全氟烷基磺酸盐(PFOS)及其替代品对两栖类胚胎的发育毒性

用非洲爪蟾胚胎致畸实验和黑斑蛙胚胎发育毒性实验,比较研究了PFOS及其4种替代品对两栖动物胚胎的发育毒性。结果发现,用调聚法合成的织物三防整理剂和50%的全氟丁基有机铵盐阳离子表面活性剂同PFOS一样对非洲爪蟾胚胎有明显毒性,且织物三防整理剂和表面活性剂的毒性强于PFOS;电解氟化法合成的C4织物及C6织物三防整理剂(以下简称C4及C6织物三防整理剂)对非洲爪蟾胚胎没有明显毒性。与非洲爪蟾不同,PFOS和4种替代品对黑斑蛙胚胎没有明显毒性。结果显示,从生物安全性的角度分析,C4和C6织物三防整理剂可作为PFOS的替代品使用,而织物三防整理剂和表面活性剂的毒性比PFOS大,作为PFOS替代品使用需要慎重考虑。     

全氟辛烷磺酸盐(PFOS)及替代品对两栖类蝌蚪的急性毒性

PFOS及其4种替代品对两栖动物非洲爪蟾和黑斑蛙蝌蚪的急性毒性结果为:用调聚法合成的织物三防整理剂对非洲爪蟾蝌蚪和黑斑蛙蝌蚪的96h-LC50分别为8和21mg·L-1,而PFOS对两种蝌蚪的96h-LC50分别为92和81mg·L-1。此实验结果说明织物三防整理剂的急性毒性高于PFOS。用电解氟化法合成的C4、C6织物三防整理剂和50%的全氟丁基有机铵盐阳离子表面活性剂浓度在100mg·L-1时,对两种蝌蚪都没有毒性。这说明,从急性毒性的角度,C4、C6织物三防整理剂和表面活性剂可作为PFOS的替代品使用,但是织物三防整理剂的急性毒性比PFOS大,作为替代品使用应慎重考虑。另外,PFOS和织物三防整理剂对黑斑蛙蝌蚪的急性毒性与对非洲爪蟾蝌蚪的急性毒性存在差异。出于保护我国本土两栖动物的目的,使用黑斑蛙开展毒性评价比使用非洲爪蟾更有现实意义。     

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。     

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.     

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。     

Surfactants in sludge-amended agricultural soils: a review

Surfactants are included in different detergent formulations and are one of the most ubiquitous and important families of organic compounds. Although the generic term applies to a great number of products, 80% of their demand is covered by only ten types of compounds. The global surfactant market volume size is more than 18 million tons per year. Large quantities of surfactants are continuously released into the environment, where they can or cannot be degraded depending on their structure. The alkylbenzenesulphonate (LAS) is the most widely used surfactant. LAS can be degraded under aerobic conditions but is persistent in the environment under anaerobic conditions. Surfactants may enter the terrestrial environment through several routes, with the use of sewage sludge as fertiliser on agricultural land being by far the most important. High concentrations of surfactants and their degradation products may affect the biota. On the other hand, due to their amphiphilic nature, surfactants may interact both with inorganic as well as organic contaminants affecting their bioavailability.     

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.     

混合表面活性剂对菲和芘的增溶作用

比较了非离子表面活性剂 (Tween2 0 ,Tween40 ,Tween60 ,Tween80 ,Brij35和Brij5 8)与SDBS混合表面活性剂对菲和芘的增溶作用 .结果表明 ,在临界胶束浓度 (CMC)以上 ,表面活性剂对菲和芘有显著的增溶作用 ,菲的增溶顺序为 :Tween40 >Tween60 >Tween2 0 >Tween80 >Brij5 8>Brij35 ;芘的增溶顺序为 :Tween60 >Tween80 >Tween40 >Brij5 8>Tween2 0 >Brij35 .阴 非离子混合表面活性剂溶液的CMC值降低 ,胶束 水中溶质的分配系数Kmc增大 ,由此对菲和芘产生协同增溶作用 ,其顺序均为 :SDBS Tween60 >SDBS Tween80 >SDBS Tween40 >SDBS Brij5 8>SDBS Tween2 0 >SDBS Brij35 ,协同增溶程度在 1 1 7%— 65 8%之间 .     

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.     

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.     

Alkyl polyglucosides as cell surface modification factors: influence of the alkyl chain length

The use of surfactants in a bioremediation process is aimed at increasing the efficiency of the removal of hydrophobic contaminants from the environment. The subjects of the study were three alkyl polyglucosides (APGs) of different alkyl chain length: Glucopon 215 CS UP, Glucopon 600 CS UP, and Glucopon 650 EC. The impact of these surfactants on the surface properties of the test strain Pseudomonas fluorescens ATCC 14700, as well as on the biodegradation of diesel was tested. It was observed, that the length of alkyl chain has an influence on the cell surface properties. The modification of the cell surface hydrophobicity and the electrokinetic potential on the bacteria cells is dependent on the structure of Glucopon molecules. The elongation of alkyl chains in surfactant molecule caused an increase of the hydrophobic properties and a reduction of the electrokinetic potential on the bacteria cells. Moreover, the use of APGs below critical micelle concentration caused an increase of diesel oil biodegradation, especially in the case of Glucopons with longer alkyl chain (Glucopon 600 CS UP and 650 EC). The better diesel oil removal by tested strain after surfactant addition was correlated with the hydrophobic properties of bacteria strain.     

对硝基苯酚在阴-阳离子有机膨润土/水间的界面行为研究

用阴、阳离子表面活性剂改性制得一系列阴-阳离子有机膨润土,表征了有机膨润土的结构特征,研究了对硝基苯酚在阴-阳离子有机膨润土/水间的界面行为,并探讨了其吸附机理.结果表明:阴-阳离子有机膨润土的层间距和有机碳含量与改性时阴、阳离子表面活性剂的组成和配比有关;阴-阳离子表面活性剂在有机膨润土中形成了增溶(分配)作用较强的有机相,在一定配比下对水中有机污染物产生协同效应.     

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。     

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。     

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。     

六种表面活性剂对斑马鱼胚胎发育的毒性效应

为评价六种常见农药表面活性剂对水生生物的风险,采用斑马鱼胚胎发育技术,研究其对斑马鱼胚胎的致死效应和致畸效应.结果表明,NP-10、OP-10、农乳700、农乳602、农乳1602、宁乳33对斑马鱼胚胎的致死中浓度分别为16.44、21.13、55.86、8446、109.90、120.08 mg·L-1,其中NP-10对斑马鱼胚胎急性毒性最大,宁乳33毒性最低;随着染毒剂量的增加,斑马鱼胚胎孵化率逐渐降低,致畸率逐渐提高,六种表面活性剂显示出相似的趋势,处理浓度与胚胎孵化率(致畸率)之间存在剂量-效应关系;NP-10、OP-10、农乳700处理组均诱导斑马鱼胚胎出现躯干侧翻、游囊关闭、躯干弯曲症状;农乳602、农乳1602、宁乳33处理组出现躯干侧翻、游囊关闭症状.     

典型全氟辛烷磺酸盐(PFOS)替代品对土壤跳虫的生态毒性

利用土壤模式动物白符跳(Folsomia candida),评价4种PFOS替代产品,包括50%的全氟丁基有机铵盐阳离子表面活性剂(简称表面活性剂)、用调聚法合成的三防织物整理剂(含固率23.7%,简称织物三防整理剂)、用电解氟化法合成的C4织物及C6织物三防整理剂的生态毒性,目的是为筛选安全高效的PFOS替代品提供科学依据。研究表明,表面活性剂与三防织物整理剂对跳虫急性毒性的LC50(7d)分别为4959和1007mg·kg-1,而C4与C6整理剂对跳虫急性毒性的LC50(7d)均大于5000mg·kg-1;表面活性剂、织物三防整理剂与C4整理剂对跳虫慢性毒性的EC50(28d)分别为0.15、0.12和0.18mg·kg-1,而C6织物三防整理剂对跳虫慢性毒性的EC50(28d)大于1mg·kg-1;4种替代品生态毒性顺序为织物三防整理剂>表面活性剂>C4>C6织物三防整理剂。通过与本实验室PFOS生态毒性的研究结果比较发现,除织物三防整理剂,其余3种替代品对跳虫的生态毒性作用均小于PFOS,其中C6整理剂对跳虫的毒性最小,有望成为替代PFOS的环保型织物整理剂。     

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).     

全氟辛烷磺酸盐(PFOS)替代品对中国白羽鹌鹑的毒性

为研究全氟辛烷磺酸盐(perfluorooctane sulfonate,PFOS)替代品对环境生物的毒害效应,选用中国白羽鹌鹑作为受试生物,建立其环境危害评价毒性测试方法,并对PFOS替代化学品进行了急性经口、急性饲喂及繁殖毒性的风险评价。结果表明,全氟丁基有机铵盐阳离子表面活性剂急性经口毒性实验的LD50为500.44mg·kg-1,其余3种替代化学品在上限浓度2000mg·kg-1,白羽鹌鹑均未出现明显死亡,4种PFOS替代品对中国白羽鹌鹑的急性经口毒性均为低毒。全氟丁基有机铵盐阳离子表面活性剂急性饲喂毒性实验的LC50为970.50mg.kg-1,对白羽鹌鹑的饲喂毒性为中毒,而其余3种替代化学品在上限浓度5000mg·kg-1,白羽鹌鹑均未出现明显死亡,对中国白羽鹌鹑的急性饲喂毒性为低毒。在长期饲喂过程中,织物三防整理剂和C6织物三防整理剂会表现出一定的生殖毒性,造成中国白羽鹌鹑的孵化率降低,胚胎死亡率及未受精率升高;全氟丁基有机铵盐阳离子表面活性剂会影响到中国白羽鹌鹑的未受精率,C4织物三防整理剂未表现出明显的生殖毒性。     

全氟辛烷磺酸盐(PFOS)替代品对家蚕大造的生态毒性

以中国本地家蚕品种大造作为受试生物,实现实验室规模化饲料饲养和初步实验动物化;建立家蚕大造环境危害评价急性毒性测试方法;对4种PFOS替代品包括:50%的全氟丁基有机铵盐阳离子表面活性剂、用调聚法合成的织物三防整理剂(含固率23.7%)、用电解氟化法合成的C4和C6织物三防整理剂,进行了急性接触毒性、急性饲喂毒性及慢性饲喂毒性的安全风险评价。实验使用的4种PFOS替代品试验急性饲喂浓度均达到或超过2000mg·L-1,家蚕未出现明显死亡;在接触实验浓度达到10g·L-1时,家蚕未出现明显死亡,以上结果证明,4种PFOS替代品对大造蚕种的急性饲喂毒性和接触毒性均为低毒。较低浓度的表面活性剂会严重影响到大造蚕种的结茧率,当表面活性剂浓度为0.4g·kg-1时,蚕种不能结茧,其余3种化学品在浓度大于0.004g·kg-1,对大造蚕种的结茧率产生一定的影响作用,但抑制作用相对较为平缓。替代品均会降低家蚕茧层率,表面活性剂在浓度为0.04g·kg-1时,茧层率剧烈下降,其他3种替代品抑制作用相对平缓。织物三防整理剂、C4和C6织物三防整理剂几乎不会影响蚕卵孵化,但表面活性剂会造成家蚕孵化率降低,在0.04g·kg-1后孵化率为0。