Identification of photocatalytic degradation products of non-ionic polyethoxylated surfactants in wastewaters by solid-phase extraction followed by liquid chromatography-mass spectrometric detection

The photodegradation of non-ionic surfactants (nonylphenol- and alcohol-polyethoxylates, NPEOx and CnEOx) was investigated in different waters with and without a photoinducter (Fe(III)). Deionized water and industrial effluent spiked at 0.5 mg/L with C10EO6 and NPEO9 were irradiated using a xenon arc lamp. Aliquots of the test solutions were taken at different time intervals and were preconcentrated using solid phase extraction (SPE) with C18 cartridges. Liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) was used to identify the chemical species generated from phototransformation of non-ionic surfactants. The intermediates detected included nonylphenol diethoxylate (NPEO2) and nonylphenol ethoxy acetic acid (NPE2C). Much smaller amounts of degradation products of NPEO9 having only the alkyl chain carboxylated were also formed in the photocatalysis experiment. The identified C10EO6 photoproducts included fatty alcohols and acids. Polyethylene glycols (PEGs) were also formed as the consequence of the central scission of C10EO6 and the deethoxylation of NPEO9. The photodegradation in wastewater samples was more efficient than in deionized water being the half-life (t(1/2)) of C10EO6, 48 h and 29 h in deionized water and wastewater, respectively, and for NPEO9, 17 h and 14 h in deionized water and wastewater, respectively. When induced photodegradation was undertaken, the t(1/2) for NPEO9 was 21 min and 29 min in deionized water and wastewater, respectively. Disappearance of parent compounds was observed after 120 h from the beginning of the photodegradation experiment, or after 210 min of irradiation for the photocatalysis.     

Solubilization Enhancing Effect of A-B-Type Silicone Surfactants in Microemulsions

We report a solubilization enhancing effect of A-B-type silicone surfactants in microemulsions. The effect of added long-chain silicone surfactants, Si₂₅C₃EO_51.6 (extended length≈21.8 nm) and Si₁₄C₃EO_15.8 (extended length≈8.5 nm) on the solubilization capacity of C₁₂EO₅ (extended length≈3 nm)/water/dodecane microemulsion was investigated at the hydrophile-lipophile balance temperature at which a microemulsion (surfactant) phase containing equal weights of oil and water touches the three-phase body. The addition of silicone surfactants exhibits an enormous increase of the swelling of the middle phase primarily with an associated increase in the structural length scale of the microemulsion. The solubilization power increases with increasing x₂ (mole fraction of silicone surfactants to the total surfactant) and going through a maximum it decreases, since a lamellar liquid crystal introduces in the multiphase region at low surfactant concentrations. The solubilization capacity reaches at the maximum to an almost equal level for different x₂ values, 0.02 for Si₂₅C₃EO_51.6 and 0.09 for Si₁₄C₃EO_15.8. The solubilization power of the lamellar phase shows a similar trend with lower magnitude.     

Phase behavior and rheology of oil-swollen micellar cubic phase and gel emulsions in nonionic surfactant systems

We have studied the phase behavior and rheological property of the cubic phase and related gel emulsions in water/nonionic/dodecane systems. In the phase behavior study, it is pointed out that the formation of the discontinuous cubic phase (I₁) is not common in all nonionic surfactant systems; however, a cubic phase (I₁) with oil-swollen micelles or a cubic phase microemulsion is found in the water/C₁₆EO₆/dodecane system, which can solubilize large amount of oil. It was also observed that water/C₁₆EO₆/dodecane system forms stable gel emulsion. In the rheological study we have found an anomalous behavior of the I₁ phase in the water/C₁₂EO₆/dodecane and the water/C₁₆EO₆/dodecane systems. In the water/C₁₂EO₆/dodecane system, the viscoelastic nature of the I₁ phase has been observed, which is shifted to the elastic nature with the addition of dodecane, whereas, highly elastic nature was observed in the water/C₁₆EO₆/dodecane system. In both the cases shear-thinning behavior were seen. The elastic modulus, G′ and complex viscosity, |η1| of the I₁ phase increase with the dodecane concentration in the water/C₁₂EO₆/dodecane system, whereas, decreasing trend have been observed in the water/C₁₆EO₆/dodecane system. This anomalous behavior is suggested due to the nonspherical shape of micelles or polydispersity of the micelles in the water/C₁₆EO₆/dodecane system. The rheological behavior of the O/I₁ gel emulsion was also studied in both the systems.     

Aqueous foam stabilized by polyoxyethylene dodecyl ether

Foaming properties of aqueous solutions of the nonionic surfactant polyoxyethylene dodecyl ether (C₁₂EO _n ) were studied at 298 K. Four different EO chain lengths, namely C₁₂EO₃, C₁₂EO₅, C₁₂EO₇, and C₁₂EO₉, were considered. The foams obtained from C₁₂EO₃ or C₁₂EO₅ were extraordinary stable retaining a constant volume for more than 20 h. The presence of lamellar liquid crystalline phases was mainly responsible for the super-stable aqueous foams.     

Effect of Polymer on Dynamic Interfacial Tensions of Anionic–nonionic Surfactant Solutions

The dynamic interfacial tensions (IFTs) of enhanced oil recovery (EOR) surfactant/polymer systems against n-decane have been investigated using a spinning drop interfacial tensiometer in this paper. Two anionic–nonionic surfactants with different hydrophilic groups, C₈PO₆EO₃S (6-3) and C₈PO₆EO₆S (6-6), were selected as model surfactants. Partially hydrolyzed polyacrylamide (HPAM) and hydrophobically modified polyacrylamide (HMPAM) were employed. The influences of surfactant concentration, temperature, polymer concentration, and oleic acid in the oil on IFTs have been studied. The experimental results show that anionic–nonionic surfactants can form compact adsorption films and reach ultralow IFT (10^?3 mN/m) under optimum conditions. The addition of polymer has great influence on dynamic IFTs between surfactant solutions and n-decane mainly by the formation of looser mixed films resulting from the penetration of polymer chains into the interface. The compact surfactant film will also be weakened by the competitive adsorption of oleic acid, which results in the increase of IFT. Moreover, the penetration of polymer chains will be further destroyed surfactant/polymer mixed layer and lead to the obvious increase of IFT. On the other hand, polymers show little effect on the IFTs of 6-6 systems than those of 6-3 because of the hindrance of longer EO chain of 6-6 at the interface.     

表面活性剂@Weakley型稀土多酸复合催化剂对甲基橙的光催化降解活性

以光催化活性高的多酸阴离子CeW_(10)O_(36)~(9-)、不同结构阳离子表面活性剂为构筑基元,通过水/氯仿两相静电包埋技术制备了一系列表面活性剂@多酸复合物,并利用傅里叶红外光谱(FTIR)、热重分析(TGA)对复合物的组成及结构进行分析;以甲基橙为光催化降解底物分子、表面活性剂@多酸复合物为催化剂,考察不同表面活性剂、催化剂用量、甲基橙浓度、有机染料对光催化降解率的影响;不同表面活性剂@稀土多酸复合催化剂的光催化活性顺序为DTAB(十二烷基三甲基溴化铵)@CeW_(10)TTAB(十四烷基三甲基溴化铵)@CeW_(10)CTAB(十六烷基三甲基溴化铵)@CeW_(10)OTAB(十八烷基三甲基溴化铵)@CeW_(10)DODA(双十八烷基二甲基溴化铵)@CeW_(10)。     

Effect of ethoxylated nonyl-phenols on interfacial rheological properties of oil/water systems

 Interfacial rheological properties of different Hungarian crude oil/water systems were determined in wide temperature and shear rate range and in presence of ethoxylated nonyl-phenols with ethoxy group number between 10 and 40. The fundamental conclusion of the experimental results is that the interfacial viscosity, the non-Newtonian flow behavior and the activation energy of the viscous flow drastically decrease in presence of non-ionic surfactants. Modification of these interfacial rheological properties increase with decreasing ethoxy group number and increasing tenside concentration and temperature. The most radical change was observed in presence of NPEO₁₀. As a summary it was evidenced that the interfacial rheology is an efficient and powerful detection technique, which may enhance our knowledge on formation, structure, properties and behavior of interfacial layers formed in oil/water systems. Thus, similar studies will probably accelerate the progress significantly not only in oil recovery but also in all areas of colloid science and technology. Received: 10 August 1996 Accepted: 29 November 1996     

Analysis of special surfactants by comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry

Multidimensional gas-chromatographic analyses of olesochemically based nonionic, anionic and several cationic surfactants in industrial cleaners are demonstrated. Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry allows the simultaneous determination of fatty alcohols, fatty alcohol sulphates and alkyl polyglucosides. In addition, the determination of fatty alcohol ethoxylates up to C₁₀EO₈ (highest degree of ethoxylation) and C₁₈EO₅ (longest C-chain at an ethoxylation degree of five) and the analysis of fatty alcohol alkoxylates that contain ethoxy (EO) and propoxy (PO) groups could be realized. Because of decomposition in the injector and a weak EI-fragmentation, cationic surfactants such as alkyl benzyl dimethyl ammonium chloride could also be identified by their characteristic fragments. Thermogravimetric analyses confirmed that the temperature in a normal GC injector is not high enough to cause thermal decomposition of esterquats. However, we could demonstrate that a modified silylation procedure forms decomposition products of esterquats in the GC injector which are detectable by GC × GC–(TOF)MS and allows the identification of such GC-atypical analytes.     

Origins of two surfactant phases (D and Dp′) in a temperature-composition space of water/C12EO6 / propanol / heptane system: tricritical point and critical double end point

The origins of middle surfactant phases (D and Dp′) were investigated in the composition-temperature (49–73 °C) space of a water/hexaethyleneglycol dodecyl ether (C₁₂EO₆)/propanol/heptane system at atmospheric pressure. Two types of three-phase bodies exist in the dilute C₁₂EO₆ region of the four-component composition tetrahedron at 49.0 °C. A cone-like three-phase body consisting of aqueous (W), Dp′, and oil (O) phases becomes thinner with increasing temperature, and collapses into the superimposed critical tie lines (CTL) at 51.7 °C. One end of the superimposed CTL is a critical double end point where the closed-loop coexistence curve of the Dp′ and O phases disappears. The chiral three-phase body consisting of W, D, and O phases shrinks with increasing temperature, and finally vanishes at the tricritical point near 72.5 °C. The roles of C₁₂EO₆ and propanol are discussed and the conditions for the middle surfactant phases are discussed on the basis of the whole series of three-phase behavior. Received: 9 July 1998 Accepted in revised form: 25 August 1998     

A structural study of the mesophases of two oxyethylene alkyl ether-decane-water systems,a comparison between technical grade C12EO〈7〉 and pure C12EO6

As part of a study polyoxyethylene alkyl ethers (C _m EO _n ), water and decane, the phase diagram and the structures of the mesophases of pure C₁₂EO₆ and technical grade C₁₂EO₇ were compared. The constructed phase diagrams of the two systems show a great resemblance except for one difference: the viscous isotropic phase is only present in the C₁₂EO₆ phase diagram.The swelling behavior of the lamellar and hexagonal phases was studied with smallangle x-ray scattering. Both the lamellar and hexagonal phases showed an ideal swelling behavior and no differences between the lamellar and hexagonal phases of the two systems were detected.With freeze-fracture electron microscopy the hexagonal and lamellar phases were visualized. No differences in the textures of the lamellar phases were found, however, the micrographs of the hexagonal phases of the two systems clearly showed different textures. While in the hexagonal phase of the C₁₂EO₆ system only infinite long rods were visualized, short interrupted rods were found in the hexagonal phase of the C₁₂EO₇ system.     

Extraction kinetics and ultrafiltration removal of Nickel (II) by long chain alkoxypicolinic acids in cationic and mixed micelles

Micellar particles can solubilize lipophilic extractants similarly to the organic phase in classical biphasic extraction. This analogy is used here to investigate the kinetics of complex formation between Ni²⁺ ions and long chain 5-alkoxypicolinic acids (C_n-PIC, withn=12, 15, 18) solubilized in different types of micelles, namely cetyl trimethylammonium bromide (CTAB), hexaethyleneglycol-dodecylether (C₁₂EO₆) and CTAB/C₁₂EO₆ mixed micelles. In the case of CTAB micelles, the interaction between the carboxylic function of the extractant and the polar head of surfactant molecules was expected to decrease the rate of complex formation so as to make possible kinetic separation of mixtures of metal ions. The observed rate constants for complex formation at pH 4.5 or 7.0 are indeed much smaller in CTAB micelles than in C₁₂EO₆ or mixed micelles, but they still remain too high for the previous purpose, although the influence of the surfactant concentration demonstrates, as expected, a much stronger partitioning in the case of CTAB in comparison to C₁₂EO₆. On the other hand, it is shown that, once complex formation has occurred the removal of Ni²⁺ ions can be achieved using ultrafiltration. The yield of extraction increases withn, with the mole fraction of C₁₂EO₆, and with the ligand to metal ratio.Institut Nancéien de Chimie Moléculaire (I.N.C.M.)     

Investigation of aqueous foam stability containing pigment colorant using polyoxyethylene nonionic surfactant

To improve foam stability in pigment foaming dispersions, a series of fatty alcohol polyoxyethylene ether (CmEOn) with different alkyl chain and ethylene oxide (EO) chain length (m = 12, 14, 16 and n = 5, 7, 9) were used as foam stabilizer to select the most superior structure for stabilizing foam. The effects of CmEOn on surface tension were investigated which revealed that the CMC of CmEOn in the pigment foaming dispersion decreased with the increase of surfactant hydrophobicity or the decrease of hydrophilicity. Compared to the alkyl chain, EO chain length influenced foam more significantly. C₁₄EO₅ in the pigment foaming dispersion showed lowest CMC and equilibrium surface tension. The presence of wormlike micelles and lamellar liquid crystal of SDS and C₁₄EO₅ endowed the C₁₄EO₅ pigment foaming dispersion with highest viscosity which was distinctly different with other CmEOn. C₁₄EO₅ showed the most superior stabilization effects with foam half-life of 172.9 min at 9 wt%. To further analyze the stabilization mechanism of C₁₄EO₅, the foam volume and bubble diameter change were observed with a digital microscope. The results demonstrated that the superior stabilization effects of C₁₄EO₅ were closely related to its high viscosity, which mainly resulted in the decrease of foam drainage and gas permeability. C₁₄EO₅, the optimal CmEOn structure for stabilizing foam, shows excellent foam stabilization capability in pigment foaming dispersions, which is a promising tool to realize pigment foam coloring.     

Determination of nonylphenol and nonylphenol ethoxylates in wastewater using MEKC

Nonylphenol ethoxylates (NPEO_x) are surfactants which are used worldwide and can be transformed in the environment by microorganisms to form nonylphenol (NP). Analysis of these compounds was carried out with micellar electrokinetic capillary chromatography (MEKC). Different parameters such as background electrolyte (BGE) solution, pH, type of surfactant, and sample stacking were optimized. The use of CHES (20 mM, pH 9.1) in combination with 50 mM sodium cholate as a surfactant as BGE solution, together with sample stacking using 50 mM NaCl in the sample and an injection time of 20 s, provided the best separation of the compounds studied. The method was applied to the determination of target analytes in two types of sludge water coming from two steps of a wastewater treatment plant. Liquid–liquid extraction was carried out using toluene as solvent, resulting in recoveries around 100% for all studied analytes. The presence of NPEO_x was observed in the first step of the sludge water treatment, based on migration time and UV spectra. Identification was confirmed using tandem MS. LOQs of the studied compounds were in the range of 12.7 to 30.8 ng/mL, which is satisfactory for the analysis of real wastewater samples.     

Thermodynamic and aggregation behavior of mixed micellar systems of sodium decanoate and ethoxylated alcohols in water at 25°C

Densities and ultrasonic velocities of binary aqueous systems of sodium decanoate (C₁₀Na), of a medium chain length alkoxyethanol with varying number of ethylene oxide groups (C₄EO_0-3), and of ternary systems of these compounds have been measured as a function of surfactant and alcohol concentrations at 25°C. The derived apparent molar volume and molar adiabatic compressibility properties of C₁₀Na in water were fitted with a mass-action model to obtain the thermodynamic micellization parameters of C₁₀Na. The infinite dilution transfer molar volume and transfer molar adiabatic compressibility properties of C₄EO_0-3 from water to aqueous C₁₀Na solutions were obtained from the corresponding apparent molar properties using a chemical equilibrium model. The results of simulating the experimental transfer function data of these alcohols at a given low concentration of 0.05m_A show that the solubilization of C₄EO_0-3 compounds in C₁₀Na micelles is enhanced by increasing the number of ethylene oxide groups (EO) in the alcohol. The mean aggregation number of C₁₀Na, which is 34 in the absence of alcohol, remains unchanged in the presence of 0.05m_A while the average number of alcohol molecules per micelle increases steadily as a function of the number of EO groups in the alcohol.     

A statistical model for non-ionic micellar solutions and their phase diagrams

The micellar phase separation (cloud-point transition) of non-ionic surfactants is studied on the basis of a statistical theory, of liquids. The low value of the critical concentration is explained by the presence of an extended repulsive intermicellar interaction due to a region of structured water. Excellent agreement with experiment is found for the polyoxyethylene surfactants C₁₂E₈ and C₆E₃. Our model can give a closed solubility loop with a very different value of the concentration of the upper and lower consolution points. We study, also the osmotic compressibility and second virial coefficient and the correlation length.     

Interaction of nonionic detergents and swelling clays

Summary The 25° sorption isotherms of a polyoxyethylated n-dodecanol with 14 ethylene oxide units (C₁₂EO₁₄) on sodium and calcium montmorillonite were determined. Sorption complexes of the two clays were also prepared with C₁₂EO₃₀, n-dodecanol, polyethylene glycol and polypropylene glycol. X-ray powder diagrams show that the sorbed organic molecules are intercalated with their chains parallel to the montmorillonite lamellae, in layers one or two molecules thick. Sodium montmorillonite sorbs C₁₂ EO₁₄ and C₁₂EO₃₀ in excess of close-packed double layers: the excess detergent is occluded in interstices and absorbs moisture at 85% relative humidity to the same extent as the bulk detergents. The double layer complexes are not swelled by water; the single layer complexes sorb a single layer of water molecules at 85% relative humidity.Apparent densities of the sorbed organic molecules decrease with increasing EO content while bulk densities increase. This is explained in terms of chain flexibility and polarity.

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Zusammenfassung Die 25°-Absorptions-Isothermen von polyoxyäthyliertem n-Dodekanol mit 14Äthylenoxyd-Einheiten(C₁₂EO₁₄) an Na- und Ca-Montmorillonit wurden bestimmt. Sorptions-Komplexe der 2 Tone wurden ebenfalls mit nDodekanol, Polyäthylenglykol und Polypropylenglykol präpariert. Pulverdiagramme zeigen, daß die sorbierten organischen Moleküle mit ihren Ketten parallel zu den Montmorillonitlamellen eingelagert sind, in Schichten 1 oder 2 Moleküle dick. Na-Montmorillonit sorbiert C₁₂EO₁₄ und C₁₂EO₃₀ im Überschuß zur dichtgepackten Doppelschicht. Der Überschuß ist in Hohlräumen eingelagert und absorbiert Wasser bei 85° relativer Feuchtigkeit im selben Ausmaß wie die reinen Detergentien. Die Doppelschichtkomplexe werden nicht durch Wasser gequollen. Die Einschichtkomplexe sorbieren eine Monoschicht von Wasser-Molekülen bei 85° relativer Luftfeuchtigkeit.Scheinbare Dichten der sorbierten organischen Moleküle nehmen mit steigendem Äthylenoxydgehalt ab, während die Dichten der reinen Substanz ansteigen. Dies läßt sich auf Grund der Kettenbeweglichkeit und Polarität erklären.

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Presented at the 145^th Meeting of the American Chemical Society, New York, N. Y., September 1963.     

Branched non-ionic oligo-oxyethylene V-amphiphiles effect of molecular geometry on LC-phase behavior 2

A homologous series of double-chain non-ionic surfactants with the general formula (C_n)₂ GE_mM, where C_n denotes an alkyl chain, G a triglyceryl, and E_mM an oligo-oxyethylene mono-methyl ether are synthesized withn=6–8 andm=6, 8, 10. The branched hydrophobic part of the surfactants introduces a large cross-section of the lipophilic surfactant moiety that is directly reflected in the shape of the micelles and the LC phase behavior in aqueous solution. The phase behavior of these V-amphiphiles is investigated with polarizing microscopy and x-ray diffraction and reveals that the branched lipophilic part strongly stabilizes the lamellar mesophase. This is in agreement with established packing models.     

The partition of ethoxylated non-ionic surfactants between two non-miscible phases

The partition of a polydispersed ethoxylated non-ionic surfactant in equilibrated oil–water systems has been studied at 25 °C. The model surfactant used was a commercial sample of nonylphenol ethoxylated with 10 moles of ethylene oxide (NPEO₁₀). The partition isotherms over the range of surfactant concentration including the critical micelle concentration (CMC) were made with n-hexane, i-octane and n-decane as oil phases. Each partition isotherm exhibits a change of slope that matched the CMC value of surfactant determined by surface tension measurements on aqueous solutions. During the partition of NPEO₁₀ in the oil–water systems, the oligomer distribution in the oil and water phases changed because of fractionation. Below CMC, the mean ethoxylation degree in the oil phase was smaller, whereas in water it was higher than the mean initial value of the surfactant. Moreover, the mean ethoxylation degree in both oil and water phase was practically independent of surfactant concentration. Above CMC, the mean distribution of ethoxymers decreased in both phases. This was ascribed to the competition between micelles from water and the oil phase for the more hydrophobic species of the surfactant. The mean distribution of ethoxymers in the aqueous phase asymptoted to a value that was the mean of the surfactant itself, whereas it steeply decreased in the organic phase.     

Determination of linear alkylbenzene sulfonates in water samples by liquid chromatography-UV detection and confirmation by liquid chromatography-mass spectrometry

A high-performance liquid chromatographic (HPLC) method was developed for the separation and determination of individual (C₁₀-C₁₃) linear alkylbenzene sulfonates (LAS). New sets of conditions have been established for routine analysis of individual chemical forms of four LAS surfactants, i.e. C₁₀-C₁₃ LAS. Under a condition set using a mobile phase containing 1.5 mM ammonium acetate in methanol/water 80:20 (v/v) mixture, detection limits obtained were in the range 1.5 ppb (for C₁₀ LAS) to 11.5 ppb (for C₁₃ LAS). This offers the advantages of significant improvement in resolution, short separation time and using less amount of common salt under isocratic condition. In addition, the use of simple mobile phase containing a simple low amount of salt cannot deposit at the entrance of mass spectrometric detector. The method is applicable to the simultaneous determination of LAS surfactants in various water samples. LAS surfactants presented in these samples were also successfully confirmed by using electrospray mass spectrometry.     

Effects of additional salts on the interfacial tension of crude oil/zwitterionic gemini surfactant solutions

Zwitterionic gemini surfactants, which have the advantages of both zwitterionic and gemini surfactants, have been widely used in various disciplines. Sulfobetaine-type zwitterionic gemini surfactants consisting of 1,2-bis[N-methyl-N-(3-sulfopropyl)-alkylammonium]ethane (2C_nSb with 6, 8 and 10 carbon atoms) were evaluated for their interfacial activities at the water/crude oil interface. The 2C₁₀Sb molecules showed a remarkable ability to decrease the interface tension (IFT) of water/crude oil, and the degree of decrease was much greater than those in either zwitterionic or gemini surfactant systems by at least two orders of magnitude. Furthermore, the effects of salts (NaCl, CaCl₂, and MgCl₂) on the IFT of the 2C₁₀Sb system were thoroughly investigated. Interestingly, the delicate balance between the effects of additional cations and the intramolecular interactions of 2C₁₀Sb molecules played crucial roles in the interfacial arrangements of 2C₁₀Sb molecules, which were mainly dependent on the bonding abilities of the cations. Moreover, a zwitterionic surfactant and a cationic gemini surfactant were employed in control experiments to verify the proposed mechanisms.