Micellar extraction preconcentration of barium with phases of nonionic surfactants at the cloud point

The micellar extraction of barium with phases of nonionic surfactant Triton X-100 was studied in the presence of aliphatic monocarboxylic acids, crown ethers, and Carboxyarsenazo and its mixtures with cetylpyridinium chloride and octylamine. It was shown that the complete extraction of barium into the micellar phase was attained using Carboxyarsenazo and cationic surfactants in the presence of octylamine through the formation of a ternary hydrophobic complex. The conditions for the determination of the atomic absorption of barium in water with preconcentration into the nonionic surfactant phase at the cloud point temperature were developed.     

The cloud point extraction of copper(II) with monocarboxylic acids into non-ionic surfactant phase

The possibility to use monocarboxylic acids and their mixtures with amines for copper concentrating by the way of micellar extraction at cloud point temperature, and later atomic absorption spectrometry (AAS) determination was investigated. Under the optimum conditions, preconcentration of 100 ml of water sample in the presence of 1% non-ionic surfactant OP-10, 0.005 M capric acid and 0.01 M octylamine permitted the detection of 0.01 μg ml⁻¹ copper. The proposed method has been applied to the AAS determination of copper in water samples after cloud point extraction.     

Spectrophotometric determination of cloud point of Brij 35 nonionic surfactant

The cloud point of nonionic surfactant polyoxyethylene (23) lauryl ether (Brij-35) was determined in the presence of various inorganic electrolytes. The measurements of cloud point (CP) were carried out with UV-vis spectrophotometer instead of visual observation. CP of Brij-35 could not be measured directly because its CP is more than 100 °C. Therefore, CP values of Brij-35 were lowered by the addition of electrolytes. In this study, NaF, NaCl, NaBr, KNO₃, K₂CO₃, K₃PO₄, Li₂SO₄, Na₂SO₄, K₂SO₄, (NH₄)₂SO₄, CuSO₄, ZnSO₄, CoSO₄ were used as electrolytes. Linear lines which were drawn with CP values were extrapolated to zero electrolyte concentration. The real CP value of Brij-35 which is merely listed as >100 °C in the literature was found as 118.5 ± 0.5 °C for all samples. Furthermore, the effects of the nature of the cation and the anion and the valencies of the cations on CP were reported and the rate of decrease in CP with concentration is discussed.     

Development of a cloud point extraction and preconcentration method for silver prior to flame atomic absorption spectrometry

The possibility was investigated of using 2-mercaptobenzothiazole (MBT) for Ag(I) concentration by micellar extraction at cloud point (CP) temperature and subsequent determination by flame atomic absorption spectrometry (FAAS). The method is based on the complexation of Ag(I) with 2-mercaptobenzothiazole (MBT) in the presence of non-ionic micelles of Triton X-114. The effect of experimental conditions such as pH, concentration of chelating agent and surfactant, equilibration temperature and time on cloud point extraction was studied. Under the optimum conditions, the preconcentration of 10 mL of water sample in the presence of 0.1% Triton X-114 and 2 × 10⁻⁴ mol L⁻¹ 2-mercaptobenzothiazole permitted the detection of 2.2 ng mL⁻¹ silver. The calibration graph was linear in the range of 10–200 ng mL⁻¹, and the recovery of more than 99% was achieved. The proposed method was used in FAAS determination of Ag(I) in water samples.     

Evaluation of a cloud point extraction method for the preconcentration and quantification of silver nanoparticles in water samples by ETAAS

ABSTRACT

A simple and reliable analytical method using instrumentation available in most of the laboratories has been developed for the separation and determination of silver nanoparticles in water samples. Cloud point extraction (CPE) was used for the separation of silver nanoparticles (AgNPs) from the sample and these nanoparticles were then determined by electrothermal atomic absorption spectrometry (ETAAS). Parameters related to the cloud point extraction procedure (Triton X-114 concentration, type of complexing agent (EDTA or Na₂S₂O₃), pH, incubation temperature, incubation and centrifugation time) were selected using a multivariate approach (designs of experiments); 8.6% (v/v) Triton X-114, 750 µL saturated EDTA and pH 7 were selected as the optimum conditions. Calibration standards in a concentration range from 0 to 10 µg L^?1 of AgNPs were subjected to the CPE procedure to obtain quantitative recoveries. The LOD and LOQ were 0.04 and 0.13 µg L^?1, respectively. The method is selective for the extraction of AgNPs, and ionic Ag remains in the aqueous phase. Single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) was used to evaluate the effect of the CPE procedure in particle size, and no changes were observed. Finally, the procedure was applied to wastewater samples spiked with nanoparticles with quantitative recoveries.     

The interaction between a nonionic surfactant and acid dyes studied by measurements of cloud point

In order to clarify the interaction behaviors between a nonionic surfactant (S) and an acid dye (D), the cloud points (CP) were measured for the solution containing S and D with increasing amounts of electrolytes and are plotted as a function of the electrolyte concentration. A clear transition point Z was observed in the CP curve. The value of C^z, the electrolyte concentration at Z, depends upon the valence number of the cation of the added electrolyte rather than that of the anion. While the value of T^z, the temperature at Z, is independent of the kind of electrolyte and dye, but depends on the molar ratio of S to D in the solution. On the basis of the phase rule, the existence of Z was interpreted in terms of a triple point of three types of mixed micelles which are formed of S and D.     

Equilibrium partition of polycyclic aromatic hydrocarbons in cloud point extraction with a silicone surfactant

In the cloud point extraction (CPE) process with PEG/PPG-18/18 dimethicone, the flexible chain structure of the silicone surfactant efficiently decreased the water content remaining in the surfactant-rich phase, compared with conventional nonionic surfactants, represented by Triton X-114. Meanwhile, the phase volume ratio of surfactant-rich phase to aqueous phase obtained in the silicone surfactant CPE system was found to be maintained at a low value with increasing surfactant concentration; whereas a rapid increase tendency was commonly observed in that of other nonionic surfactants. Based on these advantages, the equilibrium partition of three polycyclic aromatic hydrocarbons (PAHs), anthracene, phenanthrene and pyrene, was studied in the CPE process with PEG/PPG-18/18 dimethicone. Equilibrium parameters, including preconcentration factor, distribution coefficient and recovery, were determined, and the performance was compared with that of another related CPE research, where Tergitol 15-S-7 was used. Due to the low surfactant-rich phase volume, higher concentrations of the three PAHs in the surfactant-rich phase, and the resulting higher preconcentration factors and distribution coefficients were able to be achieved at the same time. Moreover, the great performance was able to be maintained even at a high surfactant concentration or PAHs initial concentration.     

Separation and preconcentration of persistent organic pollutants by cloud point extraction

Persistent organic pollutants (POPs) are recognized as a class of poisonous compounds which pose risks of causing adverse effects to human health and the environment. Thus, it is very important to detect POPs in environmental and biological samples. The identification and determination of very low levels of POPs in complex matrices is extremely difficult. Recently a promising environmentally benign extraction and preconcentration methodology based on cloud point extraction (CPE) has emerged as an efficient sample pretreatment technique for the determination of trace/ultra-trace POPs in complex matrices. The purpose of this paper is to review the past and latest use of CPE for preconcentrating POPs and its coupling to different contemporary instrumental methods of analysis. First, the comparison of various extraction techniques for POPs is described. Next, the general concept, influence factors and other methods associated with CPE technique are outlined and described. Last, the hyphenations of CPE to various instrumental methods for their determination are summarized and discussed.     

Synthesis and application of a new thiazolylazo reagent for cloud point extraction and determination of cobalt in pharmaceutical preparations

The synthesis and characterization of the reagent 2-(5-bromothiazolylazo)-4-chlorophenol and its application in the development of a preconcentration procedure for cobalt determination using flame atomic absorption spectrometry after cloud point extraction is presented. This procedure is based on cobalt complexing and entrapment of the metal chelates into micelles of a surfactant-rich phase of Triton X-114. The preconcentration procedure was optimized by using a response surface methodology through the application of the Box-Behnken matrix. Under optimum conditions, the procedure determined the presence of cobalt with an LOD of 2.8 microg/L and LOQ of 9.3 microg/L. The enrichment factor obtained was 25. The precision was evaluated as the RSD, which was 5.5% for 10 microg/L cobalt and 6.9% for 30 microg/L. The accuracy of the procedure was assessed by comparing the results with those found using inductively coupled plasma-optical emission spectrometry. After validation, the procedure was applied to the determination of cobalt in pharmaceutical preparation samples containing cobalamin (vitamin B12).     

Spectrophtometric determination of malachite green in fish farming water samples after cloud point extraction using nonionic surfactant Triton X-100

A novel and sensitive cloud point extraction procedure for the determination of trace amounts of malachite green by spectrophotometry was developed. Malachite green was extracted at pH 2.5 mediated by micelles of nonionic surfactant Triton X-100. The extracted surfactant-rich phase was diluted with ethanol and its absorbance was measured at 630 nm. The effect of different variables such as pH, Triton X-100 concentration, cloud point temperature and time and diverse ions was investigated and optimum conditions were established. The calibration graph was linear in the range of 4-500 ng mL⁻¹ of malachite green in the initial solution with r = 0.9996 (n = 10). Detection limit based on three times the standard deviation of the blank (3S_b) was 1.2 ng mL⁻¹ and the relative standard deviation (R.S.D.) for 20 and 300 ng mL⁻¹ of malachite green was 1.48 and 1.13% (n = 8), respectively. The method was applied to the determination of malachite green in different fish farming and river water samples.     

Selective cloud point extraction and preconcentration of trace amounts of silver as a dithizone complex prior to flame atomic absorption spectrometric determination

Dithizone (diphenylthiocarbazone) was used as a complexing agent in cloud point extraction for the first time and applied for selective preconcentration of trace amounts of silver. The analyte in the initial aqueous solution was acidified with sulfuric acid (pH<1) and Triton X-114 was added as a surfactant. After phase separation, based on the cloud point separation of the mixture, the surfactant rich phase was diluted with tetrahydrofuran (THF) and the analyte determined in the enriched solution by flame atomic absorption spectrometry. After optimization of the complexation and extraction conditions, a preconcentration factor of 43 was obtained for only 10 ml of sample. The analytical curve was linear in the range of 3-200 ng ml⁻¹ and the limit of detection was 0.56 ng ml⁻¹. The proposed method was applied to the determination of silver in water samples.     

Separation and preconcentration by a cloud point extraction procedure for determination of metals: an overview

Recently, cloud point extraction (CPE) has been an attractive subject as an alternative to liquid–liquid extraction. The technique is based on the property of most non-ionic surfactants in aqueous solutions to form micelles and become turbid when heated to the cloud point temperature. This review covers a selection of the literature published on applications of CPE in determination of metal ions over the period between 2004 and 2008.     

Acid-induced cloud point extraction and preconcentration of polycyclic aromatic hydrocarbons from environmental solid samples

Liquid chromatography coupled to electrospray-mass spectrometry (LC-ES-MS) with positive ion detection was evaluated for the determination of tributyltin and triphenyltin in water samples using tripropyltin as internal standard. The separation was performed in the isocratic mode on a silica-based C18 column with a mobile phase containing 0.02% trifluoroacetic acid in acetonitrile-water (50:50, v/v). The optimum LC-ES-MS conditions were established and quantification was performed on the basis of the [M]+ ions. Limits of detection for standard solutions were 100 and 200 pg Sn injected for triphenyltin and tributyltin, respectively, and good reproducibility was observed. Solid-phase extraction was carried out on C18 cartridges to preconcentrate the analytes from natural water samples, with recoveries ranging from 80 to 110%. Limits of detection for SPE-LC-ES-MS were in the range of low ng l(-1), which demonstrates the suitability of the method for environmental samples.     

Ultratrace determination of cadmium by cold vapor atomic absorption spectrometry after preconcentration with a simplified cloud point extraction methodology

A simplified micelle-mediated extraction methodology for the preconcentration of ultratrace levels of cadmium as a prior step to its determination by cold vapor atomic absorption spectrometry (CV-AAS) has been developed. The methodology is based on the cloud point extraction (CPE) of cadmium at pH 8 by using the non-ionic surfactant polyethyleneglycolmono-p-nonylphenylether (PONPE 7.5) without adding any chelating agent. Cadmium cold vapor was generated from 2 ml of the extracted surfactant-rich phase by means of sodium tetrahydroborate (3%, w/v) as a reducing agent and hydrochloric acid (0.2 mol l⁻¹) as a carrier solution. Several important variables that affect the cloud point extraction and cold vapor cadmium generation efficiency were investigated and optimized. The preconcentration of only 50 ml of solution in the presence of 0.06% (v/v) PONPE 7.5 gives an enhancement factor of 62. The calibration graph using the preconcentration system was linear in the range of 4-100 ng l⁻¹ with a correlation coefficient of 0.9992. Detection limit (3 s) obtained in the optimal conditions was 0.56 ng l⁻¹. The relative standard deviation (R.S.D.) for six replicate determinations at 20 ng l⁻¹ Cd level was 3.2%. The proposed method was successfully applied to the ultratrace determination of cadmium in water samples.     

Micellar extraction of a tin complex of phenylfluorone into a cetylpyridinium chloride-based liquid phase

Optimal conditions have been found for the modification of compact liquid phases based on a cationic surfactant, cetylpyridinium chloride, with salicylic acid. On the example of the system tin-phenylfluorone we have shown the applicability of such phases to the preconcentration of multiply charged ions readily hydrolyzed metals. The influence of concentrations on the absorbance and composition of the complex has been studied; the optimal conditions of its extraction have been found. The developed spectrophotometric procedure of tin determination with phenylfluorone using micellar-extraction preconcentration has been tested for the analysis of canned vegetables and brines.     

Evaluation of a cloud point extraction approach for the preconcentration and quantification of trace CuO nanoparticles in environmental waters

The cloud point extraction (CPE) of commercial copper(II) oxide nanoparticles (CuO NPs, mean diameter of 28 nm) in water samples was fully investigated. Factors such as Triton X-114 (TX-114) concentration, pH, incubation temperature and time, were optimized. The effects of CuO NP behavior like agglomeration, dissolution, and surface adsorption of natural organic matter, Cu²⁺, and coating chemicals, on its recovery were studied. The results indicated that all the CPE factors had significant effects on the extraction efficiency. An enrichment factor of ∼89 was obtained under optimum CPE conditions. The hydrodynamic diameter of CuO NPs increased to 4–5 μm upon agglomeration of NP-micelle assemblies, and decreased at pH >10.0 at which the extraction efficiency was also lowered. The solubility and therefore, the loss of NPs were greatly enhanced at pH <8.5 and in the first 60 min of incubation, whereas it declined at elevated incubation temperatures. Our results showed that the dissolved organic carbon (DOC) >5 mg C L⁻¹ and Cu²⁺ >2 times that of CuO NPs, lowered and enhanced the extraction efficiency, respectively. Pre-treatment of samples with 3% w v⁻¹ of hydrogen peroxide and 10 mM of ethylenediaminetetraacetic acid minimized the interferences posed by DOC and Cu²⁺, respectively. The decrease in CPE efficiency was also evident for ligands like poly(ethylene glycol). The TX-114-rich phase could be determined with either inductively coupled plasma mass spectrometry following microwave digestion, or graphite furnace atomic absorption spectrometry. The detection limits for CuO NPs were 0.02 and 0.06 μg L⁻¹ using these techniques, respectively. The optimum sample pre-treatment and CPE conditions were successfully applied to the river and wastewater samples. The relative recoveries of CuO NPs spiked at 5–100 μg L⁻¹ (as Cu) in these samples were in the range of between 59.2 and 108.2%. The approach demonstrates a robust analytical method for detecting trace levels of CuO NPs at their original states and assessing their exposure risks in real aquatic environments.     

Development of cloud point extraction using pH-sensitive hydrogel for preconcentration and determination of malachite green

A novel and sensitive cloud point extraction procedure using pH-sensitive hydrogel was developed for preconcentration and spectrophotometric determination of trace amounts of malachite green (MG). In this extraction method, appropriate amounts of poly(styrene-alt-maleic acid), as a pH-sensitive hydrogel, and HCl were added respectively into the aqueous sample so a cloudy solution was formed. The cloudy phase consists of hydrogel particles distributed entirely into the aqueous phase. Organic or inorganic compounds having the potential to interact with polymer particles (chemical interaction or physical adsorption) could be extracted to cloudy phase. After centrifuging, these particles of hydrogel were sedimented in the bottom of sample tube. The sedimented hydrogel-rich phase was diluted with acetonitrile and its absorbance was measured at 617 nm (λ_max of malachite green in hydrogel). Central composite design and response surface method were applied to design the experiments and optimize the experimental parameters such as, concentration of hydrogel and HCl, extraction time and salting out effect. Under the optimum conditions, the linear range was 1 × 10⁻⁸-5 × 10⁻⁷ mol L⁻¹ malachite green with a correlation coefficient of 0.992. The limit of detection (S/N = 3) was 4.1 × 10⁻⁹ mol L⁻¹. Relative standard deviation (RSD) for 7 replicate determinations of 10⁻⁷ mol L⁻¹ malachite green was 3.03%. In this work, the concentration factor of 20 was reached. Also the improvement factor of the proposed method was 23. The advantages of this method are simplicity of operation, rapidity and low cost.     

Surfactant cloud point extraction and preconcentration of organic compounds prior to chromatography and capillary electrophoresis

The use of preconcentration steps based on phase separation by the cloud point technique offers a convenient alternative to more conventional extraction systems. It has been used successfully for the preconcentration of species of widely differing character and nature, such as metal ions, proteins and other biomaterials, or organic compounds of strongly differing polarity. Here we address the most recent analytical applications of this methodology when used as an isolation and trace enrichment step prior to the analysis of organic compounds (polycyclic aromatic hydrocarbons, polychlorinated compounds, pesticides, phenolic derivatives, aromatic amines, vitamins, etc.) via liquid and gas chromatography or capillary electrophoresis.     

Formation of colloidal silver in the presence of a nonionic surfactant,Surfynol 465

The formation of colloidal silver in the presence of a nonionic surfactant, Surfynol 465, was studied at various temperatures. By simply mixing equal volumes of AgClO₄ aq. (1–10 mmol kg^–1) and Surfynol 465 aq., the colloidal silver was formed. The colloidal solution had well over ten times the amount of fine silver particles in the solution formed by the ordinary methods. The first factor to form the colloidal silver without aggregation was the molar ratio of Surfynol 465 to AgClO₄, and the optimum ratio increased with increasing the concentration of AgClO₄ or the temperature. In the fraction of colloidal silver collected through the gel filtration, Surfynol 465 was also found in the micellar state. From these results, it was suggested that Surfynol 465 was a protecting agent of colloidal silver as well as a reducing agent of AgClO₄ in the similar manner to the case of colloidal gold.