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。     

表面活性剂对菲的增溶动力学及质量增溶比（WSR）与亲水亲油平衡值（HLB）的关系

采用振荡实验方法,比较研究了2种非离子表面活性剂（Triton X-100和Tween80）和2种阴离子表面活性剂（SDS和SDBS）对菲的最佳增溶振荡时间及其对菲的增溶能力,同时也比较分析了表面活性剂对菲的质量增溶比（WSR）与其亲水亲油平衡值（HLB）的关系.结果表明,Triton X-100、Tween 80、S...     

稳定同位素技术在污染环境生物修复研究中的应用

稳定同位素技术主要应用于地球化学,它是将人工合成的同位素标记特定的化合物,追踪标记物在生命活动中的变化规律,目前该项技术也广泛应用于环境微生物学、生态学、生物医学等领域.生物修复是利用存在于土壤、地下水和海洋等环境中的生物特别是微生物将有毒、有害的污染物降解为二氧化碳和水,或转化为无害物质,从而使污染的生态环境修复为正常生态环境的过程.这些降解微生物都来自于小部份可培养微生物,对于大部份未可培养降解微生物,通常在实验室条件下很难得到.而利用稳定同位素技术,如13C标记底物,收集利用该底物的微生物核酸,就可以得到具有降解作用的功能微生物,为环境污染生物修复提供重要的菌源和功能基因.环境中的许多物质都可以用SIP来标记,这些标记物主要有PLFA-SIP、DNA-SIP、RNA-SIP等,它们都可以用来在复杂样本中进行有特殊代谢功能微生物的鉴定和分析,在利用微生物进行生物修复中具有重要的意义.图2表1参42     

Evaluation of linear alkylbenzenesulfonate (LAS) biodegradability in sediment by solid‐phase extraction and HPLC analysis

The linear alkylbenzenesulfonate (LAS) sorption on environmental sediments has been known long ago. Their high concentrations reflect the massive input of these chemicals from household and industrial uses. However few attempts were made to identify biodegradation metabolites of LAS in sediment. In this report, a method for the determination of these compounds in sediment samples by high‐performance liquid chromatography (HPLC) is described. The first step of our work was performed by solid‐phase extraction with octadecyl‐bonded silica (C18) mini‐columns and provided a suitable recovery of LAS (90 ± 5%) and most metabolites. Furthermore, laboratory investigations led to study the behaviour of LAS in sediment. The environmental samples used for this purpose were collected from a pond (named étang de Bolmon) located in the French Mediterranean coast. Our results were in agreement with an aerobic biodegradation process of LAS that occurred only with high values of sediment redox potential and needed the samples to be vigorously shaken to ensure adequate mixing and suspension of particulate material. In a stagnant sediment or under anaerobic conditions, LAS is not degraded. p‐Sulfophenylacetic acid and p‐sulfocinnamic acid were evidenced as predominant metabolites and were found not to be persistent.     

Dye removal by biosorption using cross-linked chitosan-based hydrogels

Environmental Chemistry Letters - Synthetic dyes are an important class of recalcitrant organic compounds that are often found in the environment as a result of their wide industrial use....     

表面活性剂对土壤中重金属清洗及有效态的影响

采用两种常用的表面活性剂-十二烷基苯磺酸钠(阴离子型)、Tween-80(非离子型),对锦州铁合金厂周边Zn、Cd及Pb重金属污染土壤进行化学修复试验,研究两种表面活性剂对重金属Zn、Cd及Pb的去除率及化学形态影响.结果表明,随着表面活性剂浓度的提高,两种表面活性剂对Pb、Cd及Zn的去除作用增强,Tween-80溶液的浓度越高,对重金属的萃取效果越好,对重金属的去除能力大小顺序为Cd>Zn>Pb,最大去除率分别为83.07%、56.78%及42.57%;十二烷基苯磺酸钠在低浓度时对Cd和Pb的去除效果不明显,而对金属Zn的去除效果较好,在0.09 mol.L-1时达到最大值83.86%;与淋溶前土壤中重金属有效态含量相比较,经不同浓度十二烷基苯磺酸钠淋洗后土壤中Cd有效态含量随LAS浓度的升高而先增加后下降,而Pb的有效态含量随十二烷基苯磺酸钠升高而增加;经不同浓度Tween-80淋洗后土壤中Zn及Cd有效态含量都是随Tween-80浓度的升高而先增加后下降,Pb有效态含量随Tween-80升高而下降.     

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%。     

Adsorption of cationic and anionic surfactants onto organic polymer resin Lewatit VPOC 1064 MD PH

The adsorption of a cationic (CTAB, cetyl trimethylammonium bromide) and an anionic surfactant (SLES, sodium dodecylethersulfate) from aqueous solution onto organic polymer resin (Lewatit VPOC 1064 MD PH) was studied. A series of batch experiments were performed to determine the sorption isotherms of surfactants to organic polymer resin. The experimental studies were analyzed by Langmuir and Freundlich isotherms. Furthermore, the isotherm parameters, average percentage errors (ε) of model data, and separation factor (R _L) were calculated. Other factors influencing the adsorption capacity (contact time, adsorbent amount, and initial surfactant concentration) were also discussed. The experimental data fitted very well to the Langmuir equilibrium model in the studied concentration range. The calculated R _L values showed that the adsorption of both surfactants were favorable. Among the surfactants, CTAB showed higher adsorption capacity onto organic polymer resin compared to SLES (Q ⁰ = 250 and 34.36 mg g⁻¹, respectively).     

Ultraviolet-H2O2 oxidation of surfactants

This paper describes a study of the treatment of surfactant synthetic solutions by chemical and photolytic oxidation. Synthetic solutions of linear alkylbenzene sulfonates (LAS) are treated in this work as this is a model compound commonly used in the formulation of detergents, with a great presence in urban and industrial waste-waters. The application of ultraviolet (UV) radiation combined with hydrogen peroxide to oxidize linear alkylbenzene sulfonates (LAS) is shown to be suitable as a primary oxidation step since conversions of about 50% of the original compounds are achieved in the most favorable cases. Initially, the influence of the operating variables on the degradation levels is analyzed in this work. A kinetic model that considers the contributions of both direct photolysis and radical attack is also worked out. Direct photolysis is performed to determine the quantum yield in the single photodecomposition reaction. In addition, the rate constant of the reaction between hydroxyl radicals and linear alkylbenzene sulfonates in the oxidizing system H₂O₂/UV is determined for different operational conditions. Finally, the contribution of each oxidation pathway is quantified, resulting in a higher contribution of the radical reaction than of photolysis in all cases.     

影响厌氧氨氧化与甲烷化反硝化耦合的因素

氨氮、氮氧化物对产甲烷菌有一定的抑制作用,但可以通过驯化去除毒性.亚硝酸盐在厌氧氨氧化菌作用下与氨发生厌氧氨氧化反应.虽然厌氧氨氧化菌是自养菌,但具有异养代谢能力,并且NO2可提高厌氧氨氧化菌的活性.因此,通过特殊的反应器技术,将厌氧氨氧化菌与甲烷菌、反硝化菌复合在一个有利的微生态环境中,充分发挥它们之间的协同耦合作用,把有机物转化为清洁能源又同时脱氮,是极有前景的废水厌氧(缺氧)处理研究新方向.表1参31     

Planning for the monitoring of pollutants from non‐stationary combustion sources†

The most important constituents of traffic exhaust are carbon monoxide, nitrogen oxides, volatile organic compounds, polycyclic hydrocarbons and lead. Satisfactory analytical methods are available for measuring these compounds, but the required expenditure in their application to air pollution studies is quite different. Due to correlations between the concentrations of several exhaust components in road air conclusions regarding the expected level of some substances can be drawn by measurement of another emitted compound. But the selection of indicator compounds must be made under the aspect of the source‐specific relationship of emitted substances. The temporal and spatial distribution of air pollutants in street air is affected by traffic emissions more than by meteorological conditions. “Fingerprints”; of typical organic gaseous components of traffic exhaust also were found in residential areas.     

微塑料与有机污染物的相互作用研究进展

微塑料(粒径小于5 mm的塑料)作为海洋中一种新型的污染物正受到越来越多的关注。微塑料在全球多个海域均有检出,根据其来源分为原生微塑料和次生微塑料。原生微塑料由人工直接制造所得,常见于日常生活用品中;次生微塑料由大块塑料制品长期风化、磨损和光解形成。塑料自身含有多种有机添加剂,不断向环境中释放,污染海洋环境;微塑料表面还可吸附有机污染物,此吸附作用受两者的物理化学性质和环境条件影响,吸附污染物后的微塑料生物毒性增强。另外,聚合物复合光催化材料可加快有机污染物如染料的光降解反应速率,因而微塑料可能会促进有机污染物的光解。针对目前微塑料对有机物光降解的贡献、机理鲜见研究的问题,未来应加强以下3方面的研究:(1)微塑料对不同有机污染物光降解是否存在影响?(2)微塑料类型、尺寸以及反应条件对有机污染物光降解如何影响?(3)微塑料对有机污染物光降解影响的内在机制是什么?     

土壤中两种手性有机氯农药的选择性降解研究

为了更深入的了解和阐释手性有机氯农药在土壤中的转化和环境归趋,采用实验室室内避光培养方法,研究了o,p＇-DDT及o,p＇-DDD 2种手性有机氯农药的外消旋体在水稻土厌氧培养体系和菜园土好氧培养体系中的选择性降解情况。为了更好的利用土壤中土著微生物的活性,我们选择了厌氧微生物比较丰富的水稻土和好氧微生物丰度比较高的菜园土来做培养实验。结果表明实验体系中o,p＇-DDT及o,p＇-DDD在水稻土和菜园土中的降解均没有明显的对映体选择性。这一结果与2种手性化合物不同对映体在自然环境中的含量普遍具有差异性有所不同,说明野外环境条件和室内模拟实验条件的差异会影响手性化合物的降解选择性。在2种体系中,o,p＇-DDT的降解速率均高于o,p＇-DDD的降解速率。这与以前的研究报道一致,DDD比DDT更难降解。通过2个体系的比较,发现DDT的降解速率在厌氧体系中高于好氧体系,而DDD的降解速率与之相反,好氧体系高于厌氧体系。这应该与DDT和DDD 2种化合物的化学结构及2种土壤中微生物群落的差异有关。对于厌氧体系中的2种水稻土,采自中山的水稻土中DDT的降解速率高于江门的水稻土,这应该与中山水稻土有机质含量高于江门的水稻土有关。有机质含量的高低直接反映了土壤中微生物的多少,进而会影响污染物的降解速率。研究发现本实验所用水稻土和菜园土总有机碳含量偏低可能是影响2种化合物的对映体无降解选择性的因素之一。此外,由于本研究采用缓冲溶液将pH 调控在中性,因此本文的土壤 pH 对降解选择性的影响仍有待进一步研究。本研究中好氧体系和厌氧体系对目标物的降解选择性无明显差异。     

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.     

草甘膦毒性研究进展

随着现代农业的飞速发展,农药的应用越来越广泛。而目前草甘膦是使用最广泛、用量最大的除草剂种类之一,其在环境中的大量残留给环境带来了巨大潜在风险。介绍了草甘膦对靶标生物（植物）的制毒机理和非靶标生物（如：水生生物、两栖类动物、土壤生物和哺乳动物）的生态毒性,总结了草甘膦在群落、个体、细胞和分子水平上的生态毒性。综合国内外最新的研究表明：草甘膦制剂具有低毒性,且毒性要远远高于草甘膦酸的毒性,农药草甘膦制剂对非光合生物产生毒性的原因主要是由于表面活性剂的存在。而大多研究都表明,不同的草甘膦制剂及其组成成分毒性强弱为表面活性剂〉草甘膦制剂〉草甘膦酸〉草甘膦异丙胺盐,而草甘膦酸产生的毒性原因主要和其产生的酸性物质有关,并认为在当前的使用品种和剂量的状况下,草甘膦对人类的危害风险是很低的。最后,分析了草甘膦在土壤中与无机重金属共存的的生态毒性研究现状,认为由于草甘膦分子结构中含有磷酸基、羧基、氨基等配位基团,能够与土壤或水体中金属离子发生络合反应,使得重金属在一定程度上能够降低草甘膦的除草效率,草甘膦一定程度上也能够降低重金属对生物的毒性和有效性,此外对今后的研究重点进行了展望。     

Hydrolysis of a model surfactant as measured using ACYL coenzyme a synthetase

Hydrolysis of a model nonionic surfactant, [1‐¹⁴C]methyl palmitate, was compared between porcine esterase and lipase using a new hydrolase assay. The assay incorporates acyl coenzyme A (CoA) synthetase to convert the hydrolytic product of methyl palmitate, palmitic acid, to its acyl CoA derivative; palmitoyl CoA is separated from unreacted substrate for quantitation by a highly efficient extraction. The assay achieves quantitative separation between product and substrate due to the high water solubility of the acyl CoA derivative, eliminating the need for time‐consuming chromatographic separations. After 60 min under optimal conditions, only 20 U/mL porcine hepatic esterase hydrolyzed 93.6+0.9% of 20μM methyl palmitate, while 100U/mL porcine pancreatic lipase was required to hydrolyze only 82.3 ±0.7% of the same substrate. While both enzymes detoxified the surfactant, esterase was more efficient, possibly indicating preferential specificity for simple monoesters; generally selective for endogenous triacylglycerols, lipase may be less specific for surfactants. However, together both enzymes may enable mammals to hydrolyze ingested nonionic surfactants from oil spill dispersants, reducing their toxicity.     

Körperpflegemittel in der aquatischen Umwelt

Personal care products (PCP) are produced and used in enormous amounts world-wide. In the early 1990s, the annual production volume was more than 550.000 metric tonnes for Germany alone, where liquid bath admixtures, soaps, skin care products, shampoos and dental care products represented the main use patterns of PCPs. These preparations and their ingredients are quasi-continuously introduced into the aquatic environment during regular use, preferably via municipal wastewater treatment plants, and may reach concentrations in the ng/l or μg/l range in surface waters. Furthermore, considerable persistence and bioaccumulation potential has been shown for a number of PCPs (e.g. musk fragrances, disinfectants, antiseptics, some repellents, sunscreen agents). Except for the most important detergents and surfactants used in PCPs, the possible consequences of a chronic exposure of aquatic organisms to these compounds have not been investigated systematically to date. The information on the occurrence of PCPs in different environmental compartments is also rather fragmentary. It is the main objective of this article to provide an overview on the available literature concerning the environmental chemistry and ecotoxicology of selected PCP ingredients (e.g. fragrances, preservatives and antioxidants, disinfectants and antiseptics, repellents, sunscreen agents) The set of data on the occurrence and concentrations of PCPs in the environment and the effects in representative aquatic organisms is insufficient for the majority of the groups of substances considered and does not allow an assessment of their environmental risk. The example of musk fragrances, which represent one of the better analysed groups of PCP ingredients, shows that these compounds tend to accumulate in sediments and biota (including human beings) due to their inherent physicochemical properties, and are likely to attain considerable concentration levels. However, the knowledge about effects in aquatic organisms is rather incomplete and partially contradictory. Furthermore, detailed investigations of their potential reproductive, neuro-, immuno-and genotoxicity are lacking not only for musk fragrances, but also for the overwhelming majority of other PCP ingredients.     

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。