有机粘土矿物对水中低浓度菲的吸附性能和机理

分别选用十六烷三甲基溴化铵(HDTMA-Br)、四甲基溴化铵(TMA-Br)、聚乙二醇(PEG)表面活性剂改性天然粘土矿物,研究其对水中低浓度多环芳烃类难降解有机物菲的吸附性能和机理,并讨论了有机粘土的用量对吸附菲的性能的影响,验证了有机粘土矿物吸附菲后的稳定性.3种有机粘土矿物对菲的吸附等温线均呈中凹型,表现为分配系数(Kp)逐渐增大,表明吸附是分配作用和溶剂化效应共同作用的结果.根据Kp及土样有机碳含量(foc)所得的经有机碳归一化的分配系数(Koc)基本为常数,远远高于天然土壤/沉积物的Koc.在相同实验条件下,3种有机粘土矿物中HDTMA改性粘土矿物对菲的吸附性能最强,PEG改性粘土矿物次之,TMA改性粘土矿物最差.     

甘氨酸-β-环糊精对菲的增溶、解吸行为研究

为改善β-环糊精的水溶性,将β-环糊精和甘氨酸在碱性条件下用环氧氯丙烷连接起来,得到水溶性极好的甘氨酸-β-环糊精,研究了甘氨酸-β-环糊精对菲的增溶、解吸行为,考察了pH、甘氨酸-β-环糊精初始浓度、温度、不同环糊精类型对菲解吸的影响。结果表明,甘氨酸-β-环糊精对菲的增溶效果显著,其初始质量浓度为30 g/L时,对菲的增溶倍数可以达到近30倍;甘氨酸-β-环糊精对菲的解吸随pH的升高而降低;升高甘氨酸-β-环糊精初始浓度和温度有利于菲的解吸;甘氨酸-β-环糊精对菲的解吸好于α-环糊精和β-环糊精,甘氨酸-β-环糊精对菲污染土壤的解吸符合准二级动力学方程。该静态解吸研究可以为菲污染土壤的修复提供基础信息。     

应用表面活性剂-生物柴油微乳液去除污染土壤中多环芳烃

针对修复焦化厂高浓度多环芳烃污染土壤高成本的现实,采用以非食用性植物油、生物柴油、表面活性剂及其乳化合成的微乳液为淋洗剂,比较不同淋洗剂的淋洗效果。结果表明乳化合成的微乳液对焦化厂土壤中多环芳烃的总去除率高于单独使用表面活性剂为淋洗剂对土壤中多环芳烃的总去除率,说明生物柴油及植物油与表面活性剂乳化形成的微乳液对原污染土壤中的多环芳烃具有显著的增溶作用。1%TW-80和2.5%TW-80对土壤中多环芳烃总去除率分别为11%和14%;以2.5%TW-80为原料乳化合成的微乳液的淋洗去除率较以1%TW-80为原料乳化合成的微乳液高,总去除率分别为15%～30%和11%～18%;以生物柴油为原料乳化合成的微乳液的淋洗去除率较以植物油为原料乳化合成的微乳液高,分别为17%～30%和15%～23%,且对多环芳烃的去除率与其辛醇水分配系数(logKow)呈线性相关关系。     

一株菲降解菌的筛选及降解动力学分析

从克拉玛依油田附近稠油污染土壤中筛选出能以菲为唯一碳源的菲降解菌y-8,通过形态观察、生理生化特性及16SrDNA比对序列分析对该菌株进行了鉴定,确定菲降解菌y-8属于弯曲假单胞菌(Pseudomonas geniculata)。菲降解菌y-8在30℃、接种量2%(体积分数)、pH=7.0、170r/min的条件下振荡培养72h,对初始质量浓度为100mg/L菲的降解率达到93.7%,同时可耐受较高质量浓度的菲(3 000mg/L)。同时,对不同初始浓度菲降解动力学曲线进行分析,建立菌降解的指数模型,得到一级反应动力学方程:lnc=-0.045 1t+A(其中,c为菲质量浓度,mg/L;t为降解时间,h;A为常数),半减期为91.01h。     

重金属-多氯联苯复合污染土壤同步洗脱

电子垃圾拆解区土壤具有重金属与有机物复合污染的特性,尤其以Cu、Pb、Cd和多氯联苯(PCBs)的复合污染较为突出。为了同步脱除土壤中重金属与PCBs,选用增溶物质:Tween 80、TX-100、SDBS、β-环糊精与螯合剂柠檬酸依次组合进行复合污染土壤淋洗实验,应用批量平衡震荡法研究它们对重金属(Cu、Pb、Cd)与PCBs(Aroclor 1254)的洗脱效果。通过比较洗脱效果、环境友好性等方面,得出非离子表面活性剂Tween 80与天然螯合剂柠檬酸2种淋洗剂复合最佳;进一步研究两者的淋洗先后顺序、浓度配比、洗脱时间及淋洗剂p H对污染土壤洗脱效果的影响,结果表明,在Tween 80和柠檬酸均为10 g/L、p H=6、淋洗时间12 h时淋洗效果达到最佳,对Cu、Pb、Cd及PCBs的洗脱率分别达到98.77%、55.92%、66.82%和58.01%。因此,利用Tween80和柠檬酸组合可同时有效去除土壤重金属和PCBs,是复合污染土壤淋洗修复的有效淋洗剂。     

菲污染土壤黑麦草/苜蓿间作修复效应

多环芳烃类化合物(PAHs)是环境中普遍存在的持久性有毒有机污染物,因具有强烈的"三致"作用,业已引起各国环境科学工作者的广泛关注,PAHs污染土壤的修复也已成为环境科学与工程领域的研究热点。以菲为PAHs的代表,研究了黑麦草/苜蓿间作对多环芳烃(菲)污染土壤的修复效应。通过温室盆栽模拟实验,观察到5 mg/kg和50 mg/kg污染水平没有明显抑制黑麦草和苜蓿的生长;黑麦草/苜蓿间作促进了植物对土壤菲的吸收,且间作体系根系富集系数大于单作;土壤中菲的可提取浓度随时间的延长逐渐减少,在菲重度污染土壤上,黑麦草/苜蓿间作修复效果明显优于单作,菲去除率可高达90.53%。因此,对于重度PAHs污染土壤该体系是一种有实际应用价值的间作修复体系。     

Fe2+-热活化过硫酸钠氧化降解菲及其对土壤的影响

在模拟菲污染土壤中用β-环糊精(β-CD)作为Fe²⁺螯合剂,考察了Fe²⁺-热(45℃)活化过硫酸钠(Na₂S₂O₈)氧化降解菲的效果及其对土壤的影响。结果表明,Na₂S₂O₈∶菲=80、Fe²⁺∶Na₂S₂O₈=1/3、β-CD∶Fe²⁺=1/10(均为摩尔比)时,菲的降解率最高,达85.1%。Fe²⁺活化时主要自由基为SO^-₄·和·OH,而热活化时主要为·OH。根据中间产物推测菲的两条降解途径为：自由基攻击菲的9、10位点生成(1,1’-联苯)-2,2’-二甲醛或攻击2、3位点氧化开环生成2-乙基-6-甲氧基萘,再形成邻苯二甲酸二丁酯,最终矿化为CO₂和H₂O。土壤氧化修复后,pH降低,氧化...     

环糊精及其衍生物对降低铅和菲的藻类毒性研究

研究了环糊精(CD)及其衍生物对重金属铅和有机物菲及其复合污染胁迫下斜生栅藻(Scenedesmus obliquus)的毒性影响。结果表明,天冬氨酸-β-CD(ACD)具有促进斜生栅藻生长的作用。在单一铅或菲胁迫下,低浓度时能促进斜生栅藻的生长作用,但当铅质量浓度≥0.10mg/L或菲质量浓度≥10μg/L时,斜生栅藻的生长都受到了不同程度的抑制。100 mg/L的ACD加入后,在相同浓度的铅或菲胁迫下,斜生栅藻抑制率明显降低。其中,铅对斜生栅藻96h的半数效应浓度(EC50)由0.96mg/L增加到了3.79mg/L,菲对斜生栅藻96h的EC50由40μg/L增加到了104μg/L,毒性明显降低。复合污染时,铅和菲对斜生栅藻的毒性表现出协同作用。不同CD(α-CD、β-CD和γ-CD)及其衍生物(ACD和羟丙基-β-CD)中,对降低斜生栅藻毒性效果最好的为ACD。     

醇对柴油微乳体系性能的影响

采用AOT为表面活性剂,不同碳链长度正构醇为助表面活性剂,通过稀释法制备了AOT/柴油/正构醇/水微乳体系。考察了醇与表面活性剂的质量比(r)和正构醇的碳链长度对柴油微乳体系的影响,对不同条件下制备的微乳体系的电导率(δ)、界面张力(γ)及运动粘度(μ)进行了表征。结果表明,采用正丁醇时,微乳体系会出现渗滤现象。采用其他醇时,微乳体系的最大增溶水量(W0)随碳链长度增加而减小,随r增大先增大后减小;随增溶水量(W)增加,δ增大直至达到稳定,γ减小,μ增大;随醇碳链长度增大,δ减小,γ、μ增大;随r增大,δ增大,γ、μ减小。采用正戊醇(r=0.4)时,微乳体系的W0最大,γ、μ均较小,柴油微乳液体系的性能较佳。     

膜生物反应器处理微污染水源水的研究与应用现状

膜生物反应器及其组合工艺能实现水源水中微污染物的有效去除,是一种新型高效水处理工艺.总结了膜生物反应器处理微污染水源水的研究与应用现状、污染物去除效果和机制;在分析膜污染机制基础上归纳了膜污染控制和污染膜清洗方式,展望了膜生物反应器在给水领域应用需克服解决的技术难点.     

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.     

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.     

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.     

Solubilization properties of polycyclic aromatic hydrocarbons by saponin, a plant-derived biosurfactant

The enhanced solubilization of polycyclic aromatic hydrocarbons (PAHs) by saponin, a plant-derived non-ionic biosurfactant, was investigated. The results indicated that the solubilization capabilities of saponin for PAHs were greater than some representative synthetic non-ionic surfactants and showed strong dependence on solution pH and ionic strength. The molar solubilization ratio (MSR) of saponin for phenanthrene was about 3-6 times of those of the synthetic non-ionic surfactants, and decreased by about 70% with the increase of solution pH from 4.0 to 8.0, but increased by approximately 1 times with NaCl concentration increased from 0.01 to 1.0 M. Heavy metal ions can enhance saponin solubilization for phenanthrene and the corresponding MSR values increased by about 25% with the presence of 0.01 M of Cd²⁺ or Zn²⁺. Saponin is more effective in enhancing PAHs solubilization than synthetic non-ionic surfactants and has potential application in removing organic pollutants from contaminated soils.     

Solubilization of PAH mixtures by three different anionic surfactants

Solubilization of naphthalene and phenanthrene into the micelles formed by three different anionic surfactants was investigated for single, binary, and ternary mixtures including pyrene. The three surfactants were sodium dodecylbenzene sulfonate (SDDBS), monoalkylated disulfonated diphenyl oxide (MADS-C12), and dialkylated disulfonated diphenyl oxide (DADS-C12). The order of increasing solubility enhancement of naphthalene and phenanthrene was SDDBS < MADS-C12 < < DADS-C12, which indicates that the hydrophobic chains in micellar core play more important role for the solubilization of polycyclic aromatic hydrocarbons (PAHs) than the benzene rings in palisade layer of a micelle. The solubility enhancement of naphthalene was slightly changed in PAH mixtures. The solubility of phenanthrene was greatly enhanced in presence of naphthalene but reduced in presence of pyrene. The explanation for these results could be that less hydrophobic compounds can be solubilized at the interfacial region of a hydrophobic core, which reduces the interfacial tension between the core and water, and then the reduced interfacial tension can support a larger core volume for the same interfacial energy.     

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.     

A compositional simulator for modeling surfactant enhanced aquifer remediation, 1 formulation

We describe a three-dimensional, multicomponent, multiphase compositional finite-difference simulator for application to the analysis of contaminant transport and surfactant enhanced aquifer remediation (SEAR) of nonaqueous-phase liquid (NAPL) pollutants. Mixtures of surfactant, water and NAPL can form many types of micellar and microemulsion phases with a complex and important dependence on many variables of which the dilute aqueous solution typically assumed in SEAR models is just one example. The phase behavior model is central to our approach and allows for the full range of the commonly observed micellar and microemulsion behavior pertinent to SEAR. The other surfactant related properties such as adsorption, interfacial tension, capillary pressure, capillary number and microemulsion viscosity are all dependent on an accurate phase behavior model. This has proven to be a highly successful approach for surfactant enhanced oil recovery modeling, so it was adapted to SEAR modeling. However, there are many significant differences between petroleum and environmental applications of surfactants, so many new features have been added to model contaminant transport and remediation and these are described and illustrated for the first time here.     

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%.     

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.     

添加剂对堆肥降解多环芳烃的影响

为了研究多环芳烃(PAHs)污染土壤堆肥修复的加速机制,在人工控温的堆肥装置中以芘、菲和芴为研究对象,采用室内模拟实验的方式研究了添加硫酸钙、过磷酸钙、草炭、竹炭、十二烷基硫酸钠(K12)和十二烷基苯磺酸钠(SD-BS)等对锯末高温堆肥降解污染土壤PAHs的影响。研究结果表明,生物堆肥可以有效的去除土壤中PAHs,堆肥7周后所有处理下芘、菲和芴的降解率基本达到80%以上。不同添加剂处理下芘、菲和芴降解率不同,尤其是添加草炭和竹炭处理中芴和菲在第4周的时候就取得90%以上的降解率,芘在第6周也取得80%以上的降解率,而且氮素的损失率也分别下降了42.6%和36.09%,比其他处理的PAHs降解率和保氮效果都要好。分析其原因,一方面可能是添加不同添加剂对堆肥过程中pH值、有机质(SOM)、总氮(TN)和过氧化氢酶(CAT)都有一定的影响,提高了土壤微生物的活性;另一方面可能是由于草炭和竹炭对氨有良好的吸附性,具有良好的保氮效果,同时也能改善了微生物和目标化合物的接触方式,从而提高了PAHs的降解率。