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.     

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.     

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.     

表面活性剂在北京碱性土壤中的吸附行为研究

通过静态吸附实验,研究了北京碱性土壤对阴离子表面活性剂SDS、阳离子表面活性剂CTAB和非离子表面活性剂Tween80的吸附行为,考察了温度对表面活性剂吸附的影响.结果表明:7种不同土样对SDS、CTAB和Tween80的吸附等温线均较好地符合Langmuir吸附模式,其吸附能力的大小顺序为2号轻壤土》轻粘土》中壤土》砂壤土》5号轻壤土》重壤土》紧砂土,这主要是由于7种土样的pH、有机质含量和机械组成不同的缘故;同一土壤中,CTAB的吸附量》Tween80的吸附量》SDS的吸附量;温度的升高,不利于SDS和CTAB在土壤中的吸附,而有利于Tween80的吸附.     

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.     

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.     

Solubility and adsorption behaviors of chlorpyriphos-methyl in the presence of surfactants

In the present work changes in the adsorption of the pesticide chlorpyrifos-methyl (CLP-m) on soil colloids induced by application of surfactants were determined using a batch equilibrium method. The surfactants used were sodium dodecyl sulphate (SDS), Tween 20, and dihexadecyldimethylammonium bromide (DHAB). The adsorption isotherms of CLP-m in aqueous medium and in surfactant solutions at concentration equal to the critical micelle concentration (CMC) fitted the Freunlich adsorption equation generally with R² values greater than 0.96. While the addition of SDS and DHAB decreased the pesticide adsorption, the addition of Tween 20 increased the pesticide adsorption. The increases or decreases in the adsorption in the experiment revealed that the behavior of CLP-m in soil water-systems mainly depends on the type of surfactant. Moreover water solubility of CLP-m changes by the three surfactants below and above their CMC were studied. While the solubility of CLP-m was enhanced by SDS both below and above the CMC, the solubility of the pesticide was enhanced by DHAB only above the CMC. Tween 20 did not influence the solubility of CLP-m.     

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.     

Biodegradation of benzene, toluene, and xylene (BTX) in liquid culture and in soil by Bacillus subtilis and Pseudomonas aeruginosa strains and a formulated bacterial consortium

Purpose

The major aromatic constituents of petroleum products viz. benzene, toluene, and mixture of xylenes (BTX) are responsible for environmental pollution and inflict serious public concern. Therefore, BTX biodegradation potential of individual as well as formulated bacterial consortium was evaluated. This study highlighted the role of hydrogen peroxide (H₂O₂), nitrate, and phosphate in stimulating the biodegradation of BTX compounds under hypoxic condition.

Materials and methods

The individual bacterium viz. Bacillus subtilis DM-04 and Pseudomonas aeruginosa M and NM strains and a consortium comprising of the above bacteria were inoculated to BTX-containing liquid medium and in soil. The bioremediation experiment was carried out for 120?h in BTX-containing liquid culture and for 90?days in BTX-contaminated soil. The kinetics of BTX degradation either in presence or absence of H₂O₂, nitrate, and phosphate was analyzed using biochemical and gas chromatographic (GC) technique.

Results

Bacterial consortium was found to be superior in degrading BTX either in soil or in liquid medium as compared to degradation of same compounds by individual strains of the consortium. The rate of BTX biodegradation was further enhanced when the liquid medium/soil was exogenously supplemented with 0.01?% (v/v) H₂O₂, phosphate, and nitrate_. The GC analysis of BTX biodegradation (90?days post-inoculation) in soil by bacterial consortium confirmed the preferential degradation of benzene compared to m-xylene and toluene.

Conclusions

It may be concluded that the bacterial consortium in the present study can degrade BTX compounds at a significantly higher rate as compared to the degradation of the same compounds by individual members of the consortium. Further, addition of H₂O₂ in the culture medium as an additional source of oxygen, and nitrate and phosphate as an alternative electron acceptor and macronutrient, respectively, significantly enhanced the rate of BTX biodegradation under oxygen-limited condition.     

Evaluation of B. subtilis SPB1 biosurfactants' potency for diesel-contaminated soil washing: optimization of oil desorption using Taguchi design

Low solubility of certain hydrophobic soil contaminants limits remediation process. Surface-active compounds can improve the solubility and removal of hydrophobic compounds from contaminated soils and, consequently, their biodegradation. Hence, this paper aims to study desorption efficiency of oil from soil of SPB1 lipopeptide biosurfactant. The effect of different physicochemical parameters on desorption potency was assessed. Taguchi experimental design method was applied in order to enhance the desorption capacity and establish the best washing parameters. Mobilization potency was compared to those of chemical surfactants under the newly defined conditions. Better desorption capacity was obtained using 0.1 % biosurfacatnt solution and the mobilization potency shows great tolerance to acidic and alkaline pH values and salinity. Results show an optimum value of oil removal from diesel-contaminated soil of about 87 %. The optimum washing conditions for surfactant solution volume, biosurfactant concentration, agitation speed, temperature, and time were found to be 12 ml/g of soil, 0.1 % biosurfactant, 200 rpm, 30 °C, and 24 h, respectively. The obtained results were compared to those of SDS and Tween 80 at the optimal conditions described above, and the study reveals an effectiveness of SPB1 biosurfactant comparable to the reported chemical emulsifiers. (1) The obtained findings suggest (a) the competence of Bacillus subtilis biosurfactant in promoting diesel desorption from soil towards chemical surfactants and (b) the applicability of this method in decontaminating crude oil-contaminated soil and, therefore, improving bioavailability of hydrophobic compounds. (2) The obtained findings also suggest the adequacy of Taguchi design in promoting process efficiency. Our findings suggest that preoptimized desorption process using microbial-derived emulsifier can contribute significantly to enhancement of hydrophobic pollutants' bioavailability. This study can be complemented with the investigation of potential role in improving the biodegradation of the diesel adsorbed to the soil.     

Environmental features of two commercial surfactants widely used in soil remediation

One of the main limitations for a wider application of surfactants in soil remediation is the lack of knowledge about environmental fate and toxicity of surfactant itself especially for in situ application. Sorption behaviour, biodegradability, toxicity of parent compound and its metabolites are important processes that affect environmental fate of surfactants in site remediation applications. Tween 80 (poly(oxyethylene)(20)-sorbitane monooleate) and Aerosol MA+80 (dihexyl sodium sulfosuccinate) are surfactants that have been tested in laboratory and field scale remediation of soil and groundwater. In this work, the sorption and biodegradability of these surfactants were assessed to provide conditions and limitations for their use. The soil used in this experimentation was analysed for organic carbon content, soil bacteria, and size fraction and resulted to be a good model because is characterised by mean values for almost all considered parameters. Tween 80 showed high degree of biodegradability but a high affinity for soil matrix. Results suggest that Tween 80 could find its best application in ex situ solid phase remediation like ex situ bioremediation; its high affinity to soil could limit in situ applications. Biodegradation tests for Aerosol MA+80 show low degree of biodegradability and mineralisation. Biodegradation experiments, coupled with analysis of toxicity, could support the hypothesis that degradation of Aerosol MA+80 is not complete and leads to an accumulation of intermediates with at least the same toxicity of the parental compound. Therefore, aquifer remediation application with Aerosol MA+80 has to be conducted with necessary precautions to avoid product loss and excess surfactant should be flushed from the soil.     

Tween-80和H2O2对Burkholderia cepacia降解油脂的影响

油脂废水是一种重要的水污染源。研究了表面活性剂和H₂O₂对洋葱伯克霍尔德氏菌(Burkholderia cepacia)降解油脂的影响。结果表明：适量的表面活性剂和H₂O₂促进油脂的降解。表面活性剂可以增强油脂在水相中的溶解度，提高油脂在水中的乳化程度从而增加其生物可利用性。当Tween-80浓度600mg/L时，油脂降解率达到91%。低浓度H₂O₂不仅能刺激微生物生长，而且使培养液中的pH值保持相对稳定，提高了微生物对油脂的降解率。H₂O₂在浓度为400mg/L时，能使油脂降解率达到90%。     

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。     

Effect of crude oil contamination on the chlorophyll content and morpho-anatomy of Cyperus brevifolius (Rottb.) Hassk

Chlorophyll plays a pivotal role in the plant physiology and its productivity. Cultivation of plants in crude oil contaminated soil has a great impact on the synthesis of chlorophyll pigment. Morpho-anatomy of the experimental plant also shows structural deformation in higher concentrations. Keeping this in mind, a laboratory investigation has been carried out to study the effect of crude oil on chlorophyll content and morpho-anatomy of Cyperus brevifolius plant. Fifteen-day-old seedling of the plant was planted in different concentrations of the crude oil mixed soil (i.e., 10,000, 20,000, 30,000, 40,000, and 50,000 ppm). A control setup was also maintained without adding crude oil. Results were recorded after 6 months of plantation. Investigation revealed that there is a great impact of crude oil contamination on chlorophyll content of the leaves of the experimental plant. It also showed that chlorophyll a, chlorophyll b, and total chlorophyll content of leaves grown in different concentrations of crude oil were found to be lower than those of the control plant. Further, results also demonstrated that chlorophyll content was lowest in the treatment that received maximum dose of crude oil. It also showed that chlorophyll content was decreased with increased concentration of crude oil. Results also demonstrated that there was a reduction in plant shoot and root biomass with the increase of crude oil concentration. Results also revealed that the shoot biomass is higher than root biomass. Morphology and anatomy of the experimental plant also show structural deformation in higher concentrations. Accumulation of crude oil on the cuticle of the transverse section of the leaves and shoot forms a thick dark layer. Estimation of the level of pollution in an environment due to oil spill is possible by the in-depth study of the harmful effects of oil on the morphology and anatomy and chlorophyll content of the plants grown in that particular environment.     

Enhancing p-cresol extraction from soil

Soil washing is a potential technology for rapid removal of organic hydrocarbons sorbed to soils. In this work, p-cresol desorption with different non-ionic surfactants (Tween 80, Brij 30 and Triton X-100) was compared to cyclodextrine and citrate as solubilizer. A series of batch extraction experiments were conducted at 20 °C using the field soil with different extracting solutions at various concentrations to investigate the removal efficiency and to optimize the concentration of the extractant. The use of the different extracting agents was very selective to p-cresol extraction, minimizing soil organic matter releasing and maintaining the natural pH of the soil. The highest asymptotic values of desorption percentages were obtained for Tween 80 and Brij 30 at 48 h. However, Brij 30 ecotoxicity (EC₅₀ = 0.5 mg L⁻¹) is in the same order of that obtained for p-cresol, being this surfactant clearly ruled out. Liquid to solid ratio of 2.5 mL g⁻¹ presented the best extraction results, while concentrations higher than 1 g L⁻¹ for Tween 80 and Citrate did not produce any significant effect on the desorption efficiency. p-Cresol extraction efficiencies higher than 70% and 60% for Tween 80 and Citrate, respectively.     

Influence of surfactants on solubilization and fungal degradation of fluorene

Eighteen fungal strains were tested in toxicity assays with surfactants in order to select surfactants and strains tolerant to surfactants for degradation assays. Two nonionic surfactants were used, an alkylphenol ethoxylate, Triton X-100, a sorbitan ester, Tween 80 and an anionic surfactant, sodium dodecyl sulfate. Solubilization and biodegradation tests were conducted in liquid medium batch; fluorene was quantified by HPLC. Results showed the enhancement of fluorene solubilization by the three surfactants, good tolerance of nonionic surfactants by the fungal strains and the enhancement of the biodegradation of fluorene by Doratomyces stemonitis (46-62%) and Penicillium chrysogenum (28-61%) in the presence of Tween 80 (0.324 mM) after 2 days.     

Evaluation of biosurfactants for crude oil contaminated soil washing

An evaluation of the ability of aqueous biosurfactant solutions (aescin, lecithin, rhamnolipid, saponin and tannin) for possible applications in washing crude oil contaminated soil was carried out. The biosurfactants behaviour in soil-water, water-oil and oil-soil systems (such as foaming, solubilization, sorption to soil, emulsification, surface and interfacial tension) was measured and compared with a well-known chemical surfactant (sodium dodecyl sulphate, SDS) at varying concentrations. Results showed that the biosurfactants were able to remove significant amount of crude oil from the contaminated soil at different solution concentrations for instance rhamnolipid and SDS removed up to 80% oil and lecithin about 42%. The performance of water alone in crude oil removal was equally as good as those of the other biosurfactants. Oil removal was due to mobilization, caused by the reduction of surface and interfacial tensions. Solubilization and emulsification effects in oil removal were negligible due to the low crude oil solubilization of 0.11%. Therefore, these studies suggest that knowledge of surfactants' behaviour across different systems is paramount before their use in the practical application of oil removal.     

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.     

Plant species affect colonization patterns and metabolic activity of associated endophytes during phytoremediation of crude oil-contaminated soil

Plants coupled with endophytic bacteria hold great potential for the remediation of polluted environment. The colonization patterns and activity of inoculated endophytes in rhizosphere and endosphere of host plant are among the primary factors that may influence the phytoremediation process. However, these colonization patterns and metabolic activity of the inoculated endophytes are in turn controlled by none other than the host plant itself. The present study aims to determine such an interaction specifically for plant-endophyte systems remediating crude oil-contaminated soil. A consortium (AP) of two oil-degrading endophytic bacteria (Acinetobacter sp. strain BRSI56 and Pseudomonas aeruginosa strain BRRI54) was inoculated to two grasses, Brachiaria mutica and Leptochloa fusca, vegetated in crude oil-contaminated soil. Colonization patterns and metabolic activity of the endophytes were monitored in the rhizosphere and endosphere of the plants. Bacterial augmentation enhanced plant growth and crude oil degradation. Maximum crude oil degradation (78 %) was achieved with B. mutica plants inoculated with AP consortium. This degradation was significantly higher than those treatments, where plants and bacteria were used individually or L. fusca and endophytes were used in combination. Moreover, colonization and metabolic activity of the endophytes were higher in the rhizosphere and endosphere of B. mutica than L. fusca. The plant species affected not only colonization pattern and biofilm formation of the inoculated bacteria in the rhizosphere and endosphere of the host plant but also affected the expression of alkane hydroxylase gene, alkB. Hence, the investigation revealed that plant species can affect colonization patterns and metabolic activity of inoculated endophytic bacteria and ultimately the phytoremediation process.     

Removal of alkylphenols from polluted sites using surfactant-assisted soil washing and photocatalysis

Background and purpose  

Surfactant-assisted soil washing and photocatalysis are well-known remediation processes of environmental concern. The application of photocatalysis to treat soil washing extracts containing 4-methylphenol, 4-ethylphenol and 4–tert-butylphenol in the presence of nonionic (C₁₂E₈ and C₁₂E₂₃) and anionic (SDS) surfactants and some of their binary mixtures was investigated in this work by studying the pollutants degradation in the presence of TiO₂ dispersions irradiated with simulated solar light.