复合表面活性剂（SDS/Tw-80）对长链烷烃的增溶和柴油污染土壤的洗脱作用

表面活性剂能够快速高效处理石油污染土壤,但由于所选用表面活性剂的类型和配比、土壤性质、污染物种类的差异,洗脱效果和作用原理不尽相同。通过研究复合表面活性剂SDS/Tw-80对石油烷烃的表观增溶和从受试土壤中的洗脱过程,探讨和阐释影响洗脱过程的各种因素。结果表明,复合表面活性剂对污染土壤中的石油烷烃洗脱效果较单一表面活性剂更好,且随复合表面活性剂SDS/Tw-80中的组分配合比例的增大而显著提高,同时能够降低胶束的成束浓度要求,扩大目标物在单位胶束内的容纳量,促使各目标长链烷烃进入胶束内部的趋势加大。复合表面活性剂的适用不仅能够改善胶束构成,且组分间表现出显著的协同作用,从而使在保证较高洗脱效率的同时能够大幅降低试剂用量,有效地克服土壤的吸附作用,把对土壤性状的影响降低,对土壤质量的恢复具有积极意义。     

热活化过硫酸盐氧化污染土壤中的石油烃

石油的开采、运输、储存和使用等过程会导致一些土壤受到石油烃的污染。土壤中的石油烃会对生态安全和人类健康造成潜在危害，因此需要开展土壤修复。本研究采用热活化过硫酸钠氧化处理污染土壤中的石油烃，考察了氧化剂剂量和超声结合热活化对石油烃去除效率的影响，并对石油烃氧化产物以及氧化后土壤理化性质进行了分析。结果表明，当过硫酸钠的用量为2.4 mmol/g土壤时，石油烃的含量从3 800 mg/kg降至1 175 mg/kg，石油烃的去除效率可以达到69%。石油烃的去除效率随着氧化剂增加呈上升趋势。但当氧化剂的剂量超过2.4 mmol/g土壤时，石油烃的去除效率不再增加。使用超声结合热活化，石油烃的去除效率可以进一步提高。过硫酸盐氧化会使土壤p H显著下降，造成土壤酸化。气相色谱质谱(GC/MS)和傅里叶变换红外光谱(FTIR)分析表明石油烃氧化后可能会生成一些醇和羧酸类含氧产物。石油烃和土壤有机质被氧化成极性小分子更易进入水相，导致水中总有机碳(TOC)含量从52.4 mg/kg增加至79.8 mg/kg。扫描电镜和粒度分析表明氧化处理会改变土壤形貌，使土壤的粒径变小。氧化导致土壤的碳、氢含量减...     

通气对石油污染土壤生物修复的影响

为了探讨石油污染土壤的生物修复的有效方法,本研究就通气对石油污染土壤生物降解的影响,在自制反应器中进行了为期50天的堆腐试验。结果表明,通气可为石油烃污染土壤中的微生物提供充足的电子受体,可保持土壤pH稳定,从而促进了微生物的生物活性,强化了它们对石油污染物的氧化降解作用。通过在反应器中,调控通气量使污染土壤中石油烃的降解率进一步提高,为石油污染土壤生物修复技术的应用奠定了科学基础。     

石油污染土壤的生物修复研究

通过田间试验研究了玉米和向日葵两种植物对石油污染土壤的修复作用,考察了外源菌（OX-9）对植物修复的强化和协同效应,对“外源菌一植物”修复效果进行了初步评价。结果表明,在10000mg·k-1污染浓度下,150d玉米、向13葵试验区土壤中石油降解率分别为42．5％和46．4％,较对照区提高了100．5％和118．9％。外源节细菌的施加可使生物修复速度显著加快,150d“DX-9-玉米”和“DX-9-向日葵”试验区石油烃降解率分别达到72．8％和76．4％,较同期单独植物修复的降解率提高了71.3％和64．7％。500d各试验区土壤中石油烃降解率分别为95．5％、96．1％、97．6％和98．9％,土壤中石油烃含量均低于国家标准规定限量（〈500mg·kg-1）;土壤主要理化性质、生物群落分布、呼吸强度及植物不同部位中石油烃的残留量与对照无显著差异。结果表明：玉米、向日葵与节细菌对石油污染土壤的联合生物修复效果显著;经过两年修复,污染土壤恢复健康状态。     

多环芳烃污染土壤表面活性剂清洗及生物柴油强化

针对某焦化厂内高浓度多环芳烃污染土壤,以烷基苷（APG）、十二烷基苯磺酸钠（SDBS）和曲拉通X-100（TX100）为表面活性剂代表物,采用静态平衡法和高效液相色谱分析,探索采用单一及混合表面活性剂清洗修复多环芳烃污染土壤,并考察生物柴油对多环芳烃去除效果的影响。结果表明,单一表面活性剂对土壤中多环芳烃去除率顺序为SDBS〉APG〉TX100。APG／SDBS混合处理及TX100/SDBS为9：1混合处理提高了土壤中多环芳烃去除率,而APG／TX100混合处理没能提高多环芳烃去除率。生物柴油对TX100及TX100／SDBS去除多环芳烃效果没有明显提高,对APG及APG/TX100去除多环芳烃略有提高。当APG／SDBS为9：1时,生物柴油可以使多环芳烃去除率从（63．3±2．0）％提高到（75．6±2．0）％。单一表面活性剂、混合表面活性剂、及表面活性剂-生物柴油乳液对多环芳烃各组分去除率比较类似,对菲的去除率最高,茚并[1,2,3-d]芘次之,其余相对较低。因此,建议采用APG／SDBS＋生物柴油的混合体系对高浓度多环芳烃污染土壤进行修复。     

表面活性剂对东北黑土中苯并[a]芘的增溶洗脱作用

研究了4种常见表面活性剂十二烷基苯磺酸钠(SDBS)、十二烷基硫酸钠(SDS)、Tween80和TritonX-100对东北农田黑土土壤中苯并[a]芘的洗脱修复效果。增溶试验结果表明,非离子表面活性剂Tween80和TritonX-100对苯并[a]芘的增溶能力显著高于阴离子表面活性剂SDBS和SDS。4种表面活性剂在单一和混合处理条件下均能不同程度地洗脱土壤中的苯并[a]芘,且洗脱率随着表面活性剂浓度的增加而增大。各表面活性剂洗脱能力大小顺序为Tween80-SDS(3:1)Tween80-SDS(1:1)Tween80-SDS(10:1)Tween80TritonX-100SDSSDBS,当Tween80和SDS质量比为3:1时对两受试土壤中苯并[a]芘的去除率分别达到最高的42.3%和44.8%,可见阴-非离子混合表面活性剂对土壤苯并[a]芘的洗脱效果好于单一表面活性剂。土壤老化70 d后,Tween 80和Tween 80-SDS(3:1)处理对苯并[a]芘的洗脱率相比老化仅14 d的土壤分别下降了20.5%和12.9%,表明土壤老化时间的增加可降低表面活性剂对苯并[a]芘的洗脱去除效果。     

塿土对阴-非离子表面活性剂的吸附特征研究

以平衡吸附法研究了塿土对阴离子表面活性剂（SDS）、非离子表面活性剂（TritonX-100、Tween80和Brij35）的吸附特征,考察了pH、阴-非离子表面活性剂混合对塿土吸附表面活性剂的影响。结果表明,非离子表面活性剂在塿土上吸附等温线均呈L型,且均符合Freundlich和Langmuir方程;塿土对SDS的吸附等温线呈LS型,可用Freundlich方程来描述;塿土对4种表面活性剂吸附量的大小顺序为Tween80〉SDS〉Brij35〉TritonX-100。当阴-非离子表面活性剂一起进入土壤中,SDS-Brij35之间的相互影响不大;TritonX-100与SDS相互作用较大,无论二者以何种方式混合都会使TritonX-100在塿土上的吸附量增加,SDS的吸附量下降;SDS与Tween80之间的相互作用最大,混合后吸附量均下降,但Tween80吸附量降低的幅度最大。pH对非离子表面活性剂的吸附影响不大,而随着pH的增加,塿土对SDS的吸附百分率明显下降;在pH为8.0时,塿土对非离子表面活性剂的吸附百分率达到80以上。因此在选择合适的表面活性剂进行有机污染土壤修复和治理时,考虑土壤的特性和表面活性剂的结构是非常重要的。     

表面活性剂对土壤中石油类污染物的洗脱效果研究

表面活性剂具有增溶和乳化性质,能够有效去除土壤中的石油类污染物。本研究以实验室配制的原油污染土壤和苯并[a]蒽污染土壤为供试土壤,采用批量洗脱方法,研究阴、阳离子和非离子等11种表面活性剂的洗脱效果,从而筛选出效果较好的单一表面活性剂进行阴–非复配,并以苯并[a]蒽污染土壤为试验土样,采用单一控制变量法研究复配比、浓度、液固比、温度和添加无机盐种类对洗脱效果的影响。结果表明:对单一表面活性剂,洗脱效果最好的为SDS、Tw80和TX100,三者在浓度10 g/L,液固比为40︰1时对苯并[a]蒽去除率分别为85.3%、74.3%和67.9%;在浓度6 g/L,液固比为20︰1时对原油的去除率分别为65.3%、57.6%和67.3%。SDS-Tw80混合表面活性剂对苯并[a]蒽有协同增溶作用,SDS-Tw80在25℃,浓度6 g/L,液固比20︰1,复配比例6︰4,添加0.02 mol/L碳酸钠为助剂条件下洗脱效果最好,苯并[a]蒽去除率为84.5%。     

表面活性剂与EDTA对雪菜吸收镉的影响

采用表面活性剂与螯合剂处理,强化雪菜吸收土壤镉的盆栽试验表明,影响植物吸收镉的主要因子是表面活性剂类型。阴离子型与非离子型表面活性剂的强化修复效果要优于阳离子型表面活性剂,其中以十二烷基硫酸钠和Tween80为好。表面活性剂与EDTA复合使用,可以降低土壤对镉的吸附(顺序依次为EDTA/DBSSEDTA/TX-100EDTA/CTABEDTADBSSTX-100CTAB),增加土壤对镉的解吸,进而促使土壤镉向植物转移,有利于强化镉污染土壤的植物修复。     

表面活性剂溶液清洗油污土壤试验研究

选用两种阴离子型表面活性剂十二烷基苯磺酸钠(LAS)和十二烷基硫酸钠(SDS)及两种非离子型表面活性剂Triton X-100和Tween 80,研究了临界胶束浓度(CMC)附近各表面活性剂溶液对柴油的增溶及一次性清洗油污土壤的能力。结果表明:在CMC附近,各表面活性剂对柴油的增溶能力大小顺序为SDSSDS>Triton X-100>Tween 80,两种阴离子型表面活性剂的清洗效果优于两种非离子型表面活性剂。     

Effects of Lumbricus terrestris, Allolobophora chlorotica and Eisenia fetida on microbial community dynamics in oil-contaminated soil

Oil spills are one of the most common types of soil pollution. Bioremediation has become an attractive alternative to physicochemical methods of remediation, where feasible. Earthworms have been shown to stimulate the degradation of petroleum hydrocarbons in soil, and it was hypothesized that the role of earthworms in remediation lies in the enhancement of an oil degrading microbial community. The aim of this study was to characterize microbial activity and community dynamics in oil-contaminated soil incubated with or without earthworms. Three earthworm species (Eisenia fetida, Allolobophora chlorotica and Lumbricus terrestris) were incubated in crude oil polluted soil (ca. 10,000 mg/kg total petroleum hydrocarbons (TPH)) and a reference soil for 28 d. Control treatments with manual mixing and/or cattle dung amendment were also included. In the oil-contaminated soil, respiration and concentration of microbial biomass was significantly enhanced by earthworm amendment, and TPH concentrations decreased significantly. These effects were less evident in treatments with A. chlorotica, possibly due to a difference in behavior, since individuals of this endogeic species were found in a state of inactivity (aestivation). Microbial community dynamics were described by phospholipid fatty acid (PLFA) analyses. After 28 d, similar shifts in the soil PLFA composition were observed in the oil-contaminated soil irrespective of worm species. Fungal:bacterial ratios were increased in the presence of worms, but also by addition of dung as a food source, indicating a non-specific effect of metabolizable substrates. In contrast, the fatty acids 17:1ω8 (=Δ9-heptadecenoic acid) and 20:4ω6c (arachidonic acid) were specifically stimulated by the presence of earthworms in the oil-contaminated soil. The results showed that earthworms can contribute positively to bioremediation of oil-contaminated soil, but that the effect may be species-dependent.     

Effect of SDBS–Tween 80 mixed surfactants on the distribution of polycyclic aromatic hydrocarbons in soil–water system

Purpose

Enhancing desorption of hydrophobic organic contaminants from soils is a promising approach for the effective remediation of soils contaminated with organic compounds. The desorption efficiency of chemical reagent, such as surfactant, should be evaluated. In this study, the effect of mixed anionic–nonionic surfactants sodium dodecylbenzene sulfonate (SDBS)–Tween 80 on the distribution of polycyclic aromatic hydrocarbons in soil–water system was evaluated.

Materials and methods

Batch desorption experiments were employed to evaluate the distribution of polycyclic aromatic hydrocarbons (PAHs) and surfactants in soil–water system. PAHs and SDBS were determined by high-performance liquid chromatography, Tween 80 by spectrophotometry, and total organic carbon with a carbon analyzer.

Results and discussion

Sorption of PAHs to soil was increased at low surfactant concentration due to the effective partition phase on soil formed by sorbed surfactants. The mixture of anionic and nonionic surfactants decreased the sorption of surfactants to soil, increasing the effective surfactant concentration in solution and thus decreasing the sorption of PAHs on soil. Anionic–nonionic mixed surfactant showed better performance on desorption of PAHs from soil than single surfactant. The greatest desorption efficiency was achieved with low proportions of SDBS (SDBS/Tween80?=?1:9).

Conclusions

SDBS–Tween 80 mixed surfactant showed the highest desorption rate with low proportion of SDBS, which indicated that the addition of relative low amount of anionic surfactant could significantly promote the desorption efficiency of PAHs by nonionic surfactants. Results obtained from this study did provide useful information in surfactant-enhanced remediation of soil and subsurface contaminated by hydrophobic organic compounds.     

假单胞菌Nwu1-mu对陕北石油污染土壤的生物修复作用研究

选用假单胞菌Nwu1-mu对陕北地区石油污染土壤进行生物修复。通过检测修复过程中土壤样品的菌体生长数量、脱氢酶活性、表面张力和石油烃及其组分降解率综合考察了菌株对石油烃类物质的降解作用。结果表明,在不添加营养物质的前提下假单胞菌Nwu1-mu在60d内对石油污染土壤中的石油烃类物质降解率达到了86.5%,尤其对石油烃中的C24～C28和〉C28组分有突出的降解效果;菌株产脱氢酶和表面活性剂显示出了良好的性能,在石油烃类物质的降解过程中均起着关键的促进作用。假单胞菌Nwu1-mu显示出的强大的生物修复潜力及其不依赖于外来营养源的特性,为黄土高原的土壤生态环境修复提供了新的解决思路。     

Phytoremediation for soils contaminated by phenanthrene and pyrene with multiple plant species

Purpose  

The remediation of soil polluted by polycyclic aromatic hydrocarbons (PAHs) is of great importance due to the persistence and carcinogenic properties of PAHs. Phytoremediation has been regarded as a promising alternative among suggested approaches. For the establishment of highly effective remediation method and better understanding of the remediation mechanisms by plants, the potentials of three plant species and their planting patterns on the remediation efficacy were studied by pot experiments.     

玉米草（Zea Mexicana）与海藻寡糖联合修复石油烃污染土壤的研究

采用玉米草及海藻寡糖联合修复技术研究了石油污染土壤的修复效果,对修复过程中酶活性变化进行了测定,并采用变性梯度凝胶电泳（DGGE）技术测定了土壤中微生物群落的变化。结果表明,种植玉米草可以有效提高土壤中石油烃的降解,与对照相比石油烃降解率增加了11%;加入不同浓度海藻寡糖进一步增加了石油烃的降解效果,降解率最高达到28.6%。种植植物及加入海藻寡糖可以有效提高多酚氧化酶、脱氢酶及尿酶的活性。PCR-DGGE结果表明植物种植及海藻寡糖的加入增加了土壤中微生物数量,其微生物群落结构与未种植植物及修复前土壤相比发生了较大的变化。     

植物和微生物修复石油污染土壤的研究进展

阐述了植物和微生物降解环境中石油污染物及PAHs的重要作用和最新进展。国内外大量实验室研究表明,不同植物和微生物(细菌、真菌和放线菌)联合修复石油污染土壤均得到了较为理想的效果,在某种程度上微生物菌群要优于单一菌株;土壤中植物根系与微生物形成根际效应对污染物的降解起到了促进作用;生物表面活性剂较合成表面活性剂具有更好的生态适宜性和石油污染土壤修复能力;土壤中多组分污染物共同修复虽处于起步阶段,其作用机理也有待进一步研究,但是,发展前景值得期待。目前该领域的研究仍存在一些问题有待解决:植物–微生物菌群降解石油污染物过程中,微生物菌群间协同和竞争机制及试验结果的可重复性尚需证实;实验室研究与大田环境条件的差异,使得目前的研究成果尚需田间试验的验证和支持;根据土壤类型和气候特点,研究极端(高含盐量;氮、磷等营养元素缺乏;低温)条件下的石油高效降解菌株/群,制备有效的便于大田应用的固体菌肥意义重大;同时在确定石油污染物对环境致害的限值的基础上,建立石油污染土壤评价体系也势在必行。     

基于风险的石油烃污染土壤环境管理与标准值确立方法

目前我国对石油烃污染土壤的环境监管十分薄弱,环境管理标准的缺位成为制约这类场地评价与修复问题的瓶颈。为此系统分析了国际上尤其是发达国家在石油烃污染土壤的环境管理方法以及标准制修订实践方面的相关动态,并结合评价指标选取、目标风险水平设定、标准取值和标准细分等方面对各相关国家的标准体系进行了比较研究,以期对我国石油烃污染土壤的环境管理与标准制订有所启发。     

Assessing the Efficiency of Humic Substances as Washing Agents for Oil–Contaminated Soils and Peats under Model Experimental Conditions

Two humic preparations of different origins have been compared as washing agents for oil-contaminated soils and peat under model experimental conditions using a sample from the plow horizon of soddypodzolic soil artificially contaminated with oil or diesel fuel and a sample of high-moor peat contaminated with crude oil because of a spill occurred 15 years ago. Soil and peat were washed by shaking with solutions of the humic preparations Gumat Sakhalinskii and Lignogumat in a 1: 10 (m/v) ratio. Control samples were washed with distilled water. Washing with a synthetic surfactant (sodium dodecyl sulfate) was also added to the experimental design. After washing, soil and peat samples were air-dried and used for the determination of the total content of petroleum hydrocarbons; the characterization of their hydrocarbon composition; and the assessment of hydrophobicity from the contact angle and the efficiency of colonization by oil-destructing microorganisms Rhodococcus sp. and Candida sp., which are components of the preparation Bioros recommended for oil contaminations. It has been shown that the extraction efficiency of petroleum hydrocarbons by humic preparations did not differ from the extraction efficiency by water and was less than that by sodium dodecyl sulfate in all cases. No appreciable changes in the contact angles of soil and peat have been observed at the use of water and humic preparations as washing agents, while the contact angle decreased to less than 90o after washing with sodium dodecyl sulfate, which indicated the hydrophobicity of the surface of substrate particles. It has been found that humic preparations favor the colonization of soil and peat by oil-destructing microorganisms Rhodococcus sp. and Candida sp. Based on the obtained results, humic preparations have been recommended for further study as preparations favoring the ability of oil-destructing microorganisms to colonize oil-contaminated substrates.     

黄河三角洲土壤土著菌的石油烃降解潜力

The bioremediation potential of bacteria indigenous to soils of the Yellow River Delta in China was evaluated as a treatment option for soil remediation. Petroleum hydrocarbon degraders were isolated from contaminated soil samples from the Yellow River Delta. Four microbial communities and eight isolates were obtained. The optimal temperature, salinity, pH, and the ratios of C, N, and P （C：N：P） for the maximum biodegradation of diesel oil, crude oil, n-alkanes, and polyaromatic hydrocarbons by indigenous bacteria were determined, and the kinetics changes in microbial communities were monitored. In general, the mixed microbial consortia demonstrated wider catabolic versatility and faster overall rate of hydrocarbon degradation than individual isolates. Our experimental results demonstrated the feasibility of biodegradation of petroleum hydrocarbon by indigenous bacteria for soil remediation in the Yellow River Delta.