A comparison of the efficiency of different surfactants for removal of crude oil from contaminated soils

This paper presents the results from study investigating the efficiency with which different surfactants remove crude oil from contaminated soil using a soil washing process. The surfactants studied were aqueous solutions of rhamnolipid, saponin and sodium dodecyl sulfate (SDS). The efficiency of surfactants' removal was quantified and then GC/MS analysis conducted to investigate the distribution of hydrocarbons remaining on the washed soil samples compared to those on a control. The results showed that SDS removed the most crude oil from soil, followed by rhamnolipid and then saponin. However, the different surfactants showed preferences in terms of which crude oil components they removed from the contaminated soil. SDS removed more of the aliphatics than aromatic hydrocarbons whereas saponin removed the aromatic hydrocarbon preferentially to the aliphatic hydrocarbons. Clearly these results provide important information for the selection of surfactants used to remove crude oil from contaminated soils.     

Conditions for effective removal of pyrene from an artificially contaminated soil using Pseudomonas aeruginosa 57SJ rhamnolipids

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.     

Crude oil contaminated soil washing in air sparging assisted stirred tank reactor using biosurfactants

This study investigated the removal of crude oil from soil using air sparging assisted stirred tank reactors. Two surfactants (rhamnolipid and sodium dodecyl sulfate, SDS) were tested and the effects of different parameters (i.e. temperature, surfactant concentrations, washing time, volume/mass ratio) were investigated under varying washing modes namely, stirring only, air sparging only and the combination of stirring and air sparging. The results showed that SDS removed more than 80% crude oil from non-weathered soil samples, whilst rhamnolipid showed similar oil removal at the third and fourth levels of the parameters tested. The oil removal ability of the seawater prepared solutions were better than those of the distilled water solutions at the first and second levels of temperature and concentration of surfactant solutions. This approach of soil washing was noted to be effective in reducing the amount of oil in soil. Therefore we suggested that a field scale test be conducted to assess the efficiency of these surfactants.     

Influence of cation type, ionic strength, and pH on solubilization and mobilization of residual hydrocarbon by a biosurfactant

This study investigated the effect of cation type, ionic strength, and pH on the performance of an anionic monorhamnolipid biosurfactant for solubilization and removal of residual hexadecane from sand. Three common soil cations, Na⁺, Mg²⁺, and Ca²⁺, were used in these experiments and hexadecane was chosen to represent a nonaqueous phase liquid (NAPL) less dense than water. Results showed that hexadecane solubility in rhamnolipid solution was significantly increased by the addition of Na⁺ and Mg²⁺. Addition of up to 0.2 mM Ca²⁺ also increased hexadecane solubility. For Ca²⁺ concentrations greater than 0.2 mM there was little effect on hexadecane solubility due to competing effects of calcium-induced rhamnolipid precipitation and enhanced hexadecane solubilization. Efficiency of NAPL solubilization can be expressed in terms of molar solubilization ratios (MSR). The results showed that MSR values for hexadecane in rhamnolipid solutions increased 7.5-fold in the presence of 500 mM Na⁺, and 25-fold in the presence of 1 mM Mg²⁺. The presence of cations also reduced the interfacial tension between rhamnolipid solutions and hexadecane. For example, an increase in Na⁺ from 0 to 800 mM caused a decrease in interfacial tension from 2.2 to 0.89 dyn cm⁻¹. Similarly, decreasing pH caused a reduction in interfacial tension. The lowest interfacial tension value observed in this study was 0.02 dyn cm⁻¹ at pH 6 in the presence of 320 mM Na⁺. These conditions were also found to be optimal for removal of hexadecane residual from sand columns, with 58% of residual removed within three pore volumes. The removal of residual NAPL from the packed columns was primarily by mobilization, even though solubilization was significantly increased in the presence of Na⁺.     

不同洗脱剂对有机氯农药污染场地土壤修复效果比较

为了筛选出能有效修复有机氯农药污染土壤的洗脱剂,选取了16种洗脱剂对2种复合有机氯农药(六六六(HCHs)和滴滴涕(DDTs)、氯丹和灭蚁灵)污染场地土壤进行超声洗脱修复。结果表明,对于HCHs和DDTs复合污染土壤,乙酸乙酯和丙酮对HCHs的洗脱率最高,分别为87.6%和87%,其余有机溶剂对其洗脱率也在70%以上。乙酸乙酯和丙酮对于DDT仍为最优,分别为86.9%与78.4%,其余有机试剂对DDT的洗脱率在60%以上。相对于有机溶剂,表面活性剂对HCHs和DDTs复合污染土壤的洗脱效果不好,总洗脱率均低于4%。同样,对于氯丹和灭蚁灵复合污染土壤,有机溶剂的洗脱效果也明显优于表面活性剂。有机溶剂对灭蚁灵的洗脱率,除了正丙醇较低(63.5%)外,其余均在80%左右。对氯丹的洗脱率,除石油醚(59.6%)、正己烷(49.3%)和正丙醇(42%),其余均在70%以上。相同摩尔浓度的表面活性剂中,吐温80对氯丹的洗脱率为54%,环糊精为20%,鼠李糖脂和曲拉通100为13%左右,其余则小于5%,吐温80对灭蚁灵的洗脱率为29.6%,曲拉通100的为12.4%,鼠李糖脂为5.7%,其余则更低。因此,高效低毒的有机试剂,如乙酸乙酯、丙酮和乙醇等可作为有机氯农药污染土壤修复的首选。     

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     

鼠李糖脂协助下的土壤中镉电动修复

实验研究了重金属Cd在生物表面活性剂鼠李糖脂协助下的电动修复过程,通过不同方式、不同浓度、不同酸碱度的鼠李糖脂溶液的添加与空白处理对比,探讨了鼠李糖脂协助下电动修复过程中的Cd在土壤介质中的迁移转化和机理,分析了鼠李糖脂溶液作为电动修复添加剂的可行性。结果表明,中等浓度酸性的鼠李糖脂溶液(pH=4.78,浓度为0.5、1和2 g/L)能对土壤中的重金属Cd进行有效的富集,富集量均在初始值的4倍以上,且其可交换态比重均大于42.07%,非常有利于土壤进行二次修复。此外,以pH=4.78,浓度为0.5 g/L的鼠李糖脂溶液作为预处理剂的Ex-08中的重金属Cd并未出现富集现象,但其对重金属的Cd的总去除效率达到了49.27%。表明利用鼠李糖脂溶液作为电动修复添加剂进行土壤重金属修复是可行的。     

Utilization of a biosurfactant foam/nanoparticle mixture for treatment of oil pollutants in soil

Oil contamination has become a primary environmental concern due to increased exploration, production, and use. When oil enters the soil, it may attach or adsorb to soil particles and stay in the soil for an extended period, contaminating the soil and surrounding areas. Nanoparticles have been widely used for the treatment of organic pollutants in the soil. Surfactant foam has effectively been employed to remediate various soil contaminants or recover oil compounds. In this research, a mixture of biosurfactant foam/nanoparticle was utilized for remediation of oil-contaminated soil. The results demonstrated that the biosurfactant/nanoparticle mixture and nitrogen gas formed high-quality and stable foams. The foam stability depended on the foam quality, biosurfactant concentration, and nanoparticle dosage. The pressure gradient change in the soil column relied on the flowrate (N₂ gas + surfactant/nanoparticle mixture), foam quality, and biosurfactant concentration. The optimal conditions to obtain good quality and stable foams and high oil removal efficiency involved 1 vol% rhamnolipid, 1 wt% nanoparticle, and 1 mL/min flowrate. Biosurfactant foam/nanoparticle mixture was effectively used to remediate oil-contaminated soil, whereas the highest treatment efficiency was 67%, 59%, and 52% for rhamnolipid biosurfactant foam/nanoparticle, rhamnolipid biosurfactant/nanoparticle, and only rhamnolipid biosurfactant, respectively. The oil removal productivity decreased with the increase of flowrate due to the shorter contact time between the foam mixture and oil droplets. The breakthrough curves of oil pollutants in the soil column also suggested that the foam mixture’s maximum oil treatment efficiency was higher than biosurfactant/nanoparticle suspension and only biosurfactant.

     

Removal of polycyclic aromatic hydrocarbons from manufactured gas plant-contaminated soils using sunflower oil: laboratory column experiments

Laboratory column experiments were performed to remove PAHs (polycyclic aromatic hydrocarbons) from two contaminated soils using sunflower oil. Two liters of sunflower oil was added to the top of the columns (33 cm x 21 cm) packed with 1 kg of PAH-contaminated soil. The sunflower oil was applied sequentially in two different ways, i.e. five additions of 400 ml or two additions of 1l. The influence of PAH concentration and the volume of sunflower oil on PAH removal were examined. A soil respiration experiment was carried out and organic carbon contents of the soils were measured to determine degradability of remaining sunflower oil in the soils. Results showed that the sunflower oil was effective in removing PAHs from the two soils, more PAHs were removed by adding sunflower oil in two steps than in five steps, probably because of the slower flow rate in the former method. More than 90% of total PAHs was removed from a heavily contaminated soil (with a total 13 PAH concentration of 4721 mg kg(-1)) using 4 l of sunflower oil. A similar removal efficiency was obtained for another contaminated soil (with a total 13 PAH concentration of 724 mg kg(-1)), while only 2l was needed to give a similar efficiency. Approximately 4-5% of the sunflower oil remained in the soils. Soil respiration curves showed that remaining sunflower oil was degraded by allowing air exchange and supplying with nutrients. Organic carbon content of the soil was restored to original level after 180 d incubation. These results indicated that the sunflower oil had a great capacity to remove PAHs from contaminated soils, and sunflower oil solubilization can be an alternative technique for remediation of PAH contaminated soils.     

Efficiency of lipopeptide biosurfactants in removal of petroleum hydrocarbons and heavy metals from contaminated soil

This study describes the potential application of lipopeptide biosurfactants in removal of petroleum hydrocarbons and heavy metals from the soil samples collected from industrial dumping site. High concentrations of heavy metals (like iron, lead, nickel, cadmium, copper, cobalt and zinc) and petroleum hydrocarbons were present in the contaminated soil samples. Lipopeptide biosurfactant, consisting of surfactin and fengycin was obtained from Bacillus subtilis A21. Soil washing with biosurfactant solution removed significant amount of petroleum hydrocarbon (64.5 %) and metals namely cadmium (44.2 %), cobalt (35.4 %), lead (40.3 %), nickel (32.2 %), copper (26.2 %) and zinc (32.07 %). Parameters like surfactant concentration, temperature, agitation condition and pH of the washing solution influenced the pollutant removing ability of biosurfactant mixture. Biosurfactant exhibited substantial hydrocarbon solubility above its critical micelle concentration. During washing, 50 % of biosurfactant was sorbed to the soil particles decreasing effective concentration during washing process. Biosurfactant washed soil exhibited 100 % mustard seed germination contradictory to water washed soil where no germination was observed. The results indicate that the soil washing with mixture of lipopeptide biosurfactants at concentrations above its critical micelle concentration can be an efficient and environment friendly approach for removing pollutants (petroleum hydrocarbon and heavy metals) from contaminated soil.     

鼠李糖脂对不同菌株降解柴油污染物的影响

通过一系列实验分析了鼠李糖脂对柴油污染物生物降解的影响。单菌株柴油降解实验结果表明,在添加生物表面活性剂鼠李糖脂后,各菌株细胞表面疏水性均发生不同程度的增加,并且对柴油的降解率均有所提高。在混合菌的柴油污染物降解实验中,发现当向土壤中添加了200 mg/L鼠李糖脂时,对柴油的降解才有较大的提高;而当添加100 mg/L的鼠李糖脂到水体中时,对柴油的降解就有较大的提高,而当鼠李糖脂浓度提高为200 mg/L时,柴油的降解率却没有进一步明显的提高。这说明鼠李糖脂对柴油降解的影响程度不仅与环境介质有关,还与添加的鼠李糖脂浓度有关。进一步分析表明,添加适当浓度的鼠李糖脂不仅可以提高对柴油的降解率,而且可加速其降解速度,缩短生物修复所需时间。     

Biosurfactant technology for remediation of cadmium and lead contaminated soils

This research focuses on column experiments conducted to evaluate the potential of environmentally compatible rhamnolipid biosurfactant produced by Pseudomonas aeruginosa strain BS2 to remove heavy metals (Cd and Pb) from artificially contaminated soil. Results have shown that di-rhamnolipid removes not only the leachable or available fraction of Cd and Pb but also the bound metals as compared to tap water which removed the mobile fraction only. Washing of contaminated soil with tap water revealed that approximately 2.7% of Cd and 9.8% of Pb in contaminated soil was in freely available or weakly bound forms whereas washing with rhamnolipid removed 92% of Cd and 88% of Pb after 36 h of leaching. This indicated that di-rhamnolipid selectively favours mobilization of metals in the order of Cd>Pb. Biosurfactant specificity observed towards specific metal will help in preferential elution of specific contaminant using di-rhamnolipid. It was further observed that pH of the leachates collected from heavy metal contaminated soil column treated with di-rhamnolipid solution was low (6.60-6.78) as compared to that of leachates from heavy metal contaminated soil column treated with tap water (pH 6.90-7.25), which showed high dissolution of metal species from the contaminated soil and effective leaching of metals with treatment with biosurfactant. The microbial population of the contaminated soil was increased after removal of metals by biosurfactant indicating the decrease of toxicity of metals to soil microflora. This study shows that biosurfactant technology can be an effective and nondestructive method for bioremediation of cadmium and lead contaminated soil.     

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.     

Soil contamination by crude oil: impact on the mycorrhizosphere and on the revegetation potential of forest trees

In vitro and greenhouse biotests were carried out to study the effects of various concentrations of crude oil on the mycorrhizosphere and the ability of ectomycorrhizal fungi to colonise Norway spruce and poplar seedlings grown on contaminated soil. Ectomycorrhizal fungi grown in pure cultures showed a variety of reactions to crude oil, ranging from growth stimulation to total inhibition of growth, depending on the species of fungi. Germination of poplar and spruce seeds was not significantly affected. The growth of spruce seedlings was not affected by crude oil, whereas that of poplar seedlings was significantly reduced at high concentrations. None of the concentrations had any effect on the degree of ectomycorrhizal and endomycorrhizal colonisation of poplar. With spruce, however, the ectomycorrhizal fungi showed species-specific reactions to increasing concentrations, in accordance with the results of the pure culture test. The length of time between soil contamination and seeding affects both seedling growth and the mycorrhizal infection potential of the soil. The results confirm the importance of mycorrhizal fungi in the bioremediation of soils contaminated by crude oil.     

Solvent extraction for heavy crude oil removal from contaminated soils

A new strategy of heavy crude oil removal from contaminated soils was studied. The hexane-acetone solvent mixture was used to investigate the ability of solvent extraction technique for cleaning up soils under various extraction conditions. The mixtures of hexane and acetone (25 vol%) were demonstrated to be the most effective in removing petroleum hydrocarbons from contaminated soils and approx 90% of saturates, naphthene aromatics, polar aromatics, and 60% of nC₇-asphaltenes were removed. Kinetic experiments demonstrated that the equilibrium was reached in 5 min and the majority of the oil pollutants were removed within 0.5 min. The effect of the ratio between solvent and soil on the extraction efficiency was also studied and results showed that the efficiency would increase following the higher solvent soil ratio. Then the multistage continuous extraction was considered to enhance the removal efficiency of oil pollutants. Three stages crosscurrent and countercurrent solvent extraction with the solvent soil ratio 6:1 removed 97% oil contaminants from soil. Clearly the results showed that the mixed-solvent of hexane and acetone (25 vol%) with character of low-toxic, acceptable cost and high efficiency was promising in solvent extraction to remove heavy oil fractions as well as petroleum hydrocarbons from contaminated soils.     

微波修复原油污染土壤的均匀设计实验

采用均匀设计实验方法,研究了微波修复原油污染土壤时原油去除率与微波能耗、含水率和含炭率等因素的关系,并应用MATLAB编程拟合出经验公式。结果分析表明:微波能耗在0～288 kJ范围内,污染土壤的原油去除率随微波能耗线性增加;在含水率为6%、含炭率为4%、微波能耗从0增加到288 kJ时,原油去除率从0%增加至92.3%;含炭率在0%～4%范围内原油去除率与含炭率成线性关系,在微波能耗为288 kJ、含水率为6%、含炭率从0%增加到4%时,原油去除率从12.3%增加至92.3%;原油去除率与含水率成二次曲线关系且开口向下,微波修复原油污染土壤的最佳含水率为6.6%。研究结果对微波修复原油污染土壤技术的优化提供了有价值的参考。     

Surfactant-enhanced biodegradation of crude oil by mixed bacterial consortium in contaminated soil

This study evaluated the effects of two surfactants (i.e., Tween 80 and SDS) on biodegradation of crude oil by mixed bacterial consortium in soil-aqueous system. The mixed bacterial consortium was domesticated from the activated sludge of cooking plant through a progressive domestication process. High-throughput sequencing analysis revealed that Rhodanobacter sp. was the dominant bacteria. The higher CMC_eff value for two surfactants was observed in soil-aqueous system compared with that in aqueous system, which was likely due to their adsorption onto soil particles. Either Tween 80 or SDS can be utilized as carbon source and promote the growth of mixed bacterial consortium. Further findings evidenced that the degradation of crude oil can be enhanced by adding either Tween 80 or SDS. The performance of Tween 80 was generally superior to SDS for the crude oil degradation. The highest crude oil degradation efficiency was 42.2 and 31.0% under the conditions of 5 CMC_eff of Tween 80 and 2 CMC_eff of SDS, respectively. Furthermore, the degradation efficiency of crude oil in remediation experiment (i.e., 77%) evidenced that the integration of adding Tween 80 and inoculating mixed bacterial consortium was effective for crude oil-contaminated soil decontamination.     

Surfactant enhanced recovery of tetrachloroethylene from a porous medium containing low permeability lenses. 2. Numerical simulation

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.     

Environmental applications for biosurfactants

Biosurfactants are surfactants that are produced extracellularly or as part of the cell membrane by bacteria, yeasts and fungi. Examples include Pseudomonas aeruginosa which produces rhamnolipids, Candida (formerly Torulopsis) bombicola, one of the few yeasts to produce biosurfactants, which produces high yields of sophorolipids from vegetable oils and sugars and Bacillus subtilis which produces a lipopeptide called surfactin. This review includes environmental applications of these biosurfactants for soil and water treatment. Biosurfactant applications in the environmental industries are promising due to their biodegradability, low toxicity and effectiveness in enhancing biodegradation and solubilization of low solubility compounds. However, more information is needed to be able to predict and model their behaviour. Full scale tests will be required. The role of biosurfactants in natural attenuation processes has not been determined. Very little information is available concerning the influence of soil components on the remediation process with biosurfactants. As most of the research until now has been performed with rhamnolipids, other biosurfactants need to be investigated as they may have more promising properties.     

The influence of defoamer on removal of PAHs in soil washing

The use of surfactants during soil washing process can create massive foam, which has a negative impact on the effective use of equipment. A series of tests was conducted to evaluate the defoaming performance of three defoamers and to investigate the influence on removal of polycyclic aromatic hydrocarbons (PAHs) during enhanced soil washing by the addition of the defoamer. Results showed that polydimethylsiloxane oil, which is the most common biomaterial used in commercial antifoaming and defoaming agents, has the best defoaming performance. With the addition of 0.1% polydimethylsiloxane oil, the removal ratios of total 16 PAHs (ΣPAHs) increased up to 53.48% and 75.92% when washing time was 5 min and 30 min, respectively, compared with the removal ratios of 44.12% and 67.28% with Triton X-100 solution only. This indicated that the proper selection of defoamer not only solves massive foaming problem but also brings out a positive influence on PAH removal during the soil washing process.

Implications: Three kinds of defoamers (kieselguhr, dodecanol, and polydimethylsiloxane oil) were collected to destroy the foam produced by Triton X-100. Among those defoamers, the polydimethylsiloxane (PDMS) oil has the best defoaming performances. The surface tension of the Triton X-100 solution with the addition of PDMS was lower. The addition of PDMS could improve the removal ratio of ΣPAHs during soil washing. That may be attributed to the addition of the nonionic surfactant Tergitol NP-10 as the emulsifier in the defoamer. After all, the results do not provide any indication of the influence on the solubilization micelles. It is thus questionable whether other components of PDMS oil could improve the PAH solubilization.