Solvent extraction and extraction–voltammetric determination of phenols using room temperature ionic liquid

The phenolic compounds phenol, 4-nitrophenol, 2,4-dinitrophenol, 2,6-dinitrophenol, 1-naphthol, 2-naphthol, and 4-chlorophenol are extracted nearly quantitatively from aqueous solution into the room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMImPF₆) in molecular form at pH<pK_a. Picric acid is extracted efficiently in anionic form. Recovery of pyrocatechol and resorcinol is much lower. The effect of pH, phenol concentration, and volume ratio of aqueous and organic phases were studied. Ionic liquid BMImPF₆ is shown to be suitable for extraction–voltammetric determination of phenols without back-extraction or addition of support electrolyte. The electrochemical window of BMImPF₆ at various electrodes was determined, and voltammetric oxidation of phenols and reduction of nitrophenols in BMImPF₆ was studied.     

Electrochemical lithium extraction from β-lithium nitride

In this paper we report the electrochemical characterization of mixtures of ball-milled lithium nitride and iron metal. Several samples were prepared with different lithium nitride to iron molar ratios. X-ray diffraction (XRD) spectra showed the presence of iron metal in all the samples and β-lithium nitride in the samples with higher Li₃N/Fe ratio. No evidence of other phases was detected. The milled powders were used to prepare composite cathodes for the electrochemical characterization. It was found that lithium can be extracted from the materials at a flat potential of 1.2 V vs. Li. The sample with Li₃N/Fe molar ratio 8:1 showed the highest specific capacity (1125 mAh g⁻¹) corresponding to the extraction of 1.8 Li equivalents per mole of lithium nitride. Only a fraction of the lithium extracted was re-inserted in the following discharge cycle. A drastic reduction of the capacity was observed for all the samples on further cycling. An enhancement of the cyclability was obtained by lowering the end-charge voltage that resulted in a reduction of the lithium extracted. The lithium extraction/insertion process was characterized by a large voltage difference indicating that the reaction is largely irreversible.     

Identification and extraction—spectrophotometric or extraction—fluorimetric determination of organic nitrogen-containing triiodides, new biologically active compounds

A method for the identification of organic triiodides is proposed, and rapid, highly sensitive procedures for the extraction-spectrophotometric and extraction-fluorometric determination of medicinal preparations as ion associates with hydroxyxanthene (Eosin) and triphenylmethane (Bromothymol Blue) dyes. The formation of 1 : 1 ion associates with an absorption maximum at 545 nm (430 nm for ion associates with Bromothymol Blue) and a fluorescence maximum at 560 nm was detected. The ion associates were extracted with chloroform from a water-ethanol solution at pH 6.86 and 9.18. The detection limits were c_min ≈ 4.3 × 10^-7 M for the extraction-spectrophotometric and c_min ≈ 8.6 sx 10^-8 M for the extraction-fluorimetric procedure; RSD ≤2%. The developed procedures can be used for controlling medicinal preparations and monitoring biological materials     

Is there a future for sequential chemical extraction?

Since their introduction in the late 1970s, sequential extraction procedures have experienced a rapid increase in use. They are now applied for a large number of potentially toxic elements in a wide range of sample types. This review uses evidence from the literature to consider the usefulness and limitations of sequential extraction and thereby to assess its future role in environmental chemical analysis. It is not the intention to provide a comprehensive survey of all applications of sequential extractions or to consider the merits and disadvantages of individual schemes. These aspects have been covered adequately in other, recent reviews. This review focuses in particular on various key issues surrounding sequential extractions such as nomenclature, methodologies, presentation of data and interpretation of data, and discusses typical applications from the recent literature for which sequential extraction can provide useful and meaningful information. Also covered are emerging developments such as accelerated procedures using ultrasound- or microwave energy-assisted extractions, dynamic extractions, the use of chemometrics, the combination of sequential extraction with isotope analysis, and the extension of the approach to non-traditional analytes such as arsenic, mercury, selenium and radionuclides.     

Trace analysis of benzophenone-derived compounds in surface waters and sediments using solid-phase extraction and microwave-assisted extraction followed by gas chromatography–mass spectrometry

This study describes a procedure for determining eight benzophenone-derived compounds in surface waters and sediments. These include the pharmaceutical ketoprofen, its phototransformation products 3-ethylbenzophenone and 3-acetylbenzophenone, and five benzophenone-type ultraviolet (UV) filters. The proposed analytical method involves the pre-concentration of water samples by solid-phase extraction (SPE) and microwave-assisted extraction (MAE) of sediment samples followed by derivatization and analysis by gas chromatography–mass spectrometry. Different parameters were investigated to achieve optimal method performance. Recoveries of 91 to 96 % from water samples were obtained using HLB Oasis SPE cartridges, whereas MAE of sediments (30 min at 150 °C) gave recoveries of 80 to 99 %. Limits of detection were between 0.1 and 1.9 ng L^?1 for water samples and from 0.1 to 1.4 ng g^?1 for sediment samples. The developed method was applied to environmental samples and revealed the presence of UV filters in the majority of the surface waters with up to 690 ng L^?1 of 2-hydroxy-4-methoxybenzophenone. By contrast, ketoprofen (≤2,900 ng L^?1) and its degradation products (≤320 ng L^?1) were found in only two rivers, both receiving wastewater treatment plant effluents. Sediment analysis revealed benzophenone to be present in concentrations up to 650 ng g^?1, whereas concentrations of other compounds were considerably lower (≤32 ng L^?1). For the first time, quantifiable amounts of two ketoprofen transformation products in the aqueous environment are reported.     

Liquid-liquid extraction of α-activation products of iron with HDEHP

The carrier-free radiotracers,^52,56Mn,^55,56,58Co and^56,57Ni were produced simultaneously by accelerated -particle activation of iron. They were subsequently studied through LLX using the liquid cation exchanger, HDEHP, as an extractant. A considerable enrichment of individual carrier free radionuclides of manganese, cobalt and nickel was achieved. Production and verification of purity of the carrier-free radiotracers at different stages of their extraction were carried out by -ray spectroscopic studies.     

Cloud point extraction of Δ9-tetrahydrocannabinol from cannabis resin

A cloud point extraction coupled with high performance liquid chromatography (HPLC/UV) method was developed for the determination of Δ⁹-tetrahydrocannabinol (THC) in micellar phase. The nonionic surfactant “Dowfax 20B102” was used to extract and pre-concentrate THC from cannabis resin, prior to its determination with a HPLC–UV system (diode array detector) with isocratic elution. The parameters and variables affecting the extraction were investigated. Under optimum conditions (1 wt.% Dowfax 20B102, 1 wt.% Na₂SO₄, T?=?318 K, t?=?30 min), this method yielded a quite satisfactory recovery rate (~81 %). The limit of detection was 0.04 μg?mL^?1, and the relative standard deviation was less than 2 %. Compared with conventional solid–liquid extraction, this new method avoids the use of volatile organic solvents, therefore is environmentally safer.     

Microfluidic lab-on-chip advances for liquid–liquid extraction process studies

The ever-increasing complexity of industrial product recycling calls for more efficient purification processes such as liquid–liquid (L/L) extraction. Because of the high complexity of L/L extraction, optimizing a large-scale extraction is both time and resource consuming and can only be justified to solve high volume and value purification problems. It is therefore difficult to apply to small scale and highly variable waste material influx. We believe using a fully automated and integrated microfluidic approach will enable fast and cost-effective studies of L/L extraction processes. This review presents an overview of L/L metal extraction performed using microfluidics platforms. We first give an overview of the extraction methods. We then review the most relevant characterization methods integrated with such platforms.     

Solvent extraction of uranium from aqueous solutions by α-benzoinoxime

Solvent extraction of uranium with α-benzoinoxime from aqueous solutions has been systematically investigated. The extraction equilibration was very fast and achieved at 60 s for uranium. The extraction of uranium was pH-dependent using α-benzoinoxime as extractant. The effect concentration of uranium and α-benzoinoxime was studied. The uranium loaded in the organic phase can be stripped efficiently with 93 % yield using 0.1 M HCl as the stripping agent in a single stripping step. A good selectivity for uranium was observed through α-benzoinoxime as extractant from aqueous solution with other interfering cation ions. Present study suggested that α-benzoinoxime can be used as a potential extractant for separation of uranium from aqueous solution using centrifugal extractor in industrial application.     

Microfluidic chip for electrochemically-modulated liquid∣liquid extraction of ions

A microfluidic device with integrated electrodes for the electrochemically-modulated extraction of ions across immiscible aqueous–organic liquid–liquid interfaces is presented. Using a Y-shaped microfluidic channel with in situ electrodes and co-flowing aqueous and organic immiscible electrolyte solutions, the manipulation of the applied interfacial potential enabled the extraction of ions from the aqueous phase into the organic phase. Data for the extraction of tetraethylammonium cations from aqueous electrolyte into 1,2-dichloroethane electrolyte are presented. The device demonstrates the benefits of combination of microfluidics and liquid–liquid electrochemistry.     

Environmentally friendly analysis of emerging contaminants by pressurized hot water extraction–stir bar sorptive extraction–derivatization and gas chromatography–mass spectrometry

This work describes the development, optimization, and validation of a new method for the simultaneous determination of a wide range of pharmaceuticals (beta-blockers, lipid regulators…) and personal care products (fragrances, UV filters, phthalates…) in both aqueous and solid environmental matrices. Target compounds were extracted from sediments using pressurized hot water extraction followed by stir bar sorptive extraction. The first stage was performed at 1,500 psi during three static extraction cycles of 5 min each after optimizing the extraction temperature (50–150 °C) and addition of organic modifiers (% methanol) to water, the extraction solvent. Next, aqueous extracts and water samples were processed using polydimethylsiloxane bars. Several parameters were optimized for this technique, including extraction and desorption time, ionic strength, presence of organic modifiers, and pH. Finally, analytes were extracted from the bars by ultrasonic irradiation using a reduced amount of solvent (0.2 mL) prior to derivatization and gas chromatography–mass spectrometry analysis. The optimized protocol uses minimal amounts of organic solvents (<10 mL/sample) and time (≈8 h/sample) compared to previous existing methodologies. Low standard deviation (usually below 10 %) and limits of detection (sub-ppb) vouch for the applicability of the methodology for the analysis of target compounds at trace levels. Once developed, the method was applied to determine concentrations of these compounds in several types of sample (wastewater, seawater, pore water, and sediment) from Cadiz Bay (SW Spain). To our knowledge, these findings represent the first information available on the presence of some of the target compounds in the marine environment.     

Development of molecularly imprinted-solid phase extraction combined with dispersive liquid–liquid microextraction for selective extraction and preconcentration of triazine herbicides from aqueous samples

In this study, a sensitive and developed method based on the use of molecularly imprinted-solid phase extraction along with dispersive liquid–liquid microextraction has been reported for selective extraction and pre-concentration of triazine pesticides from aqueous samples. Molecularly imprinted microspheres (template, atrazine) were synthesized using precipitation polymerization and used as sorbent in SPE procedure. A model solution containing the studied pesticides was slowly passed through the atrazine-MIP cartridge. The adsorbed analytes were eluted with methanol, mixed with carbon tetrachloride (as extraction solvent) and rapidly injected into deionized water. In this process, the analytes were extracted into fine droplets of carbon tetrachloride and the fine droplets were sedimented in bottom of the conical test tube by centrifugation. Finally, GC-FID was used for the separation and determination of analytes in the sedimented phase. Some important parameters affecting the performance of developed method were completely investigated. The linear ranges of calibration curves were wide and limits of detection and limits of quantification were between 0.2–7 and 0.5–20 ng mL^?1, respectively. The relative standard deviation obtained for six repeated experiments of atrazine (10 ng mL^?1) was 3.1 %. The relative recoveries obtained for the atrazine in the spiked samples were within in the range of 92–98 %.     

Analysis of PAH compounds in soil with on-line coupled pressurised hot water extraction–microporous membrane liquid–liquid extraction–gas chromatography

Pressurised hot water extraction (PHWE) was coupled on-line with microporous membrane liquid-liquid extraction (MMLLE) and gas chromatography (GC) in the analysis of polycyclic aromatic hydrocarbon (PAH) compounds in soil. The MMLLE serves as a trapping device after the PHWE. Water from PHWE is directed to the donor side of the membrane unit and the analytes are extracted to the acceptor solution on the other side of the membrane. The role of MMLLE is to clean and concentrate the extract, which is then transferred on-line to the GC via a sample loop and an on-column interface using partially concurrent solvent evaporation. Separate optimisation of MMLLE and simulations of the PHWE-MMLLE connection were carried out before the actual on-line coupling. After optimisation of the whole on-line system, the efficiencies of the PHWE-MMLLE-GC and PHWE-solid-phase trap extractions were compared. The PHWE-MMLLE-GC method allowed on-line analysis of soil samples. The method was linear, with limits of detection in the range 0.05-0.13 ng and limits of quantification 0.65-1.66 microg g(-1). Comparison of the results with those obtained by other techniques confirmed the good performance.     

Electromembrane extraction (EME)—an easy, novel and rapid extraction procedure for the HPLC determination of fluoroquinolones in wastewater samples

For the first time, an electromembrane extraction combined with a HPLC procedure using diode array and fluorescence detection has been developed for the determination of seven widely used fluoroquinolones (FQs): marbofloxacin, norfloxacin, ciprofloxacin, danofloxacin, enrofloxacin, gatifloxacin and grepafloxacin. The drugs were extracted from acid aqueous sample solutions (pH 5), through a supported liquid membrane consisting of 1-octanol impregnated in the walls of a S6/2 Accurel® polypropylene hollow fiber, to an acid (pH 2) aqueous acceptor solution inside the lumen of the hollow fiber. The main operational parameters were optimized, and extractions were carried out in 15 min using a potential of 50 V. Enrichment factors of 40–85 have been obtained using only 15 min of extraction time versus 330 min used in a previously proposed hollow-fiber liquid-phase microextraction procedure. The procedure allows low detection and quantitation limits of 0.005–0.07 and 0.007–0.15 μg?L^?1, respectively. The proposed method was successfully applied to the FQs analysis in urban wastewaters.

Airlift reactor — membrane extraction hybrid system for aroma production

In recent times, environmental production methods and organic products are increasingly sought after in food, perfume, and cosmetic industries, where the products are consumed or come into direct contact with humans. One such additive is 2-phenylethanol, an alcoholic aromatic rose like smell compound, mainly used as a flavor and aroma. 2-Phenylethanol can be produced by bioconversion from l-phenylalanine using Saccharomyces cerevisiae. This type of biotransformation is strongly limited by product inhibition which allows reaching the maximum concentration of 2-phenylethanol, 4 g L^?1, in an ordinary batch, fed-batch, or chemostat bioreactor. The main aim of the presented work was to study the possible yield increase of 2-phenylethanol in a hybrid system consisting of membrane extraction performed by a hollow fiber membrane module immersed in the downcomer of an airlift reactor. Such hybrid system can be used to remove 2-phenylethanol from the fermentation medium and thus to overcome the product inhibition of biotransformation. In this paper, the influence of biomass on membrane extraction of 2-phenylethanol from aqueous solution in an airlift reactor to alkanes at different operational conditions was studied. The measured extraction kinetics was compared with the predictions obtained by a mathematical model. Hydrodynamics of the hybrid system was also studied.     

Systematic study of the solvent extraction of metal β-diketonates

The extraction of 30 metals (Be, Mg, Ca. Sr, Ba, Sc, La, Ti, Zr, Th, Cr, Mo, U, Mn, Co, Fe, Ni, Pd, Cu, Ag, Zn, Cd, Hg, Al, Ga, In, Tl, Sn, Pb and Bi) by solutions of acetylacetone, benzoylacetone and dibenzoylmethane in benzene has been studied in relation to the pH values for extraction. The extraction constants and two-phase stability constants of the β-diketonates were calculated; these can be used to determine the optimum conditions for the separation of many metals. The linear relationship between the distribution coefficients of β-diketones and their corresponding β-diketonates has been confirmed.     

Biphasic recognition chiral extraction — novel way of separating pantoprazole enantiomers

This paper presents a biphasic recognition chiral extraction system developed as a new chiral separation technology for the separation of pantoprazole enantiomers, combining a hydrophilic β-CD derivative in the aqueous phase and a hydrophobic tartaric acid in the organic phase which preferentially recognise the (R)-enantiomer and (S)-enantiomer, respectively. In this study, a number of factors which influence the efficiency of the extraction were investigated including types of organic solvents, β-CD and tartaric acid esters and their concentrations, pH and temperature. As a result, enantioselectivity for pantoprazole enantiomers can be improved up to 1.42 under optimised conditions; in addition, it is clear that the combined action of β-CD and tartaric acid esters leads to formation of the biphasic chiral extraction system with a stronger separation capacity than a monophasic chiral extraction system.     

Lipophilic ternary complexes in liquid–liquid extraction of trivalent lanthanides

The formation of ternary complexes between lanthanide ions [Nd(III) or Eu(III)], octyl(phenyl)-N,N-diisobutyl-carbamoylmethylphosphine oxide (CMPO), and bis-(2-ethylhexyl)phosphoric acid (HDEHP) was probed by liquid–liquid extraction and spectroscopic techniques. Equilibrium modeling of data for the extraction of Nd(III) or Eu(III) from lactic acid media into n-dodecane solutions of CMPO and HDEHP indicates the predominant extracted species are of the type [Ln(AHA)₂(A)] and [Ln(CMPO)(AHA)₂(A)], where Ln?=?Nd or Eu and A represents the DEHP^? anion. FTIR (for both Eu and Nd) and visible spectrophotometry (in the case of Nd) indicate the formation of the [Ln(CMPO)(A)₃] complexes when CMPO is added to n-dodecane solutions of the LnA₃ compounds. Both techniques indicate a stronger propensity of CMPO to complex Nd(III) versus Eu(III).     

Liquid–liquid extraction of scandium with nalidixic acid in dichloromethane

The extraction behavior of nalidixic acid (HNA) in CH₂Cl₂ has been studied for various di- and trivalent metal ions such as Cu(II), Fe(II), Ni(II), Mn(II), Sb(II), Co(II), Sc(III), Y(III), Nd(III) and Eu(III) from aqueous buffer solutions of pH 1–7 with 0.1 mol dm⁻³ nalidixic acid in dichloromethane. Separation factors of Sc(III) from these metals has shown that its clean separation is possible at pH 3.4–4. The parameters affecting the extraction of Sc(III) were optimized. The composition of the extracted adduct was determined by slope analysis method that came out to be Sc(NA)₃. Extraction of Sc(III) was studied in the presence of various cations and anions. Among the anions studied only fluoride, citrate and oxalate have significant interference whereas, Fe(III) has reduced the extraction to 53% that can be removed by using ascorbic acid as reducing agent. The proposed extraction system proved good stability up to six extraction-stripping stages for the extraction of Sc(III).