Binding of dialkylated disulfonated diphenyl oxide surfactant onto alumina in the aqueous phase

Adsorption of a gemini surfactant that has two monomers and a spacer in a molecule (dialkylated disulfonated diphenyl oxide with alkyl chain lengths of twelve, DADS-C12) onto positively-charged aluminum oxide in water was studied and compared with a single-monomer anionic surfactant (sodium dodecylbenzene sulfonate, SDDBS). More mass of the gemini surfactant was adsorbed than the conventional single-monomer SDDBS. Fewer moles of the first were bound to the substrate than the second indicating that larger molecular structure of the gemini surfactant does not hinder the sorption. Both surfactants followed similar sorption mechanisms, however, stronger hydrophobic interactions were shown in the bilayer formation of the adsorbed gemini surfactant.     

Solubilization of PAH mixtures by three different anionic surfactants

Solubilization of naphthalene and phenanthrene into the micelles formed by three different anionic surfactants was investigated for single, binary, and ternary mixtures including pyrene. The three surfactants were sodium dodecylbenzene sulfonate (SDDBS), monoalkylated disulfonated diphenyl oxide (MADS-C12), and dialkylated disulfonated diphenyl oxide (DADS-C12). The order of increasing solubility enhancement of naphthalene and phenanthrene was SDDBS < MADS-C12 < < DADS-C12, which indicates that the hydrophobic chains in micellar core play more important role for the solubilization of polycyclic aromatic hydrocarbons (PAHs) than the benzene rings in palisade layer of a micelle. The solubility enhancement of naphthalene was slightly changed in PAH mixtures. The solubility of phenanthrene was greatly enhanced in presence of naphthalene but reduced in presence of pyrene. The explanation for these results could be that less hydrophobic compounds can be solubilized at the interfacial region of a hydrophobic core, which reduces the interfacial tension between the core and water, and then the reduced interfacial tension can support a larger core volume for the same interfacial energy.     

Adsorptive removal of naphthalene induced by structurally different Gemini surfactants in a soil-water system

A new generation of surfactant, Gemini surfactants, have been synthesized and have attracted the attention of various industrial and academic research groups. This study focused on the use of symmetric and dissymmetric quaternary ammonium Gemini surfactants to immobilize naphthalene onto soil particles, and is used as an example of an innovative application to remove HOC in situ using the surfactant-enhanced sorption zone. The sorption capacity of modified soils by Gemini surfactant and natural soils was compared and the naphthalene sorption efficiency, in the absence and presence of Gemini surfactants with different alkyl chain lengths, was investigated in the soil-water system. The results have shown that the increased added Gemini surfactant formed admicelles at the interface of soil/water having superior capability to retard contaminant. Symmetric and dissymmetric Gemini surfactants have opposite effect on the aspect of removing of PAH attributing to their solubilization and sorption behavior in soil-water system. Compared with the natural soil, sorption of naphthalene by Gemini-modified soil is noticeably enhanced following the order of C_12-2-16 < C_12-2-12 < C_12-2-8. However, the symmetric Gemini surfactant C_12-2-12 is the optimized one for in situ barrier remediation, which is not only has relative high retention ability but also low dosage.     

Influence of the presence of heavy metals and surface-active compounds on the sorption of bisphenol A to sediment

The effects of different heavy metals (Cd, Pb), cationic surfactants cetyltrimethylammonium bromide (CTAB), anionic surfactant sodium dodecylbenzenesulfonate (SDBS) and the chemistry of the solution (pH and ionic strength) on the sorption of bisphenol A (BPA) to sediment were studied. Results showed that the presence of Cd and Pb caused a significant increase on the sorption of BPA to sediment and the sorption isotherms were in good agreement with Freundlich equation. The effect of surfactants on the adsorption of BPA onto sediment was found to strongly depend on the type of the surfactants. The presence of CTAB promoted BPA sorption and the amount of BPA adsorbed onto sediment increased linearly with concentration of CTAB. In contrast, the presence of anionic surfactant (SDBS) caused a slight reduction on the sorption of BPA. It was also found that the sorption behavior of BPA was affected by solution pH and ionic strength. The larger amount of BPA was absorbed with higher ionic strength and lower pH. This study may provide important insights into the understanding of the transport and fate of BPA in the environment.     

Removal of perfluorinated surfactants by sorption onto granular activated carbon, zeolite and sludge

Perfluorinated surfactants are emerging pollutants of increasing public health and environmental concern due to recent reports of their world-wide distribution, environmental persistence and bioaccumulation potential. Treatment methods for the removal of anionic perfluorochemical (PFC) surfactants from industrial effluents are needed to minimize the environmental release of these pollutants. Removal of PFC surfactants from aqueous solutions by sorption onto various types of granular activated carbon was investigated. Three anionic PFC surfactants, i.e., perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutane sulfonate (PFBS), were evaluated for the ability to adsorb onto activated carbon. Additionally, the sorptive capacity of zeolites and sludge for PFOS was compared to that of granular activated carbon. Adsorption isotherms were determined at constant ionic strength in a pH 7.2 phosphate buffer at 30 degrees C. Sorption of PFOS onto activated carbon was stronger than PFOA and PFBS, suggesting that the length of the fluorocarbon chain and the nature of the functional group influenced sorption of the anionic surfactants. Among all adsorbents evaluated in this study, activated carbon (Freundlich K(F) values=36.7-60.9) showed the highest affinity for PFOS at low aqueous equilibrium concentrations, followed by the hydrophobic, high-silica zeolite NaY (Si/Al 80, K(F)=31.8), and anaerobic sludge (K(F)=0.95-1.85). Activated carbon also displayed a superior sorptive capacity at high soluble concentrations of the surfactant (up to 80 mg l(-1)). These findings indicate that activated carbon adsorption is a promising treatment technique for the removal of PFOS from dilute aqueous streams.     

Fate and effect of monoalkyl quaternary ammonium surfactants in the aquatic environment

The effect of the alkyl chain of quaternary ammonium-based surfactants on their aquatic toxicity and aerobic biodegradability has been studied. Two families of monoalkylquats surfactants were selected: alkyl trimethyl ammonium and alkyl benzyl dimethyl ammonium halides. Acute toxicity tests on Daphnia magna and Photobacterium phosphoreum were carried out and EC50 values in the range of 0.1-1 mg/l were obtained for the two series of cationic surfactants. Although the substitution of a benzyl group for a methyl group increases the toxicity, an incremental difference in toxicity between homologs of different chain length were not observed. Biodegradability of the different homologs was determined not only in standard conditions but also in coastal water, both tests yielding similar results. An increase in the alkyl chain length or the substitution of a benzyl group for a methyl group reduces the biodegradation rate. The degradation of these compounds in coastal waters was associated with an increase in bacterioplankton density, suggesting that the degradation takes place because the compound is used as a growth substrate.     

Effect of the alkyl chain length on the anaerobic biodegradability and toxicity of quaternary ammonium based surfactants

The anaerobic biodegradability and toxicity to methanogenic gas production of different alkyl chain length homologs of quaternary ammonium based surfactants were examinated. Two series of these cationic surfactants were selected: alkyl trimethyl ammonium and alkyl benzyl dimethyl ammonium compounds. A simple anaerobic gas production test containing municipal digester solids as a source of anaerobic bacteria was used. Under the applied methanogenic conditions, the cationic surfactants tested showed a very poor primary biodegradation and no evidence of any extent of ultimate biodegradation was observed. The toxicity of quaternary ammonium based surfactants to methanogenic gas production decreased with increasing the alkyl chain length.     

Different behaviours in the solubilization of polycyclic aromatic hydrocarbons in water induced by mixed surfactant solutions

Water solubility of polycyclic aromatic hydrocarbons (PAHs), viz, naphthalene and phenanthrene, in micellar solutions at 25 °C was investigated, using two series of different binary mixtures of anionic and nonionic surfactants. Tween 80 and Brij-35 were used as nonionic surfactants whereas fatty acids or amphiphilic cyclodextrins (Mod-β-CD) synthesized in our laboratory were used as anionic ones. Solubilization capacity has been quantified in terms of the molar solubilization ratio and the micelle-water partition coefficient, using UV-visible spectrophotometry. Anionic surfactants exhibited less solubilization capacity than nonionics. The mixtures between Tween 80 and Mod-β-CD did not show synergism to increase the solubilization of PAHs. On the other hand, the mixtures formed by Tween 80 and fatty acids at all mole fractions studied produced higher enhancements of the solubility of naphthalene than the individual surfactants. The critical micellar concentration of the mixtures of Tween 80/sodium laurate was determined by surface tension measurements and spectrofluorimetry using pyrene as probe. The system is characterized by a negative interaction parameter (β) indicating attractive interactions between both surfactants in the range of the compositions studied.     

Effect of surfactant alkyl chain length on soil cadmium desorption using surfactant/ligand systems

The effect of surfactant alkyl chain length on soil Cd desorption was studied using nonionic surfactants of polyethylene oxide (PEO) of PEO chain lengths of 7.5 (Triton X-114), 9.5 (Triton X-100), 30 (Triton X-305), or 40 units (Triton X-405) in combination with the I- ligand. Triplicate 1 g soil samples were equilibrated with 15 ml of surfactant-ligand mixture, at concentrations of 0.025, 0.50 or 0.10, and 0.0, 0.168 or 0.336 mol/l, respectively. After shaking the samples for 24 h, the supernatant fraction was analyzed for Cd content to determine the percent of Cd desorbed from the soil. After five successive washings, 53%, 40% and 25% of Cd had been desorbed by 0.025, 0.050 or 0.10 mol/l of Triton X-114, respectively, in the presence of 0.336 mol/l of I-, whereas with the same conditions, Triton X-100 desorbed 61%, 57% and 56% Cd and either Triton X-305 or Triton X-405 desorbed 51, 40 and 14 to 16% Cd. The most efficient Cd desorption was obtained using 0.025 mol/l Triton X-100 in admixture with 0.336 mol/l I-. Increased surfactant concentration was detrimental to Cd desorption consistent with a process that blocked ligand access to the soil particle surface. After 5 washings,the cumulative cadmium desorption decreased with increasing surfactant alkyl chain length, indicating that the metal-ligand complexes are preferably stabilized by the micelles' hydrophobic octyl phenyl (OP) group rather than by the hydrophilic PEO group. In the absence of ligand, the surfactants alone desorbed less than 1% Cd from the contaminated soil, suggesting that the ligand, rather than the surfactant, extracts the metal, to be subsequently stabilized within the surfactant micelles.     

Acute toxicity and genotoxicity of five selected anionic and nonionic surfactants

The results of four toxicity bioassays of selected anionic and nonionic surface active agents were presented. Three widely used anionic surfactants that belong to alkyl sulphates (AS), alkylbenzene sulphonates (LAS) and alkylpolyoxyethylene sulphates (AES) as well as nonionic surfactants: polyoxyethylene alkyl ethers (AE) and polyoxylethylene alkylphenyl ethers (APE) were tested. Three different toxicity assays to aquatic organisms: Physa acuta Draparnaud, Artemia salina and Raphidocelis subcapitata were applied. Additionally, the genotoxicity test with Bacillus subtilis M45 Rec- and H17 Rec+ strains was performed. The obtained results showed that none of the surfactants studied was genotoxic at the concentration 1000 mg l(-1). On the basis of toxicity tests to aquatic organisms all tested anionic surfactants were harmful (LC50 between 10 and 100 mg l(-1)), whereas nonionic ones were toxic (LC50 between 1 and 10 mg l(-1)) or even highly toxic (LC50 below 1 mg l(-1)). Moreover, the bigger was the molecular weight of the tested compound, the higher toxicity was observed.     

Removal of vaporous naphthalene using polyoxyethylenated nonionic surfactants

Previous research has demonstrated that an anionic surfactant can increase the solubility of the vapor phases of both naphthalene and sulfur dioxide in water. This study examines the feasibility of removing polycyclic aromatic hydrocarbons (PAHs) during gas absorption by adding the polyoxyethylenated nonionic surfactants tetraethylene glycol monodecyl ether (C10E4), octaethylene glycol monodecyl ether (C10E8), and octaethylene glycol monotetradecyl ether (C14E8), to water. The apparent solubility and absorption rates of naphthalene in surfactant solution were slightly higher than in pure water at a concentration lower than the critical micelle concentration (CMC). However, the apparent equilibrium naphthalene solubility increased linearly in proportion to the concentrations of nonionic surfactants because of the solubilization effect of micelles at concentrations above the CMC. The solubilization effect exceeded that of the reduced mass transfer coefficient, increasing the rate of absorption of vaporous naphthalene. For the four surfactants, the capacity to solubilize naphthalene was in the order C10E4 > C14E8 > C10E8 > sodium dodecyl sulfate (SDS) and was related to the hydrophile-lipophile balance values of the surfactants. The enrichment factors, which can express the degree of naphthalene solubility in solution, were 6.09-14.2 at a surfactant concentration of 0.01 M for the three polyoxyethylenated nonionic surfactants. Empirical findings confirm that adding nonionic surfactants increases the absorption efficiency of hydrophobic organic compounds (HOCs) using spray or packed tower.     

The relationship between surface adsorption and the hydrolysis of amitraz in anionic surfactant solutions

The adsorption of amitraz to various adsorbents was studied in terms of the amount and rate of adsorption and the effect that adsorption had on the stability of amitraz in an aqueous environment. Adsorption results showed that in terms of their ability to adsorb amitraz from solution the adsorbents tested in this study can be ordered as follows: coarse carbon > cation exchange resin > or = anion exchange resin > fine carbon. Amitraz was not adsorbed on sand and potassium oxihumate. Adding sodium lauryl sulfate and potassium oxihumate to aqueous suspensions of suspended adsorbents containing adsorbed amitraz showed that both these anionic surfactants significantly increased the hydrolysis rate because the half-lives for amitraz was reduced from 27 days for a suspension to only 8 hours for amitraz adsorbed to a cation exchange resin and suspended in an aqueous buffer pH 5.8 containing 0.5% of the anionic surfactant sodium lauryl sulfate and 12 hours when 1% potassium oxihumate was added.     

Mixtures of quaternary ammonium compounds and anionic organic compounds in the aquatic environment: Elimination and biodegradability in the closed bottle test monitored by LC-MS/MS

Quaternary ammonium compounds (QACs) are widely used as disinfectants, detergents and fabric softeners. Anionic detergents are one of the most widely used chemical substances. QACs and anionic surfactants can form ionic pairs. In the present study we investigated the biodegradability of QACs in the presence of different anionic surfactants. The biodegradability of three QACs, namely benzalkonium chloride (BAC), didecyldimethylammonium chloride (DDMAC) and ethacridine lactate (EL), when applied as single substances and in combination with anionic surfactants such as benzene sulfonic acid (BSA), LAS, naphthalene sulfonic acid (NSA) and sodium dodecylsulfonate (SDS) was studied applying the closed bottle test (CBT) [OECD 301D, 1992. Guidelines for Testing of Chemicals. Closed bottle test. Organisation of Economic Cooperation and Development, Paris] at a ratio of 1:1 (mol:mol). Biodegradation was monitored by measuring oxygen concentration in the test vessels with an oxygen electrode in accordance with international standard methods [ISO 5414, 1990. Water quality - determination of dissolved oxygen. In: German Standard Methods for the Examination of Water, Wastewater and Sludge. VCH Verlagsgesellschaft, Weinheim, New York, Basel Cambridge]. Primary elimination of the QACs and of LAS was monitored by LC-MS/MS. There was little biodegradability of the QACs as either single compounds or in the presence of organic counter ions. The biodegradability of the organic counter ions was lower in the presence of QACs as compared to the single substances. Primary elimination of the QACs by sorption took place.     

Sorption of linear alcohol ethoxylate surfactant homologs to soils

Sorption onto five saturated soils of the homologs within the commercial surfactant mixture Brij 35 (registered trademark of ICI Americas) was investigated. Brij 35 is a mixture of linear ethoxylated alcohols, having an average of 23 ethoxy (EO) groups per molecule and alcohol chain of primarily 12 carbons in length (C₁₂H₂₅(OCH₂CH₂)₂₃OH). In experiments, saturated soils were exposed to various concentrations of the surfactant mixture for specified times, the slurries were centrifuged to separate the phases, the aqueous phases were extracted with 1,2-dichloroethane, and the residual homologs were derivatized with 3,5-dinitrobenzoyl chloride and analyzed by normal phase HPLC. Homologs containing 4–43 EO groups were chromatographically separated at near baseline. At aqueous Brij 35 concentrations below the critical micelle concentration (cmc), the proportion of each homolog sorbed to each of the soils increased with increasing EO chain length through the homologous series. As a result, in experiments where a significant proportion of the surfactant adsorbed, significant shifts in the aqueous phase compositions occurred to mixtures with lower mean EO numbers. A sharp break in the adsorption isotherms occurs at the cmc.     

Kinetic study of the anaerobic biodegradation of alkyl polyglucosides and the influence of their structural parameters

This paper reports a study of the anaerobic biodegradation of non-ionic surfactants alkyl polyglucosides applying the method by measurement of the biogas production in digested sludge. Three alkyl polyglucosides with different length alkyl chain and degree of polymerization of the glucose units were tested. The influence of their structural parameters was evaluated, and the characteristics parameters of the anaerobic biodegradation were determined. Results show that alkyl polyglucosides, at the standard initial concentration of 100 mgC L^?1, are not completely biodegradable in anaerobic conditions because they inhibit the biogas production. The alkyl polyglucoside having the shortest alkyl chain showed the fastest biodegradability and reached the higher percentage of final mineralization. The anaerobic process was well adjusted to a pseudo first-order equation using the carbon produced as gas during the test; also, kinetics parameters and a global rate constant for all the involved metabolic process were determined. This modeling is helpful to evaluate the biodegradation or the persistence of alkyl polyglucosides under anaerobic conditions in the environment and in the wastewater treatment.     

Structure-activity relationships for association of linear alkylbenzene sulfonates with activated sludge

Sorption of linear alkylbenzene sulfonates (LAS) on sludge particles from wastewater treatment plants was studied. The effect of alkyl chain length and the water hardness were investigated. Sorption on sludge increases with increasing alkyl chain length in the LAS molecules. The results are interpreted in terms of a hydrophobic bonding mechanism being the critical micelle concentration a good index of the surfactant hydrophobicity. The increase in free energy of adsorption for the addition of successive methylene groups to the alkyl chain was estimated as 2.4 kJ/mol. Water hardness clearly enhances the sorption of LAS homologues on sludge and seems to promote cooperative sorption at high surfactant and calcium ion concentrations. An empirical equation was provided that allow to estimate the partition coefficient between aqueous and solid phases for LAS homologues as a function of the alkyl chain length and the water hardness.     

Predicting surfactant modified soil/water distribution coefficients using micellar HPLC

Soil water/distribution coefficients (Kd) have been measured for the partitioning of naphthalene, phenanthrene and pyrene between aqueous surfactant solutions and a clean soil. The surfactants used are ABA block copolymers constructed from ethylene oxide (the monomer used to synthesise the hydrophilic A blocks) and propylene oxide (used for the manufacture of the hydrophobic B block). Three of these surfactants comprising the same size propylene oxide block but different ethylene oxide/propylene oxide ratios were investigated. Increasing amounts of surfactant in the system result in a progressive decrease in the Kd values signifying an increasing tendency for the hydrophobic solutes to be dispersed in aqueous solution due to the action of the surfactant. More significantly for equal surfactant doses the most hydrophobic surfactant possessing the lowest ethylene oxide/propylene oxide ratio reduces Kd by the greatest amount whereas the most hydrophilic surfactant reduces Kd the least. Finally micellar HPLC using the above surfactants and hydrophobic solutes was undertaken. Interpolated capacity factors evaluated for particular surfactant doses correlated well with Kd values calculated for the same surfactant doses. The relationship between Kd and capacity was found to be log-linear and the correlation line could be fitted to the data obtained for all three surfactants. It is therefore concluded that micellar HPLC may be used for preliminary evaluations of the effectiveness of particular surfactants proposed for contaminated soils restoration schemes.     

Enhanced naphthalene solubility in the presence of sodium dodecyl sulfate: effect of critical micelle concentration

Surfactants can increase the solubility of non-polar compounds, and have been applied in areas such as soil washing and treatment of non-aqueous phase liquids (NAPLs). This investigation explored the feasibility of removing vapor phase polycyclic aromatic hydrocarbon (PAH) from gases using an anionic surfactant. The solubility of vapor phase naphthalene was measured herein using gas chromatograph (GC) with a photon ionization detector (PID). The measurement results indicated that surfactant molecules were not favorable to micelle formation when temperatures increased from 25 degrees C to 50 degrees C. Regardless of whether solutions were quiescent or agitated, equilibrium naphthalene apparent solubility increased linearly with surfactant concentrations exceeding critical micelle concentration (CMC). The pH effects on naphthalene apparent solubility were small. Agitation increased naphthalene apparent solubility and lumped mass transfer coefficients. Furthermore, lumped mass transfer coefficients decreased with increasing surfactant concentration owing to increase in interfacial resistance and viscosity and decreased spherical micelle diffusion coefficients. Finally, the net absorption rate increased because the solubilization effects of micelles exceeded the reduction effects of mass transfer coefficient above the CMC. The enhanced naphthalene apparent solubility from the addition of surfactant can be expressed by an enrichment factor (EF). The EF value of naphthalene for the surfactant solution at 0.1 M with agitation at 270 rpm relative to quiescent water could reach 18.6. This work confirms that anionic surfactant can improve the removal efficiency of hydrophobic organic compound (HOC) from the gas phase.     

Evaluation of the reaction artifacts in an annular denuder-based sampler resulting from the heterogeneous ozonolysis of naphthalene

The heterogeneous ozonolysis of naphthalene adsorbed on XAD-4 resin was studied using an annular denuder technique. The experiments involved depositing a known quantity of naphthalene on the XAD-4 resin and then measuring the quantity of the solid naphthalene that reacted away under a constant flow of gaseous ozone (0.064 to 4.9 ppm) for a defined amount of time. All experiments were performed at room temperature (26 to 30 °C) and atmospheric pressure. The kinetic rate coefficient for the ozonolysis reaction of naphthalene adsorbed on XAD-4 resin is reported to be (10.1?±?0.4)?×?10^?19 cm³ molecule^?1 s^?1 (error is 2σ, precision only). This value is five times greater than the currently recommended literature value for the homogeneous gas phase reaction of naphthalene with ozone. The obtained rate coefficient is used to evaluate reaction artifacts from field concentration measurements of naphthalene, acenaphthene, and phenanthrene. The observed uncertainties associated with field concentration measurements of naphthalene, acenaphthene, and phenanthrene are reported to be much higher than the uncertainties associated with the artifact reactions. Consequently, ozone reaction artifact appears to be negligible compared to the observed field measurement uncertainty results.     

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。