Hollow fiber liquid phase micro-extraction (LPME) of linear alkylbenzene sulfonates (LAS) from aqueous samples was studied. Ion pair extraction of C₁₀, C₁₁, C₁₂ and C₁₃ homologues was facilitated with trihexylamine as ion-pairing agent, using di-n-hexylether as solvent for the supported liquid membrane (SLM). Effects of extraction time, acceptor buffer concentration, stirring speed, sample volume, NaCl and humic acids were studied. At 10–50 µg L⁻¹ linear R²-coefficients were 0.99 for C₁₀ and C₁₁ and 0.96 for C₁₂. RSD was typically ~15%. Three observations were especially made. Firstly, LPME for these analytes was unusually slow with maximum enrichment observed after 15–24 h (depending on sample volume). Secondly, the enrichment depended on LAS sample concentration with 35–150 times enrichment below ~150 µg L⁻¹ and 1850–4400 times enrichment at 1 mg L⁻¹. Thirdly, lower homologues were enriched more than higher homologues at low sample concentrations, with reversed conditions at higher concentrations. These observations may be due to the fact that LAS and the amine counter ion themselves influence the mass transfer at the water-SLM interface. The observations on LPME of LAS may aid in LPME application to other compounds with surfactant properties or in surfactant enhanced membrane extraction of other compounds. Full article

Nickel (II) preconcentration and speciation analysis using a hollow fiber supported liquid membrane (HFSLM) device was studied. A counterflow of protons coupled to complexation with formate provided the driving force of the process, while Kelex 100 was employed as carrier. The influence of variables related to module configuration (acceptor pH and carrier concentration) and to the sample properties (donor pH) on the preconcentration factor, E, was simultaneously studied and optimized using a 3 factor Doehlert matrix response surface methodology. The effect of metal concentration was studied as well. Preconcentration factors as high as 4240 were observed depending on the values of the different variables. The effects of the presence of inorganic anions (NO₂^-, SO₄^2-, Cl^-, NO₃^-, CO₃^2-, CN^-) and dissolved organic matter (DOM) in the form of humic acids were additionally considered in order to carry out a speciation analysis study. Nickel preconcentration was observed to be independent of both effects, except when cyanide was present in the donor phase. A characterization of the transport regime was performed through the analysis of the dependence of E on the temperature. E increases with the increase in temperature according to the equation E(K) = -8617.3 + 30.5T with an activation energy of 56.7 kJ mol^-1 suggesting a kinetic-controlled regime. Sample depletion ranged from 12 to 1.2% depending on the volume of the donor phase (100 to 1000 mL, respectively). Full article

Electrochemical impedance spectroscopy (EIS) has been used to estimate the non-frequency dependent (static) dielectric constants of base polymers such as poly(vinyl chloride) (PVC), cellulose triacetate (CTA) and polystyrene (PS). Polymer inclusion membranes (PIMs) containing different amounts of PVC or CTA, along with the room temperature ionic liquid Aliquat 336 and plasticizers such as trisbutoxyethyl phosphate (TBEP), dioctyl sebecate (DOS) and 2-nitrophenyloctyl ether (NPOE) have been investigated. In this study, the complex and abstract method of EIS has been applied in a simple and easy to use way, so as to make the method accessible to membrane scientists and engineers who may not possess the detailed knowledge of electrochemistry and interfacial science needed for a rigorous interpretation of EIS results. The EIS data reported herein are internally consistent with a percolation threshold in the dielectric constant at high concentrations of Aliquat 336, which illustrates the suitability of the EIS technique since membrane percolation with ion exchangers is a well-known phenomenon. Full article

Biodegradable polymers have attracted much attention from an environmental point of view. Optically pure lactic acid that can be prepared by fermentation is one of the important raw materials for biodegradable polymer. The separation and purification of lactic acid from the fermentation broth are the major portions of the production costs. We proposed the application of supported ionic liquid membranes to recovering lactic acid. In this paper, the effect of ionic liquids, such as Aliquat 336, CYPHOS IL-101, CYPHOS IL-102, CYPHOS IL-104, CYPHOS IL-109 and CYPHOS IL-111 on the lactic acid permeation have been studied. Aliquat 336, CYPHOS IL-101 and CYPHOS IL-102 were found to be the best membrane solvents as far as membrane stability and permeation of lactic acid are concerned. CYPHOS IL-109 and CYPHOS IL-111 were found to be unsuitable, as they leak out from the pores of the supported liquid membrane (SLM), thereby allowing free transport of lactic acid as well as hydrochloric acid. CYPHOS IL-102 was found to be the most adequate (Permeation rate = 60.41%) among these ionic liquids as far as the separation of lactic acid is concerned. The permeation mechanisms, by which ionic liquid-water complexes act as the carrier of lactate and hydrochloric acid, were proposed. The experimental permeation results have been obtained as opposed to the expected values from the solution-diffusion mechanism. Full article