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.     

Influence of surfactant sorption on the removal of phenanthrene from contaminated soils

Laboratory column flushing experiments were conducted to remove phenanthrene from contaminated soils by Triton X-100 (TX100) with an aim to investigating the effect of surfactant sorption on the performance of surfactant-enhanced remediation process. The effluent concentration of phenanthrene from soil columns showed strong dependence on the sorption breakthrough curves of TX100. The removal of phenanthrene from contaminated soils was enhanced only when the sorption breakthrough of TX100 occurred and the influent concentration of TX100 was greater than the critical enhanced flushing concentration (CEFC). The sorption of surfactant onto soils and the subsequent partitioning of contaminants into soil-sorbed surfactant had a significant effect on the solute equilibrium distribution coefficient (KD) and thus the flushing efficiency for phenanthrene. A model was developed to predict KD and CEFC values for simulating the performance of surfactant-enhanced flushing for contaminated soils. These results are of practical interest in developing effective and safe surfactant-enhanced remediation technologies.     

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.     

Effects of SOM, surfactant and pH on the sorption-desorption and mobility of prometryne in soils

Sorption and desorption of the herbicide prometryne in two types of soil subjected to the changes of pH and soil organic matter and surfactant were investigated. The sorption and desorption isotherms were expressed by the Freundlich equation. Freundlich K_f and n values indicate that soil organic matter was the major factor affecting prometryne behavior in the test soils. We also quantified the prometryne sorption and desorption behavior in soils, which arose from the application of Triton X-100 (TX100), a nonionic surfactant and change in pH. Application of TX100 led to a general decrease in prometryne sorption to the soils and an increase in desorption from the soils when applied in dosages of the critical micella concentration (CMC) 0.5, 1 and 2. At the concentration below the CMC, the non-ionic surfactant showed a tendency to decrease prometryne sorption and desorption. It appeared that TX100 dosages above CMC were required to effectively mobilize prometryne. Results indicate that the maximum prometryne sorption and minimum prometryne desorption in soils were achieved when the solution pH was near its pK_a. Finally, the influence of TX100 on the mobility of prometryne in soils using soil thin-layer chromatography was examined.     

Solubilization of DNAPLs by mixed surfactant: reduction in partitioning losses of nonionic surfactant

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.     

蓖麻油衍生微乳液对菲的增溶和洗脱作用及其对菲污染土壤的修复机理

比较研究了蓖麻油硫酸盐(SCOS)与普通表面活性剂Triton X-100(TX100)、Tween 80(TW80)、Brij35、十二烷基苯磺酸钠(SDBS)和十二烷基硫酸钠(SDS)等对菲的增溶和洗脱作用.结果表明,菲表观溶解度与SCOS的浓度呈单一线性关系,SCOS微乳液对菲的增溶比SR=0.0314为最大,菲在微乳相和水相之间的分配系数logKem=4.44,大于菲在胶束相和水相之间的分配系数(logKmc).1:10土-水体系下,SCOS微乳液对菲污染土壤的清洗速率最快,清洗效率最高.SCOS有望成为土壤有机污染淋洗修复的增效试剂.     

Surfactant-induced mobilisation of trace metals from estuarine sediment: implications for contaminant bioaccessibility and remediation

The mobilisation of metals (Al, Fe, Cd, Cu, Mn, Ni, Pb, Sn, Zn) from contaminated estuarine sediment has been examined using commercially available surfactants. Metal release by the anionic surfactant, sodium dodecyl sulphate (SDS), increased with increasing amphiphile concentration up to and above its critical micelle concentration (CMC). Metal mobilisation by the bile acid salt, sodium taurocholate, and the nonionic surfactant, Triton X-100, however, did not vary with amphiphile concentration. SDS was the most efficient surfactant in mobilising metals from the sample, and Cd, Cu and Ni were released to the greatest extents (12-18% of total metal at [SDS] > CMC). Metal mobilisation appeared to proceed via complexation with anionic amphiphiles and denudation of hydrophobic host phases. Surfactants may play an important role in the solubilisation of metals in the digestive environment of deposit-feeding animals and, potentially, in the remediation of metal-contaminated soil and sediment.     

Synergistic solubilization of polycyclic aromatic hydrocarbons by mixed anionic-nonionic surfactants

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.     

Influence of anionic, cationic and nonionic surfactants on adsorption and desorption of oxytetracycline by ultrasonically treated and non-treated multiwalled carbon nanotubes

High adsorption capacity of carbon nanotubes (CNTs) may greatly determine the bioavailability and mobility of organic contaminants. The fate of contaminants adsorbed by CNTs may be substantially influenced by surfactants used both in the synthesis and dispersion of CNTs. The aim of this research was to determine the influence of surfactants (nonionic - TX100, cationic - CTAB and anionic - SDBS) on adsorption and desorption of oxytetracycline (OTC) by multiwalled carbon nanotubes (MWCNTs). The surfactants used had a substantial influence on both adsorption and desorption of OTC. The direction of changes depended clearly on the type of surfactant. In case of anionic SDBS, increased adsorption of OTC by MWCNTs was observed. The presence of TX100 and CTAB decreased the adsorption of OTC by MWCNTs significantly. The increase of OTC adsorption after ultrasonic treatment was observed in case of MWCNTs alone and MWCNTs with SDBS and TX100. However, ultrasonic treatment caused OTC adsorption decrease in the presence of CTAB. The change of pH had also an important effect on OTC adsorption in the presence of surfactants. Depending on the surfactant and pH, an increase or decrease of OTC adsorption was observed. The presence of surfactants increased OTC desorption from MWCNTs significantly as follows: SDBS = CTAB < TX100. The results obtained suggest new potential threats and constitute a basis for further research considering the bioavailability and toxicity of antibiotics in the presence of MWCNTs and surfactants.     

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.     

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.     

胶团强化超滤法(MEUF)去除废水中氯苯的研究

研究了3种单一表面活性剂十二烷基硫酸钠(SDS)、十六烷基三甲基溴化铵(CTMAB)、聚氧乙烯失水山梨脂肪酸酯醇醚(TW80)和混合表面活性剂TW80-SDS对氯苯(CB)的强化超滤,以期为有机废水胶团强化超滤技术提供参考。结果表明,进料液静置时间对去除率无显著影响,而振荡时间在1 h后对去除率影响不大。氯苯的去除率随进料液中表面活性剂浓度的增大而增大,单一的表面活性剂对氯苯的去除效果顺序为TW80CTMABSDS,且表面活性剂对氯苯的去除效果与表面活性剂的临界胶束浓度值(CMC)、亲水-亲油平衡值(HLB)呈负相关。阴-非混合表面活性剂TW80-SDS对氯苯的去除效果明显强于单一的SDS,且去除率随着非离子表面活性剂质量分数的增加而增加。渗透通量随着进料液中表面活性剂浓度的增加而下降,单一表面活性剂种类对渗透通量的影响顺序为SDSTW80CTMAB,混合表面活性剂中随着非离子表面活性剂质量分数的增加而渗透液的渗透通量越低。     

表面活性剂对黄土中石油污染物的解吸影响研究

研究了用表面活性剂去除黄土中柴油类污染物。选用阴离子表面活性剂十二烷基苯磺酸钠和十二烷基硫酸钠 (LAS和SDS)和阳离子表面活性剂十六烷基三甲基溴化铵 (CTAB)对污染的土壤进行解吸实验 ,表明阴离子表面活性剂浓度从 0 .1%增加到 1.0 %时 ,其柴油的去除率可达 2 0 % ,而阳离子表面活性剂去除作用不甚明显。利用摩尔增溶比MSR值求得LAS和SDS的logKm 值为 4.5 5 2和 3 .63 0 ,这和理论的计算值很接近     

Soil remediation: humic acids as natural surfactants in the washings of highly contaminated soils

The remediation of the highly contaminated site around the former chemical plant of ACNA (near Savona) in Northern Italy is a top priority in Italy. The aim of the present work was to contribute in finding innovative and environmental-friendly technology to remediate soils from the ACNA contaminated site. Two soils sampled from the ACNA site (A and B), differing in texture and amount and type of organic contaminants, were subjected to soil washings by comparing the removal efficiency of water, two synthetic surfactants, sodium dodecylsulphate (SDS) and Triton X-100 (TX100), and a solution of a natural surfactant, a humic acid (HA) at its critical micelle concentration (CMC). The extraction of pollutants by sonication and soxhlet was conducted before and after the soil washings. Soil A was richer in polycyclic aromatic hydrocarbons, whereas soil B had a larger content of thiophenes. Sonication resulted more analytically efficient in the fine-textured soil B. The coarse-textured soil A was extracted with a general equal efficiency also by soxhlet. Clean-up by water was unable to exhaustively remove contaminants from the two soils, whereas all the organic surfactants revealed very similar efficiencies (up to 90%) in the removal of the contaminants from the soils. Hence, the use of solutions of natural HAs appears as a better choice for soil washings of highly polluted soils due to their additional capacity to promote microbial activity, in contrast to synthetic surfactants, for a further natural attenuation in washed soils.     

TiO2 photocatalytic degradation of PCBs in soil-water systems containing fluoro surfactant

Titanium dioxide-mediated photodegradation of Polychlorinated biphenyls (PCBs) in soil/aqueous systems with added fluorinated surfactant was investigated. PCBs can bind tightly to organic matter in the soil, especially in aged, contaminated soil. Experiments showed an effective PCB photocatalytic degradation in mixed systems of soil/clay with anionic fluorinated surfactant FC-143 and TiO2. The FC-143 surfactant is stable in this photochemical process. PCB degradation rates in samples followed the order: spiked clay > spiked soil > Hudson River bank soil. The results suggest that anionic fluorinated surfactant may form semimicelles and/or admicelles on the surface of positively charged TiO2. The hydrophobic surface of TiO2 can provide a nonpolar phase that acts as a partioning medium for hydrophobic PCBs. Therefore, PCBs in soil can be released to the semimicelle and/or admicelle on the TiO2 surface and are effectively photodegraded in a dispersion containing anionic fluorinated surfactant. The combination of surfactant extraction and photooxidation forms the basis for a novel two-stage process for the removal and destruction of PCBs from soil.     

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.     

Influence of synthetic surfactants on the uptake of Pd, Cd and Pb by the marine macroalga, Ulva lactuca

Uptake of Pd, Cd and Pb by the marine macroalga, Ulva lactuca, has been studied in the presence of an anionic (sodium dodecyl sulphate, SDS), cationic (hexadecyltrimethylammonium bromide; HDTMA) and non-ionic (Triton X-100; TX) surfactant. Compared with the surfactant-free system, metal sorption was reduced in the presence of SDS or TX. Neither surfactant, however, had any measurable impact on cell membrane permeability, determined by leakage of dissolved free amino acids (DFAA), or on metal internalisation. We attribute these observations to the stabilisation of aqueous Cd and Pb by SDS and the shielding of otherwise amenable sorption sites by TX. Presence of HDTMA resulted in a reduction in the extent of both sorption and internalisation of all metals and a significant increase in the leakage of DFAA. Thus, by enhancing membrane permeability, HDTMA exerts the greatest influence on metal behaviour in the presence of U. lactuca.     

Effects of surfactants on extraction of phenanthrene in spiked sand

Problems associated with polynuclear aromatic hydrocarbon (PAH) contaminated site in environmental media have received increasing attention. To resolve such problems, innovative in situ methods are urgently required. This work investigated the feasibility of using surfactants to extract phenanthrene on spiked sand in a batch system. Phenanthrene was spiked into Ottawa sand to simulate contaminated soil. Six surfactants, Brij 30 (BR), Triton X-100 (TR), Tergitol NP-10 (TE), Igepal CA-720 (IG), sodium dodecyl sulfate (SDS) and hexadecyl trimethyl ammonium bromide (HTAB) were used. Adjusting the extraction time, mixing speed and surfactant concentration yielded the optimum extracting conditions. The concentration of phenanthrene was identified with HPLC. Under the experimental conditions, results indicated that those surfactants were highly promising on site remediation since the residual phenanthrene concentration was effectively reduced. The optimum operating conditions were obtained at 30 min, 125 rpm and surfactant concentrations in 4%.     

Joint influence of surfactants and humic matter on PAH solubility. Are mixed micelles formed?

Mobilization of polycyclic aromatic hydrocarbons (PAH) by surfactants, present at contaminated sites or deliberately introduced for remediation purposes, is inevitably associated with the influence of humic substances, which are ubiquitous in natural systems. Therefore, the solubilizing effects of anthropogenic and natural amphiphiles must be considered in their combined action since synergistic or antagonistic effects may be expected, for instance, as a consequence of mixed micellization.

In this paper, solubilization of ¹⁴C-labeled pyrene in single-component and mixed solutions of surfactants and humic acid (coal-derived) was investigated up to the micellar concentration range. At low concentrations, antagonistic effects were observed for systems with cationic as well as anionic surfactants. Solubility enhancements in the presence of humic acid were canceled on addition of a cationic surfactant (DTAB) since charge compensation at humic colloids entailed precipitation. Solubility was also found to be decreased in the presence of an anionic surfactant (SDS), which was attributed to a competitive effect in respect of pyrene–humic interaction. This explanation is based on octanol–water partitioning experiments with radiolabeled humic acid, yielding evidence of different interaction modes between humic colloids and cationic/anionic surfactants. At higher concentrations, the effects of humic acid and SDS were found to be additive. Thus, a formation of mixed micelles is very unlikely, which was confirmed by size exclusion chromatography of mixed systems. It can be concluded that remediation measures on the basis of micellar solubilization are not significantly affected by the presence of natural amphiphilic compounds.     

Benzene removal from waste water using aqueous surfactant two-phase extraction with cationic and anionic surfactant mixtures

A novel separation technique known as an aqueous surfactant two-phase (ASTP) extraction is a promising method to remove organic contaminants from wastewater. When cationic and anionic surfactants are mixed at certain surfactant concentrations and compositions, the solution separates into two immiscible aqueous phases. One is the surfactant-rich and the other is the surfactant-dilute phase. The organic contaminants will solubilize into the surfactant aggregates and concentrate in the small volume surfactant-rich phase. The other phase contains only small amount of surfactants and contaminants as the treated water. Most ASTP studies have used nonionic surfactants above the cloud point. Mixtures of anionic and cationic surfactants can also exhibit aqueous-aqueous phase separation and can be used in the ASTP extraction process. The phase behavior and performance of ASTP extraction using cationic surfactant dodecyltrimethylammonium bromide (DTAB) and anionic surfactant alkyldiphenyloxide di-sulfonate (DPDS) to extract benzene from wastewater was investigated in batch experiments. It was found that phase separation only occurs over a narrow range of molar ratios of DTAB:DPDS from 1.6:1 to 2.4:1. In this study, a 2:1 molar ratio of DTAB:DPDS at which there is no net charge in the surfactant aggregates show the highest extraction efficiency and lowest critical micelle concentration value with greatest synergism (highest negative values of the micellar interaction parameter). At a total surfactant concentration of 50mM, the benzene partition ratio is 48 and 72% of the benzene is extracted into the surfactant-rich phase solution in a single stage extraction, which is superior performance compared to ASTP extraction using nonionic surfactants.