Ecotoxicity and biodegradability of antielectrostatic dicephalic cationic surfactants

Four series of dicephalic cationic surfactants, considered as new antielectrostatic agents have been investigated in order to establish their toxicity and biodegradability. Among them N,N-bis[3,3′-(dimethylamine)propyl]alkylamides, N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides, N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dimethylsulphates with different hydrophobic chain length (n-C₉H₁₉ to n-C₁₅H₃₁) and type of counterion (chloride, bromide and methylsulfate) have been studied. The inhibitory effect against microorganisms has been examined using model gram-positive and gram-negative bacteria, and yeasts. None of the tested surfactants have shown antimicrobial activity against gram-negative bacteria (Escherichia coli, Pseudomonas putida) and yeasts (Saccharomyces cerevisiae, Rhodotorula glutinis) at a concentration below 1000 μg mL⁻¹, however some of them were moderately active against gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis). The Microtox® test was successfully applied to measure EC₅₀ values of the studied dicephalic cationic surfactants. Their toxicity to Vibrio fischeri depended upon the alkanoyl chain length with the EC₅₀ values in a range of 2.6-980 mg L⁻¹. N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides 2a-b and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides 3a-b comprising n-decanoyl and n-dodecanoyl hydrophobic tails appeared to be the least toxic. Furthermore, the biodegradability under aerobic conditions of 2a-b, 3a-b was evaluated using OECD Method 301F. According to the obtained results 2a, 3a-3b can be considered as almost readily biodegradable and they are not expected to be persistent in the environment. Additionally, partial biodegradation was observed for 2b, indicating its possible biodegradation in wastewater treatment systems.     

胶束强化超滤去除水中双酚A

采用截留分子量(MWCO)为5000 Dalton、1000 Dalton的聚砜超滤膜,MWCO为1 kDa的再生纤维素超滤膜;采用十二烷基苯磺酸钠(SDBS)、曲拉通100(TritonX-100)、吐温80(Tween-80)、烷基多苷(APG)为表面活性剂,用胶团强化超滤工艺去除水中双酚A。研究了不同材质和截留分子量的超滤膜、表面活性剂浓度、膜操作压力、溶液pH和溶液中电解质等因素对该工艺的影响。结果表明,SDBS对双酚A有较好的去除效果,去除率在80%以上。在H+和Na+存在的条件下,双酚A的截留率增加,透过液中SDBS浓度降低。SDBS与非离子表面活性剂的复配可以提高双酚A截留率,降低透过液中SDBS的浓度,复配效果优劣顺序为Tween-80TritonX-100APG。     

PM2.5中类腐殖质表面活性测定方法与实例分析

建立了大气细粒子中类腐殖质（HULIS）表面活性的动态表征方法,并以华北平原乡村站点冬季大气PM_2.5样品为例,对PM_2.5中HULIS的表面活性进行表征.HULIS碳质组分（HULIS-C）浓度为2.0~4.6μg C/m³,占水溶性有机碳和总有机碳的比例分别为31%~40%和20%~26%.浓度为88~200mg C/L的HULIS水溶液,其表面张力相对于纯水降低了18%~22%.HULIS-C浓度在低于70mg C/L时表面张力降低显著,在88~320mg C/L之间降低相对缓慢.动态表面张力随着时间变化逐渐降低,在液滴形成后200s以内表面张力下降迅速,之后趋于平缓,说明表面活性分子在液滴中扩散趋于稳定需要一定的时间,该特征时间可能影响表面活性物质在云凝结核活化时的作用.证实了在污染地区的大气PM_2.5中含有一定量的表面活性物质,这些物质可能对颗粒物活化为云滴、雾滴过程产生显著影响;表面活性物质的存在可能在外界湿度变化过程中导致颗粒物发生液-液相分离现象,在颗粒物表面形成有机膜,影响活性分子摄取以及半挥发性物质的气-粒分配过程,从而影响大气非均相反应过程.     

Perfluorinated Surfactants in Surface and Drinking Waters (9 pp)

Background, Aim and Scope In this paper recent results are provided of an investigation on the discovery of 12 perfluorinated surfactants (PS) in different surface and drinking waters (Skutlarek et al. 2006 a, Skutlarek et al. 2006 b). In the last years, many studies have reported ubiquitous distribution of this group of perfluorinated chemicals, especially perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in the environment, particularly in wildlife animal and human samples (Giesy and Kannan 2001, Houde et al. 2006, Prevedouros et al. 2006). Perfluorinated surfactants (e.g. PFOS and PFOA) have shown different potentials for reproductory interference and carcinogenity in animal experiments as well as partly long half-lives in humans (Guruge et al. 2006, FSA UK 2006a, FSA UK 2006b, 3M 2005, OECD 2002, Yao and Zhong 2005). They possess compound-dependent extreme recalcitrance against microbiological and chemical degradation and, in addition, they show variable potentials for bioaccumulation in animals and humans (Houde et al. 2006). Materials and Methods: Surface and drinking water samples were collected from different sampling sites: - Surface waters: samples taken from the rivers Rhine, Ruhr, Moehne and some of their tributaries. Further samples were taken from the Rhine-Herne-Canal and the Wesel-Datteln-Canal. - Drinking waters: samples taken in public buildings of the Rhine-Ruhr area. After sample clean-up and concentration by solid-phase extraction, the perfluorinated surfactants were determined using HPLC-MS/MS. Results: All measured concentrations (sum of seven mainly detected components) in the Rhine river and its main tributaries (mouths) were determined below 100 ng/L. The Ruhr river (tributary of the Rhine) showed the highest concentration (94 ng/L), but with a completely different pattern of components (PFOA as major component), as compared with the other tributaries and the Rhine river. Further investigations along the Ruhr river showed remarkably high concentrations of PS in the upper reaches of the Ruhr river and the Moehne river (tributary of the Ruhr) (Ruhr: up to 446 ng/L, Moehne: up to 4385 ng/L). The maximum concentration of all drinking water samples taken in the Rhine-Ruhr area was determined at 598 ng/L with the major component PFOA (519 ng/L). Discussion: The surface water contaminations most likely stem from contaminated inorganic and organic waste materials (so-called 'Abfallgemisch'). This waste material was legally applied to several agricultural areas on the upper reaches of the Moehne. Perfluorinated surfactants could be detected in some suchlike soil samples. They contaminated the river and the reservoir belonging to it, likely by superficial run-off over several months or probably years. Downstream, dilution effects are held responsible for decreasing concentrations of PS in surface waters of the Moehne and the Ruhr river. In analogy to the surface water samples, PS (major component PFOA) can be determined in many drinking water samples of the Rhine-Ruhr area where the water supplies are mainly based on bank filtration and artificial recharge. Conclusions: The concentrations found in drinking waters decreased with the concentrations of the corresponding raw water samples along the flow direction of the Ruhr river (from east to west) and were not significantly different from surface water concentrations. This indicates that perfluorinated surfactants are at present not successfully removed by water treatment steps. Recommendations and Perspectives: Because of their different problematic properties (persistence, mobility, toxicity, bioaccumulation), the concentrations of specific perfluorinated surfactants and their precursors in drinking waters and food have to be minimised. Therefore, it is of utmost importance to take the initiative to establish suitable legal regulations (limitations/ban) concerning the production and use of these surfactants and their precursors. Furthermore, it is indispensable to protect water resources from these compounds. A discussion on appropriate limit values in drinking water and foodstuffs is urgently needed. Concerning the assumed soil contamination, the corresponding regulation (Bioabfall-Verordnung 1998 – Regulation on Organic Waste 1998) should be extended to allow the control of relevant organic pollutants.     

Degradation of Poly(Ethylene Glycol)-Based Nonionic Surfactants by Different Bacterial Isolates from River Water

Different bacterial strains able to attack polyoxyethylene-type nonionic surfactants were isolated by enrichment procedure from the surface waters of the Arno River. Alkylphenol polyethoxylates and alkyl polyethoxylates, as well as polyethylene glycols, were degraded and assimilated by bacterial strains in axenic cultures. Degradative routes of polyethyleneoxide chains were investigated by matching each bacterial isolate with several types of nonionic surfactants and polyethers and by the identification of their degradation products isolated during aerobic digestion experiments. In accordance with previous reports, the first attack led to the shortening of the poly(oxyethylene) chains of the nonionic surfactants. It was found that the strains able to degrade PEG segments of nonionic surfactants possess enzymatic systems unable to degrade free PEGs, whereas those degrading the latter substrates cannot degrade PEG segments coupled to hydrophobic moieties.     

添加剂和湿法除尘主要参数对炭黑去除效率的影响

选取十六烷基三甲基溴化胺(CTAB)、十二烷基苯磺酸钠(SDBS)、月桂醇聚氧乙烯(9)醚(AEO-9)和壬基酚聚氧乙烯醚(OP-10)4种表面活性剂配制成吸收液,采用伞形罩洗涤器对燃煤窑炉黑烟进行湿法除尘净化实验,探讨添加剂种类、入口含尘浓度(Cin)、入口风速(u)和液气比(L/G)参数的不同对炭黑(BC)去除效率(η)的影响,结合压降(ΔP,Pa)的变化提出高效脱黑的可行方案.结果表明,在实验条件同为Cin=2g·m-3、u=12m·s-1和L/G=0.2L·m-3条件下,4种吸收液脱黑效果差别不大,AEO-9吸收液具有略明显的优势,炭黑去除效率可达到99.5%(0.06mmol·L-1,AEO-9);在u=12m·s-1和L/G=0.2L·m-3条件下,Cin=5g·m-3时更利于洗涤器对黑烟的净化,AEO-9吸收液的炭黑去除效率近乎100%,ΔP变化不大;入口风速的变化对炭黑去除效率和压降的影响比较明显,当Cin和L/G分别为2g·m-3、0.2L·m-3时,最佳入口风速为12～14m·s-1,炭黑去除效率保持在99%以上;最佳操作液气比可控制在0.2～0.4L·m-3.     

水中阴离子表面活性剂的测定

偶氮红两相滴定法在ｐＨ＝７．５的条件下,能测定水和废水中的各种阴离子表面活性剂的摩尔浓度。本文通过对硫酸盐、磺酸盐、苯磺酸盐、肥皂和磷酸盐等各类阴离子表面活性剂的测定,以及干扰试验和实际水样测定,表明此法优于亚甲基蓝分光光度法。方法的变异系数为１．０％（ｎ＝１１）,最小检出浓度０．０５２ｍｇ／Ｌ（ｎ＝２１）,加标回收率９２．１％－１１０．２％,平均１００．６％（ｎ＝１４）。建议水中阴离子表面活性剂     

农药助剂对蚯蚓(Eisenia foetida)的急性毒性

为评价农药助剂对土壤生物的毒性效应,分别采用滤纸接触法和人工土壤法测定了不同类别农药助剂对赤子爱胜蚓(Eis enia foetida)的急性毒性.结果表明:19种非离子表面活性剂中,烷基酚聚氧乙烯醚与脂肪醇聚氧乙烯醚毒性较高,滤纸法48 h-LC50为7.630 ～ 39.65μg·cm-2,人工土壤法14 d-LC50为876.5 ～2 786.6 mg· kg-1,其它类型非离子表面活性剂毒性较低.5种阴离子表面活性剂中,十二烷基硫酸钠、十二烷基苯磺酸钙毒性高于木质素磺酸钠、木质素磺酸钙、亚甲基双萘磺酸钠,滤纸法48 h-LC50为6575 ～ 41.89 μg· cm-2,人工土壤法14 d-LC50为1 195.0～1 911.7 mg·kg-1.13种溶剂中,二甲苯、乙苯、甲苯、正丁醇、环己酮表现出较高的毒性,滤纸法48 h-LC50为6.587 ～ 57.62 μg ·cm-2,密封人工土壤法48 h-LC50为181.9 ～781.5 mg·kg-1.采用两种方法测得的5种填料高岭土、白炭黑、硅藻土、凹凸棒土和轻质碳酸钙的毒性均较低.采用两种方法测得的毒性系统偏差接近,重现性均较好,并且滤纸接触法测得的毒力高于人工土壤法.     

湿润剂溶液在硫化矿矿尘中的反向湿润行为研究

采用毛细管反向渗透湿润实验方法,研究了两种阴离子型湿润剂对两种硫化矿矿尘的反渗长度与反渗时间的关系.在实验中,环境和溶液的温度不高(20℃左右),所选的两种湿润剂对硫化矿矿尘都具有一定的改善湿润效果作用,试剂A比试剂B稍好.在反渗长度1 cm内,其反渗长度与反渗时间接近线性关系;反渗长度增大,其反渗长度与反渗时间近乎成抛物线的关系.研究结果显示,用毛细管反渗湿润法研究湿润剂对硫化矿矿尘的湿润行为时,反渗时间与反渗长度的关系基本可用Washburn方程描述;但除了方程中所含的参数外,还存在着诸多的影响因素,如几何条件、矿尘的物理化学性质、湿润剂的种类和浓度梯度等.     

非离子表面活性剂淋洗萘污染土壤的修复研究

采用土柱实验研究了非离子表面活性剂对焦化厂萘污染砂土的淋洗效果,同时研究了超声预处理对非离子表面活性剂土壤淋洗的增强效果及粉土和粘土对非离子表面活性剂土壤淋洗的不利影响.研究表明,1)1g·L-1的TritonX-100、AEO-9和Tween80对同一萘浓度(192.4mg·kg-1)的土壤洗脱效率分别为73.0%、81.5%和59.0%,2g·L-1的表面活性剂的洗脱效率要高于1g·L-1的洗脱率,分别为96.5%、95.1%和88.2%.2)对土壤进行短时超声处理(80Hz)促进了洗脱率的提高,超声10min的淋洗效果要高于超声5min的淋洗效果;土壤分别经5min和10min超声处理后,2g·L-1浓度的TritonX-100对萘的洗脱率从94%分别提高到98.8%和99.6%,洗脱时间从255min分别减少到172min和160min.3)砂土中含有粉土和粘土对洗脱效果有不利影响,且粘土的影响要更严重,当萘污染的砂土混入5%的粘土时,2g·L-1浓度的TritonX-100对萘的洗脱率从94.7%下降至73.8%,洗脱时间从255min增加至605min,而混入20%的粉土洗脱率仅下降到88.4%,洗脱时间增加至512min.