Decontamination of oil-polluted soil by cloud point extraction

An extraction procedure based on cloud point phase separation of nonionic surfactants was used to remove oil contamination from soils. The detergent employed was Triton X-114, and its clouding behavior was monitored by means of a fluorescence probe. Changes in the I (1)I (3) ratio of pyrene indicated gradual dehydration of the detergent micelles upon heating. The rate of phase separation, and the volume and water content of the micellar phase were determined. In the practical clean-up, 85-98% of the oil present in the soil was found to enter the micellar phase of the separated washing liquid. A 15-min washing time with 3-5% detergent was found to be sufficient for this degree of contaminant removal from soil containing 0.009-0.017% oil, using a liquid:solid ratio of 5:2. The extraction efficiency decreased with increasing carbon content of the soil. The process holds promise for large-scale treatment of oil-polluted soils.     

Surfactant effects on electrokinetic processes in clay-rich soils remediation

The present work concerns the realisation of an equipment suitable for the choice of surfactants to be employed in the remediation of polluted soils by soil washing processes. The experimental activity has been focused to verify the surfactants efficiency in electrokinetic processes applied in low porosity soils, polluted with used vehicle oil. The equipment consents to estimate low electroosmotic permeabilities, electrical current and to analyse the electrolytic solutions. The concentration of the chemical species reached in both anodic and cathodic cells allows a more accurate evaluation of the ion mobility through the soil. The apparatus realised has been shown to be a useful instrument capable of providing directions for the choice of surfactants in electrokinetic soil remediation. The choice of an anionic surfactant for the oil removal has shown promising result.     

Enhanced Biodegradation of Hydrocarbons in Soil by Microbial Biosurfactant, Sophorolipid

Effectiveness of a microbial biosurfactant, sophorolipid, was evaluated in washing and biodegradation of model hydrocarbons and crude oil in soil. Thirty percent of 2-methylnaphthalene was effectively washed and solubilized with 10 g/L of sophorolipid with similar or higher efficiency than that of commercial surfactants. Addition of sophorolipid in soil increased biodegradation of model compounds: 2-methylnaphthalene (95% degradation in 2 days), hexadecane (97%, 6 days), and pristane (85%, 6 days). Also, effective biodegradation method of crude oil in soil was observed by the addition of sophorolipid, resulting in 80% biodegradation of saturates and 72% aromatics in 8 weeks. These results showed the potentials of the microbial biosurfactant, sophorolipid, as an effective surfactant for soil washing and as an in situ biodegradation enhancer.     

微乳液脱除油泥砂中的原油

以煤油为油相, 十二烷基苯磺酸钠(SDBS)为主表面活性剂, 正戊醇为助表面活性剂, 通过改变NaCl浓度分别制备出上相、 中相和下相3种类型的微乳液, 研究了其对油泥砂中原油的脱除效率, 考察了微乳液类型、 油泥砂处理量、 时间和温度等的影响. 结果表明, 油相在下相微乳液中的脱油效率最高, 在中相中次之, 在上相中最低, 且油相脱油率与油泥砂处理量间具有良好的线性关系; 在所考察的时间(10~60 min)和温度(20~70℃)范围内, 脱油效率变化幅度不显著, 表明该体系可对油泥砂进行常温快速脱油处理.     

A multi-process phytoremediation system for decontamination of persistent total petroleum hydrocarbons (TPHs) from soils

Multiple techniques that affect different aspects of contaminant removal can improve remediation of persistent hydrocarbons from soils. We have developed a multi-process phytoremediation system (MPPS) that is composed of land-farming (aeration and light exposure), contaminant degrading bacteria, plant-growth-promoting rhizobacteria (PGPR), and growth of the contaminant-tolerant plant, Tall Fescue (Festuca arundinacea). In this study, the MPPS was applied to a contaminated soil acquired from the Imperial Oil land farm site in Sarnia, Ontario, Canada. This soil was contaminated with oil refinery sludge to a level of approximately 5% (w/w) total petroleum hydrocarbons (TPHs). Over an initial 4-month period, the average efficiency of removal of persistent TPHs by the MPPS was twice that of land-farming alone, 50% more than bioremediation alone, and 45% more than phytoremediation alone. Importantly, the MPPS removed oil fractions 2, 3 and 4 with equal efficiency. Therefore, the highly hydrophobic, recalcitrant TPH fractions were remediated from the soil with the MPPS. After a second 4-month period, the MPPS removed 90% of all fractions of TPHs from the soil. Phytoremediation alone was able to remove only about 50% of TPHs in the same time period. The key elements for successful phytoremediation were the use of a plant species that can proliferate in the presence of high levels of contaminants, and strains of PGPR that increase plant tolerance and accelerate plant growth in heavily contaminated soils.     

无机盐强化烷基多苷清洗石油污染土壤的机理

研究了无机盐对一种烷基多苷(APG)产品APG1214物理化学性质的影响, 以期解释无机助剂对APG1214清洗老化石油污染土壤的强化作用. 实验发现无机助剂能够显著降低APG1214的临界胶束浓度(CMC)和浊点, 提高其表面活性, 对除油过程有促进作用. 利用动态光散射(DLS)和透射电镜(TEM)研究了无机助剂对APG1214聚集体流体力学半径(Rh)和形态的影响, 发现低浓度无机助剂可减小APG1214聚集体尺寸, 而高浓度助剂则增加聚集体尺寸. 研究结果显示出APG1214与常见非离子表面活性剂不同的特性. 洗油后溶液中表面活性剂聚集体的Rh分布明显变窄, 但平均半径有所增加; TEM观察显示, 洗油后溶液中囊泡壁明显变厚, 证明增溶是APG1214去除石油污染物的一条途径. 本实验得到的结论为APG1214在石油污染土壤修复方面的应用提供了依据, 并为在其他领域更好地利用这类绿色表面活性剂提供了参考.     

Elution of 17α 25-Norhopanes and Triaromatic Steroids from Weathered Soils by Mixed Triton X-100/Na2SiO3 Surfactant Solution

Sodium silicate(Na₂SiO₃) was used to improve the elution of super heavy oil from weathered soil on an ultrasound-enhanced elution system by the solution containing 0―6000 mg/L surfactant Triton X-100. The removal extent of three markers[C_26―34 17α 25-norhopanes, C_26―28 triaromatic steroids(TAS), and C_27―29 methyl triaromatic steroids(MTAS)] was monitored. The average elution percentages of C_26―34 norhopanes, C_26―28 TAS, and C_27―29 MTAS by Triton X-100/Na₂SiO₃ solutions were increased by 11%―13%, 9%―11% and 8%―13% with increasing Triton X-100 concentrations from 150 mg/L to 6000 mg/L. All the concentrations of Triton X-100 improved the elution of TAS homologs containing fewer carbon atoms, whereas high concentrations improved the elution of larger 17α 25-norhopane and MTAS species. Addition of Na₂SiO₃ produced a noticeable increase in elution, particularly for lower-weight species. Scanning electron microscope(SEM) images and energy spectroscopy data reveal that surfactant solution of 6000 mg/L Triton X-100 and 4000 mg/L Na₂SiO₃ produced the greatest improvement in the elution of super heavy oil aggregates encapsulating the soil surface and the emulsification of particle dispersions. That is to say mixed solutions of Triton X-100 and Na₂SiO₃ in combination with ultrasound are a potential means of removing super heavy oil from weathered soils.     

Synergistic effect of mixed anionic and cationic surfactant systems on the interfacial tension of crude oil-water and enhanced oil recovery

Surfactant based enhanced oil recovery (EOR) is an interesting area of research for several petroleum researchers. In the present work, individual and mixed systems of anionic and cationic surfactants consisting of sodium dodecyl sulphate (SDS) and cetyltrimethylammonium bromide (CTAB) in different molar ratios were tested for their synergistic effect on the crude oil-water interfacial tension (IFT) and enhanced oil recovery performance. The combination of these two surfactant systems showed a higher surface activity as compared to individual surfactants. The effect of mixed surfactant systems on the IFT and critical micellar concentration (CMC) is strongly depends on molar ratios of the two surfactant. Much lower CMC values were observed in case of mixed surfactant systems prepared at different molar ratios as compared to individual surfactant systems. The lowest CMC value was found when the molar concentration of SDS was higher than the CTAB. When the individual and mixed surfacant systems were tested for EOR performance through flooding experiments, higher ultimate oil recovery was obtained from mixed surfactant flooding compared to individual surfactants. Combination of SDS and CTAB or probably other anionic-cationic surfactants show synergism with substantial ability to reduce crude oil water IFT and can be a promising EOR method.     

Effects of additives on the structure of rhamnolipid (biosurfactant): a small-angle neutron scattering (SANS) study

Pollution of soils and sediments by heavy metals is an environmental concern. Among the remedial techniques, soil washing is proving to be reliable. Biosurfactant rhamnolipid has shown its potential as a washing agent. In this research, small angle neutron scattering (SANS) was employed to investigate the size and morphology of rhamnolipid aggregates and micelle structure in the presence of heavy metals Cu, Zn, and Ni. The results indicate the importance of the pH of the system in the morphology of the aggregates in the rhamnolipid solution. Creation of a basic condition by addition of 1% NaOH led to the formation of large aggregates (>2000 A) + micelles with RG approximately 17 A while in the acidic environment with 1% NaCl, large polydisperse vesicles with a radius about 550-600 A were formed. The size of the aggregates in both acidic and basic condition is fine enough to ease the flow of the rhamnolipid solution through the porous media with the pore sizes as small as 200 nm.     

Phenanthrene removal in unsaturated soils treated by electrokinetics with different surfactants—Triton X-100 and rhamnolipid

In this study, the remediation performance of electrokinetic (EK) technology integrated with different surfactants for removing phenanthrene from unsaturated soils was investigated. A synthetic surfactant (Triton X-100) and a biosurfactant (rhamnolipid) were used to enhance phenanthrene solubility and removal efficiency during EK process. Results indicate that the electro-osmotic flow (EOF) rate in the rhamnolipid system is higher than that in Triton X-100. Using the EK technology for the removal of phenanthrene in the presence of rhamnolipid was more efficient than in the presence of Triton X-100. In addition to the transport mechanism of phenanthrene in EK system, the presence of rhamnolipid may promote microbial growth in the soil–water system and bring about biodegradation of phenanthrene. A diffusion–advection–sorption (DAS) model was solved by MATLAB, based on the linear sorption isotherm at the non-equilibrium condition, which is feasible to simulate the movement of phenanthrene during the EK + Triton X-100 treatment.     

Enhancement of rhamnoplipid production in residual soybean oil by an isolated strain of Pseudomonas aeruginosa

In the present work, the production of rhamnolipid from residual soybean oil (RSO) from food frying facilities was studied using a strain of Pseudomonas aeruginosa of contaminated lagoon, isolated from a hydrocarbon contaminated soil. The optimization of RSO, ammonium nitrate, and brewery residual yeast concentrations was accomplished by a central composite experimental design and surface response analysis. The experiments were performed in 500-mL Erlenmeyer flasks containing 50 mL of mineral medium, at 170 rpm and 30 +/- 1 degrees C, for a 48-h fermentation period. Rhamnolipid production has been monitored by measurements of surface tension, rhamnose concentration, and emulsifying activity. The best-planned results, located on the central point, have corresponded to 22 g/L of RSO, 5.625 g/L of NH(4)NO(3), and 11.5 g/L of brewery yeast. At the maximum point the values for rhamnose and emulsifying index were 2.2 g/L and 100%, respectively.     

Extraction of hydrocarbon contamination from soils using accelerated solvent extraction

Accelerated solvent extraction was studied as a method for the extraction of hydrocarbon contamination from wet and dry soils. Temperatures from 125 to 200 degrees C and six different solvents were investigated. Nonpolar solvents could not achieve complete recovery from wet soils at the temperatures studied. Optimum conditions were found to be 175 degrees C with dichloromethane-acetone (1:1, v/v) with 8 min heat-up time and 5 min static time. Quantitative recoveries for diesel range organics (DROs) and waste oil organics (WOOs) were obtained using the optimized conditions. The recovery of DROs and WOOs from three matrices at two concentrations (5 and 2000 mg/kg) averaged 115%. These results show that accelerated solvent extraction can generate results comparable to those obtained using Soxhlet or sonication.     

FLOW PROPERTIES OF WEATHERED CRUDE OILS AND THEIR EMULSIONS

The present paper proposes the emulsification of weathered crude oils in water as a competitive and cost effective method for reducing their viscosities. Weathered crude oil samples were collected from major Kuwaiti oil lakes. Emulsion preparation involved using, either a nonionic surfactant or alkali, as well as both alkali and fatty acid. The obtained emulsions were characterized by measuring the droplet size distribution of the dispersed phase using optical microscopy. Emulsion stability was also examined in terms of the system breakdown. The rheological properties were measured using a concentric cylinder rotary rheometer. The emulsion rheological behavior has been studied as a function of composition, temperature, and shear rate. A constitutive model was developed to characterize the pseudoplastic behavior of the crude oil and the emulsion systems. The model fitted well the experimental results with a correlation coefficient higher than 95%. Associated with the pseudoplastic behavior, viscoelastic behavior has been observed with emulsions and some oils at high shear rates.

The results of this investigation indicated that the examined weathered crude oils can be transported through pipelines as emulsions of up to 80 vol.% oil concentrations. The proposed method of treatment with NaOH and oleic acid offers several advantages over the surfactant treatment. It exhibited comparable rheological behavior at lower cost and less mixing energy. It also provided higher emulsion stability, which favors oil transportation for longer distances.     

Using Surfactant System to Wash a Polluted Soil by Petroleum Derivatives in Egyptian Abu Madi Fields in Terms of Emulsification

The exploration and production activities of the natural gas in Abu Madi region (in middle delta) progressed in the last decade. The condensate hydrocarbon and formation water are bi‐products produced during the natural gas industry. The accompanied water contains 10–15% condensate (gasoline). This water with gasoline was drained into the Shehab El‐Din drain. The farmers were used this water to irrigate their fields. Great areas of the fields were out of order of planting as the result of gasoline pollution. This work concentrates on washing the polluted soil using locally prepared surfactant (LABSA‐Na) in the washing process. The soil sample was picked up from the Abu Madi field and was divided into pots (four pots for each treatment). The experiment was designed on the basis of polluting the soil by gasoline (condensate) from 1 to 10%. The washing process was carried out in presence of 0.1, 0.3, and 0.5% surfactant solutions. The control and blank sample were taken in consideration. The washed and the latent oil percentages were determined using the spectrophotometric method. After polluting and washing the soil, the pots were fertilized and planted by Zea Mays. The pots were irrigated twice a week. The length of plants was followed up. The obtained results cleared that, the efficiency of washing process increases with increasing of the pollutant percentage and also with increasing of surfactant concentration. The maximum washed oil (gasoline) was obtained at 10% gasoline and 0.5% surfactant concentration. The length of plants after 21 days of planting were; 0 (no planting), 24, 34, 39, 54, and 57 cm against polluted soil and planted (control) washed soil by water only; washed soil by 0.1%; washed soil by 0.3%; washed soil by 0.5% and no polluted soil (blank) respectively. These data revealed that, removing the hydrocarbon from the soil by washing using surfactants is the most effective method as the result of solubilization and emulsification of the hydrocarbon by surfactant which make it more removable.     

表面活性剂泡沫强化修复污染土壤研究进展

全球土壤资源污染严重,表面活性剂泡沫强化修复技术因泡沫流动受重力影响小、避免淋洗液难控制使区域扩大引发二次污染、修复效果好等备受关注。本文综述了表面活性剂泡沫强化修复技术在治理污染土壤中的研究进展,详细阐述了表面活性剂泡沫强化修复污染物的效果、机理、影响因素及应用前景,并就表面活性剂泡沫强化修复技术今后的研究方向进行了展望。     

Efficiency of Different Methods and Solvents for the Extraction of Polycyclic Aromatic Hydrocarbons from Soils

The efficiencies of supercritical fluid extraction (SFE), accelerated solvent extraction (ASE), Soxhlet, and ultrasonic extraction in the analysis of polycyclic aromatic hydrocarbons (PAHs) in soils were evaluated. Solvents with different polarity were used to extract the PAHs from two soils, one with high and one with low contamination level. ASE showed good results with all solvents almost independent of the solvent polarity and the best results with acetone-toluene (1 : 1). Ultrasonic extraction with acetone-toluene for the uncontaminated soil and acetone-ethanolamine for the highly contaminated also showed good recoveries. The time-consuming Soxhlet extraction with pentane or dichloromethane was less effective. The PAH recovery from SFE was related to the soil matrix or the contamination level. The best extraction conditions (CO 2 /10% pentane) are successful for the soil with a low contamination level and a high humic acid content whereas the extractions of the highly contaminated soil gave poor results irrespective of the solvent used.     

气相色谱-质谱分析新种海绵Reniochalina sp.中的低极性组分

采用气相色谱-质谱联用技术（GC-MS）与核磁共振氢谱（1H-NMR）相结合的方法,对中国黄海肾指海绵属新种海绵Reniochalina sp.中的低极性组分进行了研究。实验首先采用环己烷对海绵进行提取,然后将提取液浓缩,用硅胶柱对其进行柱色谱分离。取乙酸乙酯-环己烷（体积比为1∶9）混合液梯度洗脱所得油状物用于连续两次制备色谱分离,得到两个样品,对其进行1H-NMR及GC-MS分析。此次实验共从该海绵中分离鉴定出10种链烃、2种脂肪酸、2种脂肪酸酯、邻苯二甲酸以及3种邻苯二甲酸二酯共18种化学成分。该研     

An unusual morphological transformation of rhamnolipid aggregates induced by concentration and addition of styrene: A small angle neutron scattering (SANS) study

The aggregation behaviour of rhamnolipid as mixed with styrene (as a representative of hydrophobic molecules commonly found in contaminated soils) was investigated by small angle neutron scattering (SANS) as a function of both rhamnolipid and styrene concentrations. Contrast variation was applied (i.e., deuterated and hydrogenated styrene) to resolve the morphologies of aggregates. A structural transformation from cylindrical micelles to a binary mixture of cylindrical micelles and vesicles induced by both elevated rhamnolipid and styrene concentration is proposed based on the analysis of the SANS data. The resultant structure of the aggregates, vesicle, is different from the “oil droplets” commonly reported in the microemulsions of water-oil-surfactant mixtures. It is also found that this transformation is far from being complete even at the highest styrene solubility, implying that further dissolution of styrene may be constrained by other factors.     

Use of Cyclodextrins as An Environmentally Friendly Extracting Agent in Organic Aged-contaminated Soil Remediation

The removal of Polycyclic Aromatic Hydrocarbons (PAHs) from soil using pure water is quite ineffective due to␣their low aqueous solubility. Most of present processes are based on organic cosolvents or surfactants, leading to potential environmental hazard. Addition of cyclodextrin (CD) in aqueous washing solutions has been shown to␣increase the removal efficiency several times, while being non-toxic agents. Herein are investigated the effectiveness of cyclodextrins to remove PAHs occurring in industrially aged-contaminated soil. β-cyclodextrin (BCD), hydroxypropyl-β-cyclodextrin (HPCD) and methyl-β-cyclodextrin (MCD) solutions were used for soil flushing in column test or batch experiments to evaluate some influent parameters that can significantly increase the removal efficiency. The process parameters chosen were CD concentration, ratio of washing solution volume to soil weight, and temperature of washing solution. These parameters were found to have a significant and almost linear effect on PAHs removal from the contaminated soil, except the temperature where no significant enhancement in PAHs extraction was observed for temperature range from 5 to 35 °C. Removal capacity of HPCD and MCD was higher than BCD one. The PAHs extraction enhancement factor compared to water was about 200.     

Possible remediation of dioxin-polluted soil by steam distillation

2,7-Dichlorodibenzo-p-dioxin (DCDD) was found to evaporate easily with water vapor from a heated solution. Steam distillation was also effective for the removal of DCDD from DCDD-applied soil; its concentration (250 microg/50g soil) in the original soil decreased to less than 5% after steam distillation for only 20 min. Actual dioxin-polluted soil in Tokorozawa City was partially decontaminated using the same method. These results suggest that steam distillation could be a new remedial method for soils contaminated with persistent environmental pollutants, such as dioxins and polychlorinated biphenyls.