and the surfactant monomers adsorbed at the gas?Cliquid interface, promoting the volatilization of PAHs from solution. However, when DDPB was greater than the CMC, volatilization was inhibited due to the solubilization of PAHs by micelles. On the other hand, the formation of sorbed surfactant significantly inhibited the solid?Cvapor volatilization of PAHs.

Conclusions

The overall effect of the two simultaneous effects of DDPB on liquid?Cvapor and solid?Cvapor processes was a decreased volatilization loss of PAHs from soil. Inhibition of PAH volatilization was more significant for the soil with a lower moisture content.  相似文献   

19.
Computational simulations of two-phase flow in porous media are used to investigate the feasibility of replacing a porous medium containing heterogeneities with an equivalent homogeneous medium. Simulations are performed for the case of infiltration of a dense nonaqueous phase liquid (DNAPL) in a water-saturated, heterogeneous porous medium. For two specific porous media, with periodic and rather simple heterogeneity patterns, the existence of a representative elementary volume (REV) is studied. Upscaled intrinsic permeabilities and upscaled nonlinear constitutive relationships for two-phase flow systems are numerically calculated and the effects of heterogeneities are evaluated. Upscaled capillary pressure-saturation curves for drainage are found to be distinctly different from the lower-scale curves for individual regions of heterogeneity. Irreducible water saturation for the homogenized medium is found to be much larger than the corresponding lower-scale values. Numerical simulations for both heterogeneous and homogeneous representations of the considered porous media are carried out. Although the homogenized model simulates the spreading behavior of DNAPL reasonably well, it still fails to match completely the results form the heterogeneous simulations. This seems to be due, in part, to the nonlinearities inherent to multiphase flow systems. Although we have focussed on a periodic heterogeneous medium in this study, our methodology is applicable to other forms of heterogeneous media. In particular, the procedure for identification of a REV, and associated upscaled constitutive relations, can be used for randomly heterogeneous or layered media as well.  相似文献   

20.
The biotransformation and mineralization of a mixture of two polycyclic aromatic hydrocarbons (PAHs), anthracene and pyrene, which are known contaminants of soil and groundwater, by an enrichment culture in the presence or absence of 100 mg l(-1) Tergitol NP-10, a non-ionic surfactant, and at temperatures of 10 degrees C and 25 degrees C were investigated. The overall biotransformation of 2 mg l(-1) total PAHs with free cell suspensions in batch culture was greater than 97.2% at both examined temperatures. At 25 degrees C, the overall mineralization of anthracene was 48.8% and that of pyrene was 66.1%. However, the decrease of temperature to 10 degrees C had a negative effect on the mineralization of PAHs and reduced it to 18.5% and 61.5% for anthracene and pyrene, respectively. Using a higher PAHs concentration of 20 mg l(-1) at 25 degrees C, the overall biotransformation of anthracene was 80.7% and that of pyrene was 100%, where only 17.3% anthracene and 7.6% pyrene were mineralized to carbon dioxide and water. The addition of surfactant at 25 degrees C increased the overall mineralization of anthracene and pyrene to 33.0% and 27.6%, respectively. However, the addition of surfactant at 10 degrees C had a negative impact on the overall biotransformation of anthracene and pyrene, reducing them to 20.6% and 14.0%, respectively. These results have significant implications in the bioremediation of PAHs-contaminated sites.  相似文献   

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