Solubilization of nitrotoluenes in micellar nonionic surfactant solutions

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.     

Solubilization and biodegradation of phenanthrene in mixed anionic-nonionic surfactant solutions

The effects of mixed anionic-nonionic surfactants, sodium dodecyl sulfate (SDS) mixed with Tween80 (TW80), Triton X-100 (TX100) and Brij35 respectively on the solubility enhancement and biodegradation of phenanthrene in the aqueous phase were investigated. The efficiency of solubilization and biodegradation of phenanthrene in single-, and mixed-surfactant solutions were also compared. The critical micellar concentrations (CMCs) of mixed surfactants were sharply lower than that of sole SDS. The degree of solubility enhancements by the mixed surfactants followed the order of SDS-TW80>SDS-Brij35>SDS-TX100. Synergistic solubilization was observed in the mixed surfactant solutions, in which the molar ratios of SDS to nonionic surfactant were 1:0, 9:1, 7:3, 5:5, 3:7, 1:9 and 0:1 while the total concentration of surfactants was kept at 5.0 and 10.0 mM, respectively. SDS-Brij35 exhibited more significant degree of synergistic solubility enhancement for phenanthrene. The mixed surfactants exhibited no inhibitory effect on biodegradation of phenanthrene. Substantial amounts of the solubilized phenanthrene by mixed surfactants were completely degraded by phenanthrene-degrading microorganisms within 96 h. The results suggested that anionic-nonionic surfactants would improve the performance of remediation of PAH-contaminated soils.     

Enhanced desorption of phenanthrene from contaminated soil using anionic/nonionic mixed surfactant

A new approach using an anionic/nonionic mixed surfactant, sodium dodecyl sulphate (SDS) with Triton X-100 (TX100), was utilized for the desorption of phenanthrene from an artificial contaminated natural soil in an aim to improve the efficiency of surfactant remediation technology. The experimental results showed that the presence of SDS not only reduced the sorption of TX100 onto the natural soil, but also enhanced the solubilization of TX100 for phenanthrene, both of which resulted in the distribution of phenanthrene in soil-water systems decreasing with increasing mole fraction of SDS in surfactant solutions. These results can be attributed to the formation of mixed micelles in surfactant solution and the corresponding decrease in the critical micelle concentration of TX100 in mixed solution. The batch desorption experiments showed that the desorption percentage of phenanthrene from the contaminated soil with mixed solution was greater than that with single TX100 solution and appeared to be positively related to the mole fraction of SDS in surfactant solution. Thus, the anionic/nonionic mixed surfactants are more effective for the desorption of phenanthrene from the contaminated soil than a single nonionic surfactant.     

Effect of nonionic surfactant partitioning on the dissolution kinetics of residual perchloroethylene in a model porous medium

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.     

非离子型表面活性剂吐温80增溶条件下菲的生物降解

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     

Environmental properties and effects of nonionic surfactant adjuvants in pesticides: a review

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.     

Photocatalytic demulsification of oil/water emulsions containing nonionic surfactant

Environmental Science and Pollution Research - Separation of oil-water (OW) emulsions is investigated using a photocatalytic demulsification approach. Experiments were conducted using two types of...     

Distribution of polycyclic aromatic hydrocarbons in soil-water system containing a nonionic surfactant

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.     

Adsorption of anionic and nonionic surfactant mixtures from synthetic detergents on soils

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.     

Uptake of polycyclic aromatic hydrocarbons by Trifolium pretense L. from water in the presence of a nonionic surfactant

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.     

Phenanthrene partitioning in sediment–surfactant–fresh/saline water systems

The objective of this study was to investigate the influence of salinity on the effectiveness of surfactants in the remediation of sediments contaminated with phenanthrene (PHE). This is an example of a more general application of surfactants in removing hydrophobic organic compounds (HOCs) from contaminated soil/sediment in saline environments via in-situ enhanced sorption or ex-situ soil washing. Salinity effects on surfactant micelle formation and PHE partitioning into solution surfactant micelles and sorbed surfactant were investigated. The critical micelle concentration of surfactants decreased, and PHE partition between surfactant micelles and water increased with increasing salinity. Carbon-normalized partition coefficients (K_ss) of PHE onto the sorbed cationic surfactant increased significantly with increasing salinity, which illustrates a more pronounced immobilization of PHE by cationic surfactant in a saline system. Reduction of PHE sorption by anionic surfactant was more pronounced in the saline system, indicating that the anionic surfactant has a higher soil washing effectiveness in saline systems.     

Nonionic surfactant enhanced biodegradation of m-xylene by mixed bacteria and its application in biotrickling filter

In this study, m-xylene biodegradation was examined in bacteria-water mixed solution and biotrickling filter (BTF) systems amended with the nonionic surfactant Tween 80. The mixed bacteria were obtained from the activated sludge of a coking plant through a multisubstrate acclimatization process. High-throughput sequencing analysis revealed that Rhodanobacter sp. was the dominant species among the mixed bacteria. In the bacteria-water mixed solution, the bacterial density increased with increasing Tween 80 concentration. Hence, Tween 80 could be utilized as substrate by the mixed bacteria. Tween 80, with concentrations of 50–100 mg L^?1, could enhance the bioavailability of m-xylene and consequently improve the degradation efficiency of m-xylene. However, further increasing the initial concentration of Tween 80 would decrease the degradation efficiency of m-xylene. At concentrations exceeding 100 mg L^?1, Tween 80 was preferentially degraded by the mixed bacteria over m-xylene. In BTF systems, when the m-xylene inlet concentration was 1200 mg m^?3 and the empty bed residence time was 20 sec, the removal efficiency and elimination capacity of BTF1 with Tween 80 addition were at most 20% and 24% higher than those of BTF2 without Tween 80 addition. Overall, the integrated application of the mixed bacteria and surfactant was demonstrated to be a highly effective strategy for m-xylene waste gas treatment.

Implications: The integrated application of mixed bacteria and surfactant was demonstrated to be a promising approach for the highly efficient removal of m-xylene. Surfactant can activate mixed bacteria to degrade m-xylene by increasing its bioavailability. Besides, surfactant can be utilized as carbon source by the mixed bacteria so that the growth of mixed bacteria can be promoted. It is expected that the integrated application of both technologies will become more common in future chemical industry.     

Different behaviours in the solubilization of polycyclic aromatic hydrocarbons in water induced by mixed surfactant solutions

Water solubility of polycyclic aromatic hydrocarbons (PAHs), viz, naphthalene and phenanthrene, in micellar solutions at 25 °C was investigated, using two series of different binary mixtures of anionic and nonionic surfactants. Tween 80 and Brij-35 were used as nonionic surfactants whereas fatty acids or amphiphilic cyclodextrins (Mod-β-CD) synthesized in our laboratory were used as anionic ones. Solubilization capacity has been quantified in terms of the molar solubilization ratio and the micelle-water partition coefficient, using UV-visible spectrophotometry. Anionic surfactants exhibited less solubilization capacity than nonionics. The mixtures between Tween 80 and Mod-β-CD did not show synergism to increase the solubilization of PAHs. On the other hand, the mixtures formed by Tween 80 and fatty acids at all mole fractions studied produced higher enhancements of the solubility of naphthalene than the individual surfactants. The critical micellar concentration of the mixtures of Tween 80/sodium laurate was determined by surface tension measurements and spectrofluorimetry using pyrene as probe. The system is characterized by a negative interaction parameter (β) indicating attractive interactions between both surfactants in the range of the compositions studied.     

Combined effect of nonionic surfactant Tween 80 and DOM on the behaviors of PAHs in soil--water system

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.     

Biotoxicity and bioavailability of hydrophobic organic compounds solubilized in nonionic surfactant micelle phase and cloud point system

Environmental Science and Pollution Research - A recent work has shown that hydrophobic organic compounds solubilized in the micelle phase of some nonionic surfactants present substrate toxicity to...     

Entrapment and dissolution of DNAPLs in heterogeneous porous media

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.     

Mechanism for the destruction of carbon tetrachloride and chloroform DNAPLs by modified Fenton's reagent

The destruction of a carbon tetrachloride DNAPL and a chloroform DNAPL was investigated in reactions containing 0.5 mL of DNAPL and a solution of modified Fenton's reagent (2M H2O2 and 5mM iron(III)-chelate). Carbon tetrachloride and chloroform masses were followed in the DNAPLs, the aqueous phases, and the off gasses. In addition, the rate of DNAPL destruction was compared to the rate of gas-purge dissolution. Carbon tetrachloride DNAPLs were rapidly destroyed by modified Fenton's reagent at 6.5 times the rate of gas purge dissolution, with 74% of the DNAPL destroyed within 24h. Use of reactions in which a single reactive oxygen species (hydroxyl radical, hydroperoxide anion, or superoxide radical anion) was generated showed that superoxide is the reactive species in modified Fenton's reagent responsible for carbon tetrachloride DNAPL destruction. Chloroform DNAPLs were also destroyed by modified Fenton's reagent, but at a rate slower than the rate of gas purge dissolution. Reactions generating a single reactive oxygen species demonstrated that chloroform destruction was the result of both superoxide and hydroxyl radical activity. Such a mechanism of chloroform DNAPL destruction is in agreement with the slow but relatively equal reactivity of chloroform with both superoxide and hydroxyl radical. The results of this research demonstrate that modified Fenton's reagent can rapidly and effectively destroy DNAPLs of contaminants characterized by minimal reactivity with hydroxyl radical, and should receive more consideration as a DNAPL cleanup technology.     

Solubilization of substituted indole compounds by beta-cyclodextrin in water

The solubilization of four pairs of substituted indole compounds (SICs) by β-cyclodextrin (β-CD) in water was investigated. The results show that 1,2,3,4-tetrahydrocarbazole and N-methyl-1,2,3,4-tetrahydrocarbazole form 1:1 inclusion complexes with β-CD, while the other six SICs form 1:2 inclusion complexes, respectively. To each pair of SICs with similar structures, the differences between their solubilization in β-CD/water solutions has been explained by the difference of their contact area within the β-CD cavity, the difference of their molecule polarity, or the presence of hydrogen bond between SIC molecule and β-CD molecule.     

Selection of surfactant in remediation of DDT-contaminated soil by comparison of surfactant effectiveness

With an aim to select the most appropriate surfactant for remediation of DDT-contaminated soil, the performance of nonionic surfactants Tween80, TX-100, and Brij35 and one anionic surfactant sodium dodecyl benzene sulfonate (SDBS) in enhancement of DDT water solubility and desorption of DDT from contaminated soil and their adsorption onto soil and ecotoxicities were investigated in this study. Tween80 had the highest solubilizing and soil-washing ability for DDT among the four experimental surfactants. The adsorption loss of surfactants onto soil followed the order of TX-100 > Tween80 > Brij35 > SDBS. The ecotoxicity of Tween80 to ryegrass (Lolium perenne L.) was lowest. The overall performance considering about the above four aspects suggested that Tween80 should be selected for the remediation of DDT-contaminated soil, because Tween80 had the greatest solubilizing and soil-washing ability for DDT, less adsorption loss onto soil, and the lowest ecotoxicity in this experiment.     

原位热处理技术修复重质非水相液体污染场地研究进展

重质非水相液体(DNAPLs)是土壤及地下水中广泛存在的有机污染物,原位热处理技术是目前修复受DNAPLs污染土壤及地下水的最具潜力的技术之一。综述了国内外常用原位热处理技术的基本原理及其影响因素,介绍了相关现场应用实例,并展望了该技术未来的应用前景和发展趋势,以期为中国污染土壤及地下水的原位修复提供有益借鉴。