Primary aerobic biodegradation of linear and oxo alcohol alkylpolyglucosides (APG)

Alkylpolyglucosides (APG) prepared on the basis of renewable raw materials have been proven ultimately readily biodegradable. They are completely green surfactants. With the development of the petrochemical industry, APG prepared by oxo alcohol have been widely used recently. They have equal physicochemical properties with those prepared with renewable raw materials, but there is little information about their environmental compatibility. Primary aerobic biodegradability of linear alcohol and oxo alcohol APG was compared in this study. The results showed that oxo APG had similar good blodegradability with linear alcohol APG. In a shaking-flask test, more than 87% APG could be degraded after 21 d and are therefore completely green surfactants. The relationship between structure and biodegradability was studied. The hydrophobic and hydrophilic groups affected their biodegradation. Biodegradability deteriorated with increasing chain length and size of head groups. Branching did not affect their biodegradation. The degradation rate decreased with increasing head group size. Monoglucoside degraded faster than diglucosides, and diglucosides degraded faster than polyglucosides. Accordingly, a potential degradation pathway was proposed. APG were hydrolyzed to alcohol and polysaccharide in the first step, then the alcohol was oxidized to CO₂ and H₂O by β or α oxidation. The polysaccharide was hydrolyzed to glucose, and then the glucose was degraded by a glucose metabolism mechanism. This pathway provided a good explanation of the experiment results.     

Micellar and Interfacial Behavior of Mixed Systems Containing Glycoside‐Based Surfactant and Cationic Didecyldimethylammonium Chloride

The behavior of binary mixtures of glycoside‐based surfactants in combination with didecyldimethylammonium chloride (DDAC) has been studied using surface tension measurements. The three glycoside‐based surfactants are nonionic decyl glycoside (APG), nonionic dodecyl ethoxy glycoside (AEG) and anionic disodium dodecyl ethoxy glycoside citrate (AEG‐EC). Lower critical micelle concentrations (CMC) and minimum molecular area (A_min) values were obtained for all the mixed systems. The pC₂₀ values of APG/DDAC and AEG‐EC/DDAC mixtures are larger than pure surfactants, while the values of AEG/DDAC are between those of AEG and DDAC. Interactions between the monomers have also been investigated by determining the interaction parameters. Negative β_m and β_s values indicate synergistic effects in both the mixed micelle and monolayer formation. For different mixed systems, interaction in the mixed micelle formation becomes stronger in the order: AEG/DDAC < AEG‐EC/DDAC < APG/DDAC. The degree of synergism in the mixed monolayer formation follows the order: AEG/DDAC < APG/DDAC < AEG‐EC/DDAC.     

醇醚糖苷的提纯及其物化性能研究

采用环氧乙烷(EO)平均加合数分别为0.8和3.0的脂肪醇醚AEO08和AEO30为原料,直接与葡萄糖进行催化缩合反应,反应混合物用超临界CO2萃取技术提纯,分别得到醇醚糖苷AEG08和AEG30,并用气相色谱法定量分析了AEG08和AEG30的组成.对烷基糖苷(APG),AEG08和AEG30进行的物化性能检测结果表明,由于醇醚糖苷分子结构中引入了聚氧乙烯(EO)链,其抗硬水能力明显提高,且表面活性剂EO链越长,其在硬水中的稳定性、表面活性及泡沫等性能越好.     

Biodegradation and Ecotoxicity of Branched Alcohol Ethoxylates: Application of the Target Lipid Model and Implications for Environmental Classification

With the advent of global regulations for safer detergent and an emphasis on a shift toward more environmentally friendly formulations, the environmental profile of surfactant chemistries have moved to the forefront of product formulation and design. The two cornerstones of surfactant environmental profiles are the ability to biodegrade in the natural environment and the ecological hazard profile. The objectives of this article are to describe biodegradation and aquatic toxicity data for a series of branched oxo-alcohol ethoxylate (AEO) surfactants; to apply the target lipid model (TLM) for deriving model-based threshold hazard concentrations (HC5) of AEO; and, finally, to accurately determine aquatic classifications for AEO surfactants for use in regulatory classification frameworks. Biodegradation results indicate a high level of biodegradability of branched AEO, with C8–C13-rich oxo-alcohols with 1–20 mol of ethoxylate meeting the readily biodegradable criteria. Results from acute and chronic toxicity tests indicated comparable or lesser aquatic toxicity versus linear AEO structures previously reported in the literature. The TLM model, applied a priori, resulted in good agreement with acute toxicity data (RMSE = 0.49) and is comparable to the root mean square errors (RMSE) previously determined for other narcotic chemicals (RMSE = 0.46–0.57). Model errors for invertebrates and fish were smaller than those for algae, with the TLM systematically overpredicting acute and chronic classification of two of seven branched AEO. Furthermore, TLM-predicted HC5 values were determined to be sufficiently conservative, with 100% of observed chronic data (N = 79) falling above the HC5 threshold values, providing a useful tool for the risk assessment of AEO.     

油溶性表面活性剂生物降解度的测定

对ISO 10634-1995“水质———水介质中用于难溶有机物生物降解性能评价水溶液的制备与处理指南”推荐的方法进行逐一筛选,以期建立油溶性表面活性剂生物降解度测定的标准方法。实验结果表明,将油溶性表面活性剂超声乳化后,制备成粒径200 nm~300 nm乳液后,立即分散于水体系中进行降解,结果重复性较好,并且不影响油溶性表面活性剂生物降解度。用该方法对常见的油溶性表面活性剂的生物降解度进行了测定,结果表明大部分油溶性表面活性剂具有很好的生物降解性能;其降解规律与水溶性表面活性剂类似,疏水链长决定油溶性表面活性剂的生物降解性能,而亲水基团影响其生物降解速度。     

Surface Properties and Solubility Enhancement of Anionic/Nonionic Surfactant Mixtures Based on Sulfonate Gemini Surfactants

As a class of novel surfactants, Gemini surfactants usually exhibit fairly excellent interfacial properties in aqueous solutions on account of the unique structure. They have significant application and development potential for industrial production. However, the mixing properties of Gemini surfactants with conventional surfactants are the key to their application. The equilibrium surface tension curves of anionic/nonionic surfactant mixtures based on the sulfonate Gemini surfactant (SGS-12) were measured using the Wilhelmy Plate method. The parameters of surface adsorption, the interaction parameters between anionic and nonionic surfactants, and the thermodynamic parameters of micelle formation were calculated from the corresponding equations. In addition, the dynamic surface tension (DST) curves of anionic/nonionic surfactant mixtures were examined through bubble profile analysis, and the diffusion performance parameters were acquired from empirical formulas. The solubilization of pyrene in micelle solutions was studied using UV–vis absorption spectroscopy. The results show that the interaction parameters of all anionic/nonionic surfactants are negative, indicating that there is a synergistic effect on reducing the surface tension. For the SGS-12/OP-10, SGS-12/Tween 80, SGS-12/AEO9, and SGS-12/APG0810 mixtures, the optimum mixing ratios are 6:4, 7:3, 7:3, and 8:2, respectively. The thermodynamic data of micelles show that the formation of mixed micelles for SGS-12/APG0810 mixtures is an enthalpy-driven process. The tendency of DST curves of the SGS-12/APG0810 mixture is similar to that of SGS-12. In comparison with single-surfactant solutions, the anionic/nonionic surfactant mixtures show stronger solubilization capacity toward pyrene.     

糖苷类表面活性剂与双癸基二甲基氯化铵复配体系的物化性能及相行为

研究了糖苷类表面活性剂C8/10烷基糖苷(APG)、C12/14醇醚糖苷(AEG)和C12/14醇醚糖苷柠檬酸单酯二钠盐(AEG-EC)与双癸基二甲基氯化铵(DDAC)复配体系的物化性能和相行为。结果表明,APG/DDAC体系的表面张力、泡沫性能和乳化性能有增效作用,润湿性能无增效作用。AEG/DDAC体系的泡沫性能和乳化性能有增效作用,润湿性能无增效作用。AEG-EC/DDAC体系的表面张力和润湿性能有增效作用,泡沫性能无增效作用。用偏光显微镜研究了三元体系的相行为,结果表明,随着DDAC含量的增加,糖苷类表面活性剂/DDAC/水体系的三元相图依次出现胶束相、胶束-液晶共存相和层状液晶相。     

常用表面活性剂在彩漂液中的稳定性研究

研究了10种常用表面活性剂在含氧系彩漂液中的应用,并追踪了22个月的稳定性测试。结果表明,APG(650EC)、XP-80、AEO9、15-S-9、TO-10这5种非离子表面活性剂和烷基苯磺酸、SAS这类磺酸类物质的阴离子表面活性剂和AES均具有保持彩漂液中有效氧的稳定性,而C16MES和国产APG则不能保持彩漂液中有效氧的稳定性。     

半连续活性污泥法测定表面活性剂的好氧生物降解度

用半连续活性污泥(SCAS)法测定表面活性剂的生物降解度,考察了表面活性剂分子在活性污泥体系中的吸附-脱附作用所导致的假降解现象,研究了活性污泥浓度对降解性能的影响,并用SCAS法对AEO7、L-64、LAS和AES进行了初级和最终生物降解度的测定,结果表明以上4种表面活性剂的初级生物降解度均>90%、最终生物降解度均>70%,达到了欧盟洗涤剂法规的相关标准,均属易降解表面活性剂。     

液体洗涤剂组分对青霉脂肪酶活性的影响

研究了液体洗涤剂中常用的表面活性剂如LAS、SAS、AES、AOS、MES、烷基醇酰胺、APG、OB2 以及常用助剂如增溶剂、增稠剂、防腐剂等对青霉脂肪酶活性的影响 ,还研究了阳离子表面活性剂以及淀粉酶对青霉脂肪酶活性的影响。结果表明 ,AES、MES、AOS对酶活的影响比LAS小 ,且AES与LAS复配有利于减低LAS对酶活的影响 ;烷基醇酰胺和AEO9、TX -10一样 ,对酶活的影响较小 ;APG和OB2 则有较大影响 ;阳离子表面活性剂在较低的浓度下对酶无影响 ,有的甚至还有激活作用。液体洗涤剂中的增溶剂、增稠剂、防腐剂等在配方浓度范围内对酶活影响不大 ;淀粉酶对青霉脂肪酶的活性几乎没有影响     

表面活性剂对土壤石油污染物微生物降解的影响

选用了四种表面活性剂对辽河油田石油污染土壤微生物降解的影响进行了研究。研究表明，表面活性剂在浓度低于50mg/L时，促进作用和抑制作用都不明显；而当浓度高于100mg/L时，即高浓度时，对微生物除油有显著抑制作用。当添加H2O2和不同氮源时，发现与上述结果相类似。     

Sugar fatty acid ester surfactants: Structure and ultimate aerobic biodegradability

Ultimate aerobic biodegradabilities of an array of sugar ester surfactants were determined by International Standards Organisation method 7827, “Water Quality—Evaluation in an Aqueous Medium of the Aerobic Biodegradability of Organic Compounds, Method by Dissolved Organic Carbon” (1984). The surfactants were nonionic sugar esters with different-sized sugar head groups (formed from glucose, sucrose, or raffinose) and different lengths and numbers of alkyl chains [formed from lauric (C₁₂) or palmitic (C₁₆) acid]. Analogous anionic sugar ester surfactants, formed by attaching an α-sulfonyl group adjacent to the ester bond, and sugar esters with α-alkyl substituents were also studied. It was found that variations in sugar head group size or in alkyl chain length and number do not significantly affect biodegradability. In contrast, the biodegradation rate of sugar esters with α-sulfonyl or α-alkyl groups, although sufficient for them to be classified as readily biodegradable, was dramatically reduced compared to that of the unsubstituted sugar esters. An understanding of the relationship between structure and biodegradability provided by the results of this study will aid the targeted design of readily biodegradable sugar ester surfactants for use in consumer products.     

Environmental Impact of Ether Carboxylic Derivative Surfactants

The ultimate aerobic biodegradability and toxicity of three ether carboxylic derivative surfactants having different alkyl chains and degrees of ethoxylation were investigated. Ultimate aerobic biodegradability was screened by means of dissolved organic carbon determinations at different initial surfactant concentrations. For comparison, the characteristic parameters of the biodegradation process, such as half-life, mean biodegradation rate, and residual surfactant concentration, were determined. Increased surfactant concentrations decreased mineralization and lengthened the estimated half-life. The results demonstrate that the ultimate aerobic biodegradability is higher for the surfactants with the shortest alkyl chain and highest degree of ethoxylation. Toxicity values of the surfactants, and their binary mixtures, were determined using three test organisms, the freshwater crustacea Daphnia magna, the luminescent bacterium Vibrio fischeri and the microalgae Selenastrum capricornutum. The toxicity is lower for the surfactants with the shortest alkyl chain and highest degree of ethoxylation. The toxicity of binary mixtures of the three ether carboxylate surfactants at a 1:1 weight ratio was also measured. The least toxic mixture is formed by the surfactants having lower individual toxicity.     

Effects of polymer concentration and zone drawing on the structure and properties of biodegradable poly(butylene succinate) film

To produce various biodegradable poly(butylene succinate) (PBS) films for particular use, the effects of initial polymer concentration and zone drawing on the structure, physical properties, and hydrolytic degradation of PBS film were investigated. PBS films were prepared from chloroform solutions with different initial concentrations of 8, 11, 14, 17 and 20 g/dl. In order to investigate the drawing behavior of the PBS films with different solution concentrations, the films were drawn under various zone drawing conditions. Through a series of experiments, it turned out that the initial concentration of PBS solution in chloroform caused significant changes in the draw ratio of the PBS film. That is, the zone draw ratios of the film at initial concentration of 14 g/dl exhibited its maximum values and gradually decreased at higher or lower concentrations. Thus, it was concluded that the initial concentration of 14 g/dl is the optimum polymer concentration to produce maximum draw ratio in this work. In addition, the crystal and amorphous orientations and tensile properties of PBS film having similar draw ratio and similar crystallinity were highest at 14 g/dl and surface crystal morphologies of these films were absolutely different. The hydrolytic degradation rate of the film at 14 g/dl was lowest, but with similar draw ratio, film dimension, and crystallinity, indicating that the degradation behaviors were greatly affected by the initial polymer concentration, orientation, and crystal morphology.     

我国洗涤用绿色表面活性剂最新进展

随着石油价格的不断上涨,以油脂和淀粉等生物质资源为原料的表面活性剂越来越受到重视。以脂肪酸甲酯磺酸盐（MES）、脂肪酸甲酯乙氧基化物（FMEE）、烷基葡萄糖苷（APG）、聚甘油脂肪酸酯（PGFE）以及改性油脂和植物油酸等为代表的一系列绿色表面活性剂的生产和应用技术趋于成熟。在各类清洁产品中将逐步取代传统的石油基表面活性剂,如烷基苯磺酸钠和脂肪醇聚氧乙烯醚等。新型绿色表面活性剂的应用将推动我国洗涤剂行业逐步走上可持续发展之路。     

Studies on replacement of phosphate builders in laundry detergents using radiolabeled soils

The fabric detergency performance of systems containing different types of surfactants and several builders of reduced phosphate content has been compared using a radiolabeled sebum-clay soil. Use of this soil allows quantitative measurement of both sebum and clay removal from soiled swatches, generally cotton and permanent press Dacron-cotton. One study compared alkylbenzene sulfonate (LAS), alcohol sulfate (AS), alcohol ethoxysulfate (AEOS) and alcohol ethoxylate (AEO) as surfactants in formulations containing from 0–45% sodium tripolyphosphate (STPP). Especially under hard water conditions, the AEO and AEOS considerably out-perform the LAS and AS at equal use concentrations and are less sensitive to phosphate reduction. Tests with cotton swatches soiled with five different carbon black-oil mixtures generally rank the surfactants in the same order, although individual responses of the cloths vary considerably. A further study compares the effect of replacing STPP with sodium nitrilotriacetate (NTA) in formulations containing varying amounts of AEO or LAS. Detergency improves significantly with increasing surfactant concentration, particularly with AEO, and declines as builder strength is reduced. AEO exceeds LAS considerably in performance under the test conditions even at relatively high concentrations of LAS. Another study compares the performance of AEO and LAS at equal concentrations in formulations containing a variety of builders. AEO is generally superior to LAS in removing both sebum and clay soils and is less sensitive to builders and water hardness. The builders generally rank in this order: STPP > NTA = citrate > carbonate > sulfate. Presented at the AOCS Short Course, “Update on Detergents and Raw Materials,” Lake Placid, N.Y., June 1971.     

醇醚糖苷在农药微乳液中的应用

[目的]醇醚糖苷(AEG)是一种新型绿色功能性表面活性剂,在农药制剂中尚少有应用。研制含醇醚糖苷的啶虫脒微乳液,并将其与常规的乳油制剂做润湿力、动态接触角和药液沉积量对比试验,考察醇醚糖苷在农药制剂中应用的实际效果及可行性。[结果]通过溶剂、表面活性剂复配的筛选及拟三元相图的绘制,确定了以醇醚糖苷与十二烷基苯磺酸钠(LAS)复配作乳化剂,制备了3%和5%啶虫脒微乳液。与常规的乳油制剂相比,用醇醚糖苷制备的微乳液表面活性剂用量低,润湿性和药液沉积量优于同类乳油产品。[结论]醇醚糖苷性能优越,可作为农药乳化剂和增效剂使用。     

Primary aerobic biodegradation of cationic and amphoteric surfactants

The primary aerobic biodegradation of several cationic and amphoteric surfactants has been studied by using the shaking-flask degradation test and orange II spectrophotometric analysis. The results show that cationic and amphoteric surfactants can be readily biodegraded, with their degradation exceeding 94%. The degradation kinetics can be accurately described by the Boltzmann model. The relationship between structure and biodegradability is discussed. The presence of hydrophobic groups has a strong effect on the biodegradability of these surfactants. Biodegradability decreases with increasing chain length. The presence of hydrophilic groups mainly affects the degradation rate of these surfactants, but not their ultimate biodegradeability. Bio-degradability is deterred and degradation is slowed as steric hindrance increases. Degradation rates increase markedly when hydrophilic groups containing an amide bond are pres-ent.     

Synthesis, Characterization, Biodegradation and Evaluation of the Surface Active Properties of Nonionic Surfactants Derived from Jatropha Oil

Four nonionic surface active agents were synthesized using the fatty acids obtained from the hydrolysis of Jatropha oil. The fatty acids obtained contained different fatty acids including: palmitic, stearic, oleic, linoleic and linolenic acids in different proportions. The chemical structures of the obtained surfactants were characterized using elemental analysis and FTIR spectroscopy. The surface activities of the different surfactants were determined using surface and interfacial tension measurements. The surfactants showed good surface and interfacial activities, which are dependent on their chemical structures. Thermodynamic parameters of adsorption and micellization confirmed these results. The biodegradation tests in river water showed that the surfactants are readily biodegradable, and reached the European standards after 24 days. Surfactants containing longer nonionic chains formed stable emulsions with paraffin oil, while shorter chains exhibit a lower emulsion stability performance.     

PAH biodegradation in surfactant‐water systems based on the theory of cohesive energy density (CED)

The influence of two non‐ionic surfactant additives (Triton X‐100 and Brij 35) on polycyclic aromatic hydrocarbon (PAH) biodegradation was evaluated using the chemical molecular interaction method, which is based on the theory of cohesive energy density (CED). The results indicated that PAHs have relatively higher CED values because aromatic compounds with labile π are more polarized and this encourages molecular attractions involving induced dipole force. Under different PAH‐surfactant compositions, similar CED values, which facilitated their intermolecular attractions through π–π electron interactions, gave rise to a similar biodegradation pattern. For example, when induced enzymes were able to target the same molecular bonding on the PAH and Triton X‐100, rapid degradation rates were observed in both systems. The distribution of the PAH in the monomer or micelle surfactant bulk affected the rate of PAH biodegradation. Quantification of the bacterial activity by applying specific oxygen uptake requirements (SOUR) identified an effect involving chemical molecular interaction. Changes in the physiological characteristics as measured by BioLog GN microplate measurements were identifiable and also could be related to the chemical structure of the dual substrates. Community‐level physiological profiling (CLPP) changed when PAH biodegradation took place in the presence of the different surfactants. Cluster analysis using matching coefficient and carbon degradation potential values also varied with the different PAH‐surfactant compositions. Copyright © 2007 Society of Chemical Industry