Controlling microbiological interfacial behaviors of hydrophobic organic compounds by surfactants in biodegradation process

Bioremediation of hydrophobic organic compounds （HOCs） contanlinated soils involves several physicochemical and microbiological interracial processes among the soil-water-microorganism interfaces. The participation of surfactants facilitates the mass transport of HOCs in both the physicochemical and microbiological interfaces by reducing the interfacial tension. The effects and underlying mechanisms of surfactants on the physi-cochemical desorption of soil-sorbed HOCs have been widely studied. This paper reviewed the progress made in understanding the effects of surfactant on microbiological interlhcial transport of HOCs and the underlying mechanisms, which is vital for a better understanding and control of the mass transfer of HOCs in the biodegradation process. In summary, surfactants affect the microbiological interfacial behaviors of HOCs during three consecutive processes： the soil solution-microorganism sorption, the transmembrane process, and the intracellular metabolism. Surfactant could promote cell sorption of HOCs depending on the compatibility of surfactant hydrophile hydrophilic balance （HLB） with cell surface properties; while the dose ratio between surfactant and biologic mass （membrane lipids） determined the transmembrane processes. Although surfactants cannot easily directly affect the intracellular enzymatic metabolism of HOCs due to the steric hindrace, the presence of surfactants can indirectly enhanced the metabolism by increasing the substrate concentrations.     

产表面活性剂降解石油菌株产物性质及降解性能研究

微生物是组成生态系统的重要成员,在污染物去除中发挥着重要作用,是生物修复中的主力,然而在石油污染修复过程中,石油烃的疏水性会限制微生物对石油的降解,但一些微生物的细胞代谢物即生物表面活性剂,它是微生物在一定条件下代谢分泌产生的具有一定表面活性,集亲水基和疏水基结构于一分子的两亲性化合物,可以促进油的乳化,提高油的分散程度,增大菌株和油珠的接触机会,促进对石油烃的吸收和降解。在实验室分离得到了7株产表面活性剂石油降解菌株,经分子鉴定可知菌1和菌2都为粘质沙雷氏菌Serratia marcescens,菌3为居植物柔武氏菌Raoultella planticola,菌4,菌6和菌7都为克雷伯氏菌Klebsiella variicola,菌5为蜡状芽孢杆菌Bacillus cereus。主要研究了它们的生长与表面活性剂物质分泌状况的关系,发现随着时间增加,OD值随之增大,表面张力呈现下降趋势;并对菌株产物进行提取和薄层层析,离子型分析和红外光谱分析,初步判断其产物均为阴离子糖脂类;通过pH,初始油质量浓度,接种量和盐度4个单因素的变化研究菌1粘质沙雷氏菌,菌3居植物柔武士菌,菌5蜡状芽孢杆菌和菌6克雷伯氏菌对石油类物质降解能力,发现菌3居植物柔武氏菌和菌5蜡状芽孢杆菌降解性能较好;通过响应曲面法优化蜡状芽孢杆菌的降解条件,得出其最佳降解条件为pH为5.02,油质量浓度为3 g·L-1,接种量为1199.98μL,盐度为0.5 g·L-1时,在此条件下,菌株对石油的降解率为66.94%。     

Effect of surfactants on Fenton's reagent-mediated degradation of Kraft black liquor

One of the limitations of the biodegradation of hydrophobic chemical compounds, like lignins, is their low solubility in the aqueous solution where this process takes place. To resolve this problem, surfactants have been used to improve the solubility of these hydrophobic compounds. In this investigation, we studied the effect of surfactants (anionic, cationic, and non-ionic) on the treatment of Kraft black liquor with Fenton's reagent. In the Fenton reaction, H2O2 (two different concentrations, 10 mM and 20 mM), FeCl2 (1 mM) and surfactant solution (10%) were used. Black liquor degradation was determined by UV/Visible spectrophotometry and by measuring phenolic groups. In the presence of Fenton's reagent, the optimum conditions for the oxidative degradation of black liquor were 10 mM H2O2, 1 microL of 10% solution of anionic surfactant (SDS). The importance of the use of surfactants for preparing black liquor for subsequent Fenton's reagent-mediated degradation was discussed.     

不同类型表面活性剂对1，2，4-三氯苯的增溶作用

研究了阴离子表面活性剂十二烷基硫酸钠、阳离子表面活性剂十六烷基三甲基溴化铵和非离子表面活性剂脂肪醇聚氧乙烯醚LAE对1,2,4-三氯苯（TCB）的增溶作用。讨论了表面活性剂类型对增溶作用的影响。比较发现,非离子型表面活性剂的增溶能力高于离子型表面活性剂。其原因主要是疏水有机物在非离子表面活性剂胶束中的增溶方式不同造成的。3种表面活性剂对TCB的增溶数据还表明,增港作用不仅在临界胶束浓度（MC）以上发生,而且在表面活性剂浓度低于CMC时亦有明显的增溶作用。     

生物修复中有机污染物的生物可利用性

论述了土壤和地下水生物修复中有机污染物的生物可利用性。污染物的可利用性对生物修复速率和生物强化效率有重要影响。生物可利用性是指土壤和地下水中的微生物或其胞外酶对有机污染物的可接近性，它受土壤理化性质、污染物和微生物性质、污染接触时问等许多因素的综合影响。污染物的介质吸附、多相分配、老化和形成非水相基质，以及土壤微生物的吸附、过滤和沉降作用降低了污染物的可利用性。促进土壤中污染物和微生物的解吸附，增强非水相基质的溶解，加速土壤污染物与微生物之间的质量传递，可以增强污染物的可利用性和生物降解的速率。施用表面活性剂和电动力学方法可有效地增强污染物的生物可利用性。     

A Biosurfactant-Enhanced Soil Flushing for the Removal of Phenanthrene and Diesel in Sand

In order to examine the potential of biosurfactants in soil remediation, and to investigate the effects of several operating conditions, such as flow rate, biosurfactant concentration and surfactant type, biosurfactant-enhanced soil flushing was conducted. In the biosurfactant-enhanced soil flushing process, the removal efficiency increased as the flow rate decreased. Rhamnolipid showed no effect on the removal efficiency of phenanthrene and diesel from sand in the concentration range 0.3-0.5%. However, rhamnolipid showed higher efficiencies for the removal of phenanthrene and diesel from sand than Tween 80. Based on total recovery, following an equivalent pore volume flush, it was more difficult to remove diesel than phenanthrene. In order to obtain the specific removal efficiency, more pore volumes of surfactant solution may be required in field applications. Under optimum conditions, the biosurfactant removed as much as 70% of the phenanthrene and 60% of the diesel in the sand. These results indicate that the use of biosurfactants in the flushing process is favorable, not only with respect to the environment, but also on removal efficiencies.     

一株新的反硝化短程除硫菌的鉴定及主要培养因素筛选

依据反硝化除硫原理,以味精废水污泥为种泥,利用全混流反应器富集并分离出同步反硝化短程除硫菌(SNBI),采用传统与现代分子生物学相结合的手段对其鉴定,以确定其分类地位;同时对SNB1的主要培养因素(营养和环境)进行筛选.结果表明:SNB1的形态特征及生理生化指标与Thauera selenatis最相似,同源性达99.0%,属短杆菌属,尚无中文命名;生理生化指标、富集条件及富集过程物料平衡显示SNB1是一株兼性厌氧反硝化除硫菌;培养SNB1的最佳碳源为蔗糖,最佳氮源为蛋白胨,最佳培养温度为35℃,最适宜pH范围为7～9;最佳条件培养时,OD_(650)和对数细菌数量(CFU)呈直线相关,相关系数R~2=0.981.     

应用化学清洗剂去除包气带石油污染物的实验研究

本文探讨了应用化学法清除包气带残油的技术，研究分两个方面，（１）分析包气带土壤与第四纪沉积物对石油烃类的吸附特征，（二）在对单种表面活性剂优选的基础上，确定了清洗效率较高的阴离子－非离子表面活性剂的混合配方，通过一次性淋洗和土柱淋洗实验，了解表面活性剂等清洗剂对油类物质的去除效率。     

Biodegradation of phenol by native microorganisms isolated from coke processing wastewater

The present investigation was undertaken to assess the biodegradation of phenol by native bacteria strains isolated from coke oven processing wastewater. The strains were designated ESDSPB1, ESDSPB2 and ESDSPB3 and examined for colony morphology Gram stain characters and biochemical tests. Phenol degrading performance of all the strains was evaluated initially. One of the strains namely ESDSPB2 was found to be highly effective for the removal of phenol, which was used as sole carbon and energy source. From an initial concentration of 200 mg I(-1) it degraded to 79.84 +/- 1.23 mg l(-1). In turn the effect of temperature (20 to 45 degrees C), pH (5-10) and glucose concentration (0, 0.25 and 0.5%) on the rate of phenol degradation by that particular strain was investigated. Observations revealed that the rate of phenol biodegradation was significantly affected by pH, temperature of incubation and glucose concentration. The optimal conditions for phenol removal were found to be pH of 7 (84.63% removal), temperature, 30 degrees C (76.69% removal) and 0.25% supplemented glucose level (97.88% removal). The main significance of the study is the utilization of native bacterial strains from the waste water itself having potential of bioremediation.     

Mikrobieller PAK-Abbau

The biodegradation of the five ring PAH benzo[a]pyrene (BaP) is assumed to be limited by the low water solubility of this compound. A mixed culture of microorganisms — isolated from a PAH-contaminated soil — was able to degrade¹⁴C labelled BaP in mineral medium by cometabolism with phenanthrene, fluoranthene, anthracene and pyrene as sources of carbon and energy. The mineralisation of these compounds to low levels resulted in an inhibition of the degradation of BaP. After the new addition of the four PAH compounds to the culture medium the mineralisation of BaP started again. A non-ionic surfactant of the alkylpolyglycoside type (Plantacare 2000 UP) increased the concentration of BaP in the culture medium because of solubilization. At high Plantacare concentrations, the degradation of BaP was completely inhibited above the critical micelle concentration (cmc). The degradation of the three and four ring PAHs was also inhibited. If the surfactant was metabolised to concentrations below the cmc, an increase of mineralisation of BaP could occur up to 24% in 384 days.     

城市污泥中邻苯二甲酸酯的好氧降解规律研究

为评价邻苯二甲酸酯类环境激素在环境中的滞留情况,妥善解决城市污泥的处理处置问题,对城市污泥中6种邻苯二甲酸酯的好氧生物降解规律进行了研究。结果表明,邻苯二甲酸酯的好氧生物降解性随烷基链含碳数的增加而降低;其好氧降解过程可用一级动力学模型描述;其好氧生物降解速率常数与烷基链含碳数、降解半衰期与烷基链含碳数、降解速率常数与正辛醇—水分配系数之间存在良好的相关性。     

溢油分散剂中吐温80对石油中多环芳烃在海水中光降解的影响

溢油事故发生后喷洒溢油分散剂是常用的应急措施之一,这使得溢油分散剂中的表面活性剂与石油中的重要污染物多环芳烃(PAHs)在海水中共存。光化学转化是水中PAHs的重要转化途径,这些共存表面活性剂如何影响PAHs在海水中的光化学消减还有待阐明。本研究选取溢油分散剂的重要活性成分吐温80和石油中2种不同类型的PAHs(菲和二苯并噻吩),通过光化学实验考察不同浓度吐温80对菲(PHE)和二苯并噻吩(DBT)在海水中的光降解速率常数和光解量子产率的影响,并通过量子化学计算的手段研究其影响机制。研究发现:吐温80可以使PHE和DBT的阳离子自由基回到稳定的基态,降低PHE和DBT的光解量子产率,从而抑制PHE和DBT的光降解。该结果表明,在评价溢油分散剂的风险性时不可忽视其对PAHs环境转化行为的影响。     

有机酸与表面活性剂联合作用对土壤重金属的浸提效果研究

重金属污染土壤的原位淋洗修复既要实现对重金属的高效去除,还要尽量减少对土壤性质的破坏,这一点在农业污染土壤修复中尤为重要。以张士污灌区农田土壤为研究对象,利用振荡浸提技术筛选有机酸和表面活性剂组合,并确定了两者联合淋洗修复污染土壤的最佳配比。结果表明：有机酸（酒石酸、乙酸、柠檬酸和苹果酸）中的酒石酸浓度为0.5 mol.L-1和表面活性剂（SDBS、鼠李糖和皂素）中的皂素质量分数为0.7%时对土壤Cd、Pb、Zn的浸提效果较好;在酒石酸与皂素体积配比为1∶1时,对重金属Cd、Pb、Zn浸提效果最好,浸提率分别为87.62%、36.30%、20.67%;单一有机酸、表面活性剂或者有机酸与表面活性剂的混合溶液,对土壤重金属的浸提效果均为Cd〉Pb〉Zn。虽然有机酸与表面活性剂联合浸提效果略低于酒石酸浸提,但其弱酸性对土壤性质影响较小,在原位淋洗修复工程中有较好的应用前景。     

Effect of surfactants on phosphatase level of fresh water fish Labeo rohita

Alterations in the activity of enzymes Acid phosphatase (E.C.3.1.3.2) and Alkaline phosphatase (EC 3.1.3.1) in organs such as liver, gills and muscle of rohu following its exposure to surfactants viz. CTAB, SDS and Triton X-100 were analyzed. Different levels of exposure were given depending on the LC50 value of the surfactant used. Also, the influence of age and weight of the organisms was tested simultaneously. The activity of ACP in the tissues of fish exposed to all the three surfactants showed marked enhancement after exposure; the effect being highest in the liver followed by gill and muscle. Activity levels of ALP in different tissues of the fish exposed to the surfactants also showed an increase. Maximum increase was found in the liver followed by muscle, and gill. The increase in the levels of these enzymes indicates a stressful condition of the fish.     

螯合剂和表面活性剂辅助金福菇修复重金属污染土壤

通过温室大棚盆栽试验,研究螯合剂和表面活性剂单独或复合处理辅助金福菇修复重金属污染土壤的效果.结果表明,单独添加EDTA(乙二胺四乙酸)时,高浓度的EDTA(E2,5 mmol kg-1)使金福菇的生物量比对照降低26%,子实体Pb、Cu和Cd的浓度分别比对照提高15～88倍、0.8～3.3倍和0.5～0.6倍.单独添加表面活性剂时,各处理生物量与对照没有显著差异,且重金属浓度变化幅度没有单独添加EDTA的处理大.低浓度的表面活性剂对金福菇吸收各种重金属的影响较小,而高浓度则影响较大,但与表面活性剂及重金属种类有关.共同添加EDTA和表面活性剂时,只有当EDTA和CTAB(溴化十六烷基三甲铵)共同添加时,EC2(EDTA:CTAB=1:1)和EC3(EDTA:CTAB=2:1)的生物量显著降低,其余处理与对照差异不明显.EC3的子实体Pb和Cu浓度达到所有处理中的最大值,分别为(1 533.61±131.34)、(1 786.11±328.33)mg kg-1.EDTA和SDS(十二烷基磺酸钠)浓度比为2:1(ES3)时,子实体Cd浓度达到最大值,为(50.56±11.55)mg kg-1.此外,还分析了不同处理的重金属总积累量和富集系数.结果显示,在螯合剂和表面活性剂辅助下,金福菇修复复合重金属污染土壤具有很大的潜能.     

鼠李糖脂强化多环芳烃微生物修复的研究进展

多环芳烃(PAHs)是普遍存在于环境中具有强烈毒性、致突变性和致癌性的难降解有机物,可造成严重的环境污染.由于低水溶性而导致的低生物可利用率是限制PAHs微生物降解的主要因素.生物表面活性剂鼠李糖脂由于在形成胶束后能够大幅提高PAHs的表观溶解度,且毒性低、无二次污染,因而在PAHs微生物降解的研究中得到广泛关注.目前...     

Electrocatalytic biofilm reactor for effective and energy-efficient azo dye degradation: the synergistic effect of MnOx/Ti flow-through anode and biofilm on the cathode

● MnO _x /Ti flow-through anode was coupled with the biofilm-attached cathode in ECBR. ● ECBR was able to enhance the azo dye removal and reduce the energy consumption. ● Mn^IV=O generated on the electrified MnO _x /Ti anode catalyzed the azo dye oxidation. ● Aerobic heterotrophic bacteria on the cathode degraded azo dye intermediate products. ● Biodegradation of intermediate products was stimulated under the electric field. Dyeing wastewater treatment remains a challenge. Although effective, the in-series process using electrochemical oxidation as the pre- or post-treatment of biodegradation is long. This study proposes a compact dual-chamber electrocatalytic biofilm reactor (ECBR) to complete azo dye decolorization and mineralization in a single unit via anodic oxidation on a MnO_x/Ti flow-through anode followed by cathodic biodegradation on carbon felts. Compared with the electrocatalytic reactor with a stainless-steel cathode (ECR-SS) and the biofilm reactor (BR), the ECBR increased the chemical oxygen demand (COD) removal efficiency by 24 % and 31 % (600 mg/L Acid Orange 7 as the feed, current of 6 mA), respectively. The COD removal efficiency of the ECBR was even higher than the sum of those of ECR-SS and BR. The ECBR also reduced the energy consumption (3.07 kWh/kg COD) by approximately half compared with ECR-SS. The advantages of the ECBR in azo dye removal were attributed to the synergistic effect of the MnO_x/Ti flow-through anode and cathodic biofilms. Catalyzed by Mn^IV=O generated on the MnO_x/Ti anode under a low applied current, azo dyes were oxidized and decolored. The intermediate products with improved biodegradability were further mineralized by the cathodic aerobic heterotrophic bacteria (non-electrochemically active) under the stimulation of the applied current. Taking advantage of the mutual interactions among the electricity, anode, and bacteria, this study provides a novel and compact process for the effective and energy-efficient treatment of azo dye wastewater.     

多环芳烃生物修复中的表面活性剂

由于其致癌、致突变和致畸性，多环芳烃(PAHs)成为环境中一类重要的有机污染物。生物修复是一种经济和有效的修复污染土壤的方法。由于PAHs低的水溶性、强的吸附性，使其生物可利用性降低，不利于生物修复。添加表面活性剂是一种常见的加强PAHs生物利用性的方法。文章概述了近年来在多环芳烃生物修复中关于表面活性剂的研究进展。     

全氟化合物在阳离子表面活性剂改性碳纳米管上的吸附

采用两种阳离子表面活性剂,四丁基溴化铵(TBA)及聚乙烯亚胺(PEI)对碳纳米管进行改性,并研究了全氟辛酸(PFOA)、全氟辛烷磺酸盐(PFOS)、全氟己烷磺酸盐(PFHxS)在改性碳纳米管上的吸附行为.研究结果显示,除PFOS在TBA修饰的碳纳米管(TBA-MWCNTs)上的吸附等温线呈线性外,全氟化合物在原碳纳米管(Pri-MWCNTs)、TBA-MWCNTs及PEI修饰的碳纳米管(PEI-MWCNTs)上的吸附均为非线性.吸附等温线可以用Freundlich及Langmuir模型拟合.与Pri-MWCNTs相比,PEI-MWCNTs的零电荷点(pHzpc)增加了6.2个单位,全氟化合物的吸附系数Kd值增加2—3倍;而TBA-MWCNTs的pHzpc增加了1.0个单位,PFOS在高平衡浓度下的Kd值增加了两倍.随着溶液pH值的降低,全氟化合物在Pri-MWCNTs和PEI-MWCNTs上的吸附量有所增加,而在TBA-MWCNTs上的吸附受pH值的影响不大.这说明疏水作用及静电作用是全氟化合物在Pri-MWCNTs和PEI-MWCNTs上吸附的主要机制,而疏水作用则为TBA-MWCNTs上吸附的主要机制.与单溶质体系相比,PFOS与PFOA同时存在时二者在PEI-MWCNTs上吸附的Kd值均有所减小,且PFOA的减小程度大于PFOS.PFOS在TBA-MWCNTs上吸附的Kd值在高浓度下几乎不受PFOA的影响.