Liquid-liquid-liquid microextraction for sample preparation of biological fluids prior to capillary electrophoresis.

Methamphetamine as a model compound was extracted from 2.5-mL aqueous samples adjusted to pH 13 (donor solution) through a thin phase of 1-octanol inside the pores of a polypropylene hollow fiber and finally into a 25-microL acidic acceptor solution inside the hollow fiber. Following this liquid-liquid-liquid microextraction (LLLME), the acceptor solutions were analyzed by capillary zone electrophoresis (CE). Extractions were performed in simple disposable devices each consisting of a conventional 4-mL sample vial, two needles for introduction and collection of the acceptor solution, and a 8-cm piece of a porous polypropylene hollow fiber. From 5 to 20 different samples were extracted in parallel for 45 min, providing a high sample capacity. Methamphetamine was preconcentrated by a factor of 75 from aqueous standard solutions, human urine, and human plasma utilizing 10(-1) M HCl as the acceptor phase and 10(-1) M NaOH in the donor solution. In addition to preconcentration, LLLME also served as a technique for sample cleanup since large molecules, acidic compounds, and neutral components were not extracted into the acceptor phase. Utilizing diphenhydramine hydrochloride as internal standard, repetitive extractions varied less than 5.2% RSD (n = 6), while the calibration curve for methamphetamine was linear within the range 20 ng/microL to 10 micrograms/mL (r = 0.9983). The detection limit of methamphetamine utilizing LLLME/CE was 5 ng/mL (S/N = 3) in both human urine and plasma.     

Dynamic liquid-liquid-liquid microextraction with automated movement of the acceptor phase

A new dynamic liquid-liquid-liquid microextraction procedure, with the automated movement of acceptor phase (LLLME/AMAP) to facilitate mass transfer, was developed in this study. Four compounds, 3-nitrophenol, 4-nitrophenol, 3,4-dinitrophenol, and 2,4-dichlorophenol, were used as model compounds to be preconcentrated from water samples. The extraction involved filling a 2-cm length of hollow fiber with 4 muL of acceptor solution using a conventional microsyringe, followed by impregnation of the pores of the fiber wall with 1-octanol. The fiber was then immersed in 4 mL of aqueous sample solution. The analytes in the sample solution were extracted into the organic solvent and then back-extracted into the acceptor solution. During extraction, the acceptor phase was repeatedly moved in and out of the hollow fiber channel and the syringe controlled by a syringe pump. Separation and quantitative analyses were then performed by using high-performance liquid chromatography. The results indicated that up to 400-fold enrichment of the analytes could be obtained under the optimized conditions. The enrichment factors were two times those of static liquid-liquid-liquid microextraction. Good repeatabilities (RSD values below 9.30%) were obtained. The calibration linear range was from 10 to 1000 ng/mL with the square of the correlation coefficient (r2) >0.9916. Detection limits were in the range of 0.45-0.98 ng/mL. In addition, as compared with the previously reported dynamic three-phase microextraction in which there was no relative movement between the acceptor and the organic phase (which is not conducive to effective mass transfer), this new method shows much higher extraction efficiency. All these results suggest that this new dynamic LLLME/AMAP technique could be a better alternative to the previous LLLME for the extraction of analytes from aqueous samples.     

Dynamic three-phase microextraction as a sample preparation technique prior to capillary electrophoresis

Dynamic three-phase (liquid-liquid-liquid) microextraction was developed for capillary electrophoresis. Four aromatic amines as model compounds were extracted from 4-mL aqueous samples adjusted to basic condition (donor solution) through a small volume of organic solvent impregnated in a hollow fiber, which was held by the needle of a conventional syringe, and retracted into a 5-microL acidic acceptor solution inside the syringe. A renewable organic film and aqueous sample plug were formed inside the hollow fiber with the repeated movement of the syringe plunger enabled by a programmable syringe pump. This is believed to be the first reported instance of a semiautomated dynamic liquid-liquid-liquid microextraction (LLLME) procedure. Following this microextraction, the 5-microL acceptor solution was analyzed by capillary zone electrophoresis (CE). This new technique provided approximately 140-fold enrichment in 20 min. Utilizing 4-chloroaniline as internal standard, dynamic LLLME could provide good reproducibility (<4.0%). In addition, this method allowed the direct transfer of extracted analytes to a CE system for analysis.     

Solvent bar microextraction

In this work, a new and simple microextraction method termed solvent bar microextraction (SBME) was developed. In this method, the organic extractant solvent (1-octanol) was confined within a short length of a hollow fiber membrane (sealed at both ends) that was placed in a stirred aqueous sample solution. Tumbling of the extraction device within the sample solution facilitated extraction. Pentachlorobenzene (PCB) and hexachlorobenzene (HCB) were used as model compounds to investigate the extraction performance. Analysis was carried out by gas chromatography/electron capture detection. This new method provided very high enrichment (approximately 110-fold for PCB and approximately 70-fold for HCB) in 10 min and good reproducibility (<4%, n = 6). Since the hollow fiber membrane was sealed, it could be used for extraction from "dirty" samples, such soil slurries. This novel microextraction method was compared with single-drop microextraction and static hollow fiber membrane microextraction in which the extractant solvent was also held within a hollow fiber but with the latter fixed to a syringe needle (i.e., there was no tumbling effect). Comparison between SBME and conventional solid-phase microextraction in a soil slurry sample was also investigated.     

Liquid-phase microextraction of phenolic compounds combined with on-line preconcentration by field-amplified sample injection at low pH in micellar electrokinetic chromatography.

This paper describes a novel method that applies field-amplified sample injection (FASI) in micellar electrokinetic chromatography (MEKC) with a low pH background electrolyte (BGE). Six phenolic compounds prepared in water or NaOH solution were used as the test analytes. Sample was injected electrokinetically after the introduction of a plug of water. During the injection, the water plug was pumped out of the capillary inlet by the electroosmotic flow, and the phenolic anions migrated very quickly in the direction of the outlet. When the anions reached the boundary between the water plug and BGE, they were neutralized and ceased moving. Thereafter, MEKC was initiated for the separation. This on-line preconcentration method could be conveniently coupled with a liquid-liquid-liquid microextraction procedure, in which a hollow fiber was used as an extraction solvent support to extract the analytes from the water sample. The acceptor phase consisted of 8 mM NaOH. After extraction, the extract was analyzed directly by MEKC, as described.     

Liquid-phase microextraction combined with hollow fiber as a sample preparation technique prior to gas chromatography/mass spectrometry

Two modes of liquid-phase microextraction (LPME) combined with hollow fiber (HF) were developed for gas chromatography/mass spectrometry (GC/MS). Both methodologies, that is, static LPME with HF and dynamic LPME with HF, involved the use of a small volume of organic solvent impregnated in the hollow fiber, which was held by the needle of a conventional GC syringe. In static LPME/HF, the hollow fiber impregnated with solvent was immersed in the aqueous sample, and the extraction processed under stirring; in dynamic LPME/HF, the solvent was repeatedly withdrawn into and discharged from the hollow fiber by a syringe pump. This is believed to be the first reported instance of a semiautomated liquid microextraction procedure. The performance of the two techniques was demonstrated in the analysis of two PAH compounds in an aqueous sample. Static LPME/HF provided approximately 35-fold enrichment in 10 min and good reproducibility (approximately 4%). Dynamic LPME/HF could provide higher enrichment (approximately 75-fold) in 10 min and even better reproducibility (approximately 3%). Both methods allow the direct transfer of extracted analytes to a GC/MS system for analysis.     

Equilibrium sampling through membranes of freely dissolved chlorophenols in water samples with hollow fiber supported liquid membrane

The freely dissolved concentration (C(free)) of pollutants is generally believed to be bioavailable and thus responsible for toxic effects. The C(free) of organic weak acids and bases consists of a dissociated and a nondissociated fraction. By using chlorophenols as model compounds, a negligible-depletion extraction technique, equilibrium sampling through membranes (ESTM), was developed for the measurement of the nondissociated part of the C(free). Polypropylene hollow fiber membranes (280-microm i.d., 50-microm wall thickness, 0.1-microm pore size, 15-cm length) were impregnated with undecane in the pores in the fiber wall as liquid membrane and filled with buffer solution in the lumen as acceptor. Then, the hollow fiber membranes were placed into the sample (donor) for an equilibrium extraction after sealing the two ends. The chlorophenol concentrations in the acceptor were then determined by direct injection into a HPLC system. Finally, the C(free) of the nondissociated and the dissociated species of a chlorophenol were calculated based on its measured concentration in the acceptor, its pK(a) value, and the measured pH in sample and acceptor. Theoretically calculated distribution coefficients (D = 8-970) agree well with the experimental enrichment factors (E(e(max)) = 6-1124), and the equilibration time was observed to increase with increasing distribution coefficients (hours to days). The freely dissolved concentration of five chlorophenols, with a wide range of pK(a) (4.9-9.2) and log K(ow) (2.35-5.24), were successfully determined in model solutions of humic acids and at low-ppb levels in river and leachate water.     

Sample preparation using a miniaturized supported liquid membrane device connected on-line to packed capillary liquid chromatography

A miniaturized supported liquid membrane device has been developed for sample preparation and connected on-line to a packed capillary liquid chromatograph. The device consists of hydrophobic polypropylene hollow fiber, inserted and fastened in a cylindrical channel in a Kel-F piece. The pores of the fiber are filled with an organic solvent, in this study 6-undecanone, thus forming a liquid membrane. The sample is pumped on the outside of the hollow fiber (donor), and the analytes are selectively enriched and trapped in the fiber lumen (acceptor). With this approach, the volume of the acceptor solution can be kept as low as 1-2 μL. This stagnant acceptor solution is then transferred through capillaries attached to the fiber ends to the LC system. The system was tested with a secondary amine (bambuterol), as a model substance in aqueous standard solutions as well as in plasma. The best extraction efficiency in aqueous solution, with an acceptor volume of 1.9 μL, was 32.5% at a donor flow rate of 2.5 μL/min. At flow rates above 20 μL/min, the concentration enrichment per time unit was approximately constant, at 0.9 times/min, i.e., 9 times enrichment in about 10 min. The overall repeatability (RSD) for spiked plasma samples was ～4% (n = 12). Linear calibration curves of peak area versus bambuterol concentration were obtained for both aqueous standard solutions and spiked plasma samples. The detection limit for bambuterol in plasma, after 10 min of extraction at a flow rate of 24 μL/min, was 80 nM.     

The XT-tube extractor: a hollow fiber-based supported liquid membrane extractor for bioanalytical sample preparation

A new supported liquid membrane extractor for bioanalytical sample preparation is presented. The extractor consists of a polypropylene hollow fiber mounted inside a PTFE tube by means of a cross-connector and a tee-connector. All parts are commercially available, inexpensive, and easily assembled. An organic solvent in the pores of the fiber forms a liquid membrane that separates the sample, which is pumped along the outside of the fiber, from the acceptor phase, which is pumped inside. The length of the hollow fiber may easily be varied to meet different demands on extractive surface and extract volumes. To test the system, the strongly acidic plasticizer/flame retardant metabolite diphenyl phosphate ester (DPhP), with a pKa value of 0.26, was extracted from urine. DPhP was protonated using 4 M hydrochloric acid and extracted into an acceptor phase at pH 9. Thirty extractions were made with the same liquid membrane without any decrease in extraction efficiency and with a relative standard deviation <7%. An analyte concentration enrichment of 5-10 times was achieved in the extraction step, giving a limit of detection (S/N = 3) of 0.014 microg/mL with LC/ESI-MS and 0.18 microg/mL with CE-UV. The effects on extraction efficiency using different sample pH, organic solvents, sample flow rates, and lengths of the fiber were evaluated.     

In situ hydrothermal grown silicalite-1 coating for solid-phase microextraction

A novel fiber coated with silicalite-1 for solid-phase microextraction (SPME) was prepared by in situ hydrothermal growth method. Six substituted benzenes (nitrobenzene, p-dichlorobenzene, m-dichlorobenzene, 1,3,5-trichlorobenzene, p-chloronitrobenzene, and m-chloronitrobenzene) were employed as model analytes. The fiber exhibited high thermal stability (little weight loss up to 600 °C) and high chemical stability (no loss of function after sequential immersion in 0.1 M HCl, 0.01 M NaOH, methanol, and n-hexane each for at least 4 h). Compared with commercial fibers, 3-6 times higher extraction efficiencies were shown on the fiber for mono- and p-substituted benzenes. Under the preoptimized conditions, the fiber afforded satisfactory enhancement factors (517-1292), wide linear ranges (more than 2 orders of magnitude), low limits of detection (0.001-0.130 μg/L), and acceptable repeatability (<9.6%) and reproducibility (<8.8%). Furthermore, the fiber offered distinct shape-selectivity attributed to the uniform molecular-scale pore structure of silicalite-1. The ratios of extraction were approximately 70 between p-dichlorobenzene and 1,3,5-trichlorobenzene, 30 between p-chloronitrobenzene and m-chloronitrobenzene, and 3 between p-dichlorobenzene and m-dichlorobenzene. After pore narrowing by surface modification with SiCl(4), the selectivity for p-dichlorobenzene over m-dichlorobenzene was further enhanced by another 10 times. Finally, the fiber was successfully applied to analysis of a real water sample.     

Equilibrium sampling of freely dissolved alkylphenols into a thin film of 1-octanol supported on a hollow fiber membrane

A new negligible depletion extraction procedure was proposed for equilibrium sampling of 4-tert-octylphenol (OP) and 4-nonylphenol (NP) into a thin film of 1-octanol supported on a hollow fiber membrane. This thin liquid film extraction technique was directed at the determination of (1) freely dissolved concentrations, (2) distribution coefficients to 1-octanol (D(ow)), and (3) binding to dissolved organic matter (DDOC). The sampling device was prepared by dipping pieces of polypropylene microporous hollow fiber membrane (10-mm length, 30-microm wall thickness, 240-microm inner diameter) into 1-octanol for a few seconds to impregnate the pores of the hollow fiber wall. After stirring in 100 mL of sample solution for 24 h, the sampling device was harvested and desorbed with 30 microL of methanol, of which 20 microL was injected for HPLC analysis. With the measured D(ow) of a chemical and its equilibrium concentration in the 1-octanol sampling phase (C(octanol)), the freely dissolved concentration (Cfree) was calibrated based on Cfree = C(octanol)/D(ow). Measured log Dow values of OP (4.32 +/- 0.06) and NP (4.79 +/- 0.02) were independent of the chemical concentration, only minimally affected by the environmentally relevant pH, buffering capacity, and salinity of samples, and agreed well with reported values. Log DDOC values of OP (4.89 +/- 0.43) and NP (5.14 +/- 0.37), determined in Aldrich humic acid solution, agreed with reported partition coefficients to organic carbon (log Koc) for particles in river water and effluent wastewater. Short equilibration times and high enrichment factors were obtained for both analytes due to the high surface to volume ratio of the new sampler. The technique was successfully applied to determine Cfree of OP and NP in real water samples and to study their association with humic acids and bovine albumin.     

Combining drop-to-drop solvent microextraction with gas chromatography/mass spectrometry using electronic ionization and self-ion/molecule reaction method to determine methoxyacetophenone isomers in one drop of water

A novel analytical technique termed drop-to-drop solvent microextraction (DDSME) was developed to determine three methoxyacetophenone isomers in one drop of water, which were then detected by gas chromatography/mass spectrometry using electronic ionization mass spectrometry for quantification analysis and self-ion/molecule reaction/tandem mass spectrometry for isomer differentiation. The best optimum parameters for the DDSME technique were as follows: extraction time, 5 min; using toluene as the extraction solvent; volume of extraction solvent, 0.5 microL and no salt addition. The advantages of this method are rapidity, convenience, ease of operation, simplicity of the device, and extremely little solvent and sample consumption. The limit of detection (LOD) for this technique was 1 ng/mL. The relative standard deviation was less than 2.6% (n = 5). The linear range of the calibration curve of DDSME is from 0.01 to 5 microg/mL with correlation coefficient (r2) of >0.954. In the comparison of the LOD of DDSME with other sample pretreatment methods including liquid/liquid extraction (LLE), single-drop microextraction (SDME), solid-phase microextraction (SPME), and liquid-phase microextraction (LPME) using a dual gauge microsyringe with hollow fiber methods, this method shows much better in sensitivity than the LLE (25 ng/mL) and it is compatible with SDME (0.5 ng/mL), SPME (0.5 ng/mL), and LPME using a dual gauge microsyringe with a hollow fiber (1 ng/mL). However, DDSME was more convenient than the LPME using a dual gauge microsyringe with a hollow fiber method and much lower cost than the SPME technique.     

Identification of peptides using gold nanoparticle-assisted single-drop microextraction coupled with AP-MALDI mass spectrometry

A novel technique, gold nanoparticle-assisted single-drop microextraction (SDME) combined with atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry (AP-MALDI-MS) for the identification of peptides has been described. The SDME of peptides from aqueous solution was achieved using gold nanoparticles prepared in toluene as the acceptor phase. A simple phenomenon of isoelectric point (pI) of the peptides has been utilized successfully to extract the peptides into a single drop of nanogold in toluene. After extraction, a single-drop nano gold solution was directly spotted onto the target plate with an equal volume of matrix, proportional, variant-cyanohydroxy cinnamic acid ( proportional, variant-CHCA) and analyzed in AP-MALDI-MS. The parameters, such as solvent selection, extraction time, agitation rate, and pH effect, were optimized for the SDME technique. Using this technique, in aqueous solution, the lowest concentration detected for Met- and Leu-enkephalin peptides was 0.2 and 0.17 microM, respectively. In addition, the application of this technique to obtain the signal for the selected peptides in a mass spectrum in the presence of matrix interferences such as 1% Triton X-100 and 6.5 M urea has been showed. The application was extended to identify the peptides spiked into urine.     

Determination of boron by flow injection analysis using a conductivity detector

A flow injection method for the determination of boron using a conductivity detector has been described. Boric acid injected into the flow system reacts with mannitol (0.3 M) in the mobile phase and an equivalent amount of H(+) is liberated in the stream. The increase in the conductance of the mobile phase due to the liberated H(+) has been equated to the boron concentration in the sample. A linear calibration for light- and heavy-water samples containing 0-20 μg/mL boron was obtained. Boron concentrations in the samples of light and heavy water and lithium pentaborate solution have been measured. The interferences due to various ions such as Na(+), Li(+), Cu(2+), Ni(2+), Co(2+), Fe(3+), Al(3+), SO(4)(2-), NO(3)(-), F(-), and Cl(-) could be eliminated by adopting a two-step sample pretreatment procedure. In the first step, all the anions were converted to Cl(-) by treating the sample solution with a strong anion-exchange resin. In the second step, the solution obtained from the first step was passed through a silver-guard cartridge to remove interfering cations and Cl(-). The relative standard deviation was ±0.25% for the determination of 1 μg of boron in light water, and the limit of detection was 0.01 μg present in an injection volume of 100 μL. The corresponding values for heavy water were ±0.38% and 0.1 μg, respectively.     

Equilibrium sampling through membranes of freely dissolved copper concentrations with selective hollow fiber membranes and the spectrophotometric detection of a metal stripping agent

A sensitive spectrophotometric method for the determination of freely dissolved copper concentrations in aqueous samples after preconcentration with hollow fiber membrane extraction has been developed. The method is based on the equilibrium sampling through a selective membrane into an acceptor solution containing 4-(pyridyl-2-azo)resorcinol (PAR), which serves as stripping agent and metal indicator. Negligible extraction of interferences and equilibrium enrichment of copper allowed for selective spectrophotometric determination of the Cu-PAR complex. Some important extraction parameters such as acceptor composition, shaking, equilibrium time, and sample volume were studied. The optimized methodology showed good linearity in the range of 5-100 microg/L, an enrichment factor of 93, good repeatability and reproducibility (RSDs < 6%, n = 6), and a detection limit of 4 microg/L. The cationic metals Ni2+, C(2+, Cd2+, Fe3+, Pb2+, Zn2+, and Mn2+ were shown not to interfere with the measurement of Cu2+. Measurements on samples containing mixtures of various ligands and cations were in good agreement with theoretically calculated concentrations, and the method was also applied to environmental samples. The developed technique requires less labor and less sophisticated equipment than conventional methods typically based on atomic absorption spectrometry or ICP.     

Determination of polychlorinated biphenyls in milk samples by saponification-solid-phase microextraction.

A saponification-HSSPME procedure has been developed for the extraction of PCBs from milk samples. Saponification of the samples improves the PCB extraction efficiency and allows attaining lower background. A mixed-level fractional design has been used to optimize the sample preparation process. Five variables have been considered: extraction time, agitation, kind of microextraction fiber, concentration, and volume of NaOH aqueous solution. Also the kinetic of the process has been studied with the two fibers (100-microm PDMS and 65-microm PDMS-DVB) included in this study. Analyses were performed on a gas chromatograph equipped with an electron capture detector and a gas chromatograph coupled to a mass selective detector working in MS-MS mode. The proposed method is simple and rapid, and yields high sensitivity, with detection limits below 1 ng/mL, good linearity, and reproducibility. The method has been applied to liquid milk samples with different fat content covering the whole commercial range, and it has been validated with powdered milk certified reference material.     

Liquid-phase microextraction as an on-line preconcentration method in capillary electrophoresis

A simple and efficient sample preconcentration method for capillary electrophoresis has been developed using liquid-phase microextraction (LPME). A thin layer of an organic liquid was used to separate a drop of the aqueous acceptor phase hanging at the inlet of a capillary from the bulk aqueous donor phase. The donor-phase pH was 1.0, and the acceptor phase pH was 9.5. This pH difference caused the preconcentration of the acidic compounds, fluorescein and fluorescein isothiocyanate, into the acceptor-phase drop. Enrichment factors of 3 orders of magnitude were obtained with 30-min LPME at 35 degrees C.     

Immunologic trapping in supported liquid membrane extraction

To obtain a high degree of selectivity in sample preparation, supported liquid membrane (SLM) extraction was combined with immunologic recognition. The SLM employs a hydrophobic polymer for supporting the immobilization of an organic solvent, thus forming a nonporous membrane. Said membrane separates the aqueous sample on one side (donor) from a receiving aqueous phase on the other (acceptor). The extraction involves the partitioning of neutral compounds between the sample solution, continuously pumped alongside the membrane, and the membrane. From the membrane, reextraction takes place into a second aqueous phase containing antibodies specific for the target compound(s). Hence, there is a formation of an antibody-antigen complex at the heart of the sample preparation (ImmunoSLM). When the immunocomplex forms, the antigen can no longer redissolve in the organic membrane, thus being trapped in the acceptor. Consequently, the concentration gradient of free antigen over the membrane is ideally unaffected, this being the driving force for the process. With a surplus of antibody, the concentration of analyte in the receiving phase will easily exceed the initial sample concentration. In this work, the so formed immunocomplex was quantified on-line, using a fluorescein flow immunoassay in a sequential injection analysis (SIA) setup. The outlined ImmunoSLM-SIA scheme was successfully applied for the extraction of 4-nitrophenol from spiked water solutions as well as from a spiked wastewater sample, indicating that the immunoextraction can be suitable when dealing with difficult matrixes.     

Exhaustive removal of thorium and uranium traces from neodymium by liquid extraction

The Th content in commercially available Nd₂O₃ samples with the main substance content of 99.0–99.998% was found to be 2–8, and that of U, 3–230 ppb. Therefore, to obtain Nd meeting the requirements of the experiment on studying neutrinoless double β-decay, it should be purified to reduce the content of Th and U impurities by a factor of 10³–10⁴. To this end, the extraction of Nd, Th, and U from hydrochloric acid media with solutions of trioctylphosphine oxide (TOPO) in toluene was studied. The distribution ratios of Th increase with a decrease in the HCl concentration in the initial aqueous solution. With an increase in the Cl^? concentration in the aqueous phase, the U distribution ratios decrease, probably because of a decrease in the concentration of the free extractant due to the extraction of Nd and HCl. On the contrary, the distribution ratios of Th increase with an increase in the Cl^? concentration in the aqueous phase, with the slope of the straight line in the coordinates logD _Th-log[Cl^?]_aq close to 7, which may be due to coextraction of Th with Nd in the form of the complex ThNdCl₇. The enthalpies of formation of the extractable complexes of Th and U were determined from the temperature dependence of the extraction of Nd, Th, and U chlorides with a 0.1 M solution of TOPO in toluene. The optimal extraction system was chosen for Nd purification to remove traces of Th and U: organic phase, 0.1 M solution of TOPO in toluene; aqueous phase, 2.4 M NdCl₃ + 0.1 M HCl. From the initial aqueous solution contaning 574 ppt Th and 2837 ppt U, by single extraction with an equal volume of 0.1 M TOPO in toluene, an aqueous solution containing <10 ppt Th and 31 ppt U (detection limit 10 ppt) was obtained. By semicountercurrent extraction, from the initial aqueous NdCl3 solution containing 200 ppb Th, the raffinate containing <10 ppt Th was obtained in one extraction step. The results obtained confirm the possibility of exhaustive removal of Th and U impurities (to the level of ≤1 ppt) from Nd by extraction with TOPO solutions from chloride solutions.     

Extractive removal of chromium (VI) from industrial waste solution

Extractive removal of Cr (VI) was carried out from chloride solutions using cyanex 923 mixed with kerosene. The efficiency of this extractant was studied under various experimental conditions, such as concentration of different mineral acids in the aqueous phase, concentration of cyanex 923 and Cr (VI) present in the initial aqueous feed, temperature and time of extraction, organic to aqueous (O/A) phase ratio. Percentage Cr (VI) extraction decreases with the increase in temperature at varying concentration of cyanex 923. The interference of the impurities usually associated with Cr (VI) such as Cr (III), Cu, Ni, Fe (II), Zn, Chloride and sulphate, etc., were examined under the optimized conditions and only Zn was found to interfere. Under the optimum experimental conditions 98.6-99.9% of Cr (VI) was extracted in 3-5 min at O/A of 2 with the initial feed concentration of 1g/L of Cr (VI). The extracted Cr (VI) was quantitatively stripped with 1M NaOH and the organic phase obtained after the stripping of Cr (VI) was washed with dilute HCl solution to neutralize any NaOH trapped/adhered to the solvent and then with distilled water. This regenerated solvent was reused in succeeding extraction of chromium (VI). Finally a few experiments were performed with the synthetic effluent from an electroplating industry.