Low-density solvent-based solvent demulsification dispersive liquid-liquid microextraction for the fast determination of trace levels of sixteen priority polycyclic aromatic hydrocarbons in environmental water samples

For the first time, the low-density solvent-based solvent demulsification dispersive liquid-liquid microextraction was developed for the fast, simple, and efficient determination of 16 priority polycyclic aromatic hydrocarbons (PAHs) in environmental samples followed by gas chromatography-mass spectrometric (GC-MS) analysis. In the extraction procedure, a mixture of extraction solvent (n-hexane) and dispersive solvent (acetone) was injected into the aqueous sample solution to form an emulsion. A demulsification solvent was then injected into the aqueous solution to break up the emulsion, which turned clear and was separated into two layers. The upper layer (n-hexane) was collected and analyzed by GC-MS. No centrifugation was required in this procedure. Significantly, the extraction needed only 2-3 min, faster than conventional DLLME or similar techniques. Another feature of the procedure was the use of a flexible and disposable polyethylene pipette as the extraction device, which permitted a solvent with a density lighter than water to be used as extraction solvent. This novel method expands the applicability of DLLME to a wider range of solvents. Furthermore, the method was simple and easy to use, and some additional steps usually required in conventional DLLME or similar techniques, such as the aforementioned centrifugation, ultrasonication or agitation of the sample solution, or refrigeration of the extraction solvent were not necessary. Important parameters affecting the extraction efficiency were investigated in detail. Under the optimized conditions, the proposed method provided a good linearity in the range of 0.05-50 μg/L, low limits of detection (3.7-39.1 ng/L), and good repeatability of the extractions (RSDs below 11%, n=5). The proposed method was successfully applied to the extraction of PAHs in rainwater samples, and was demonstrated to be fast, efficient, and convenient.     

The electroanalytical detection and determination of copper in heavily passivating media: ultrasonically enhanced solvent extraction by N-benzoyl-N-phenyl-hydroxylamine in ethyl acetate coupled with electrochemical detection by sono-square wave stripping voltammetry analysis.

N-benzoyl-N-phenyl-hydroxylamine dissolved in ethyl acetate was employed as a ligand for the solvent extraction of copper. Ultrasonic emulsification was shown to be effective both in the extraction of copper from an aqueous phase into ethyl acetate and its recovery or "back extraction" into a fresh clean aqueous solution. Experimental determination of thermodynamic parameters governing the extraction process via UV/visible spectroscopy is reported. This permitted theoretical predictions for the amount of copper transferred into the final aqueous solution to be fitted to experimental data. Quantitative analysis of copper removed via double sono-extraction from an aqueous medium hostile to voltammetric analysis proceeded via sono-square wave anodic stripping voltammetry analysis (sono-SWASV). This resulted in very high sensitivity in the relatively clean medium. The technique was then applied to the analysis of copper in the soft drink 'Ribena Light'. In the absence of sample preparation by solvent extraction sono-SWASV yields a measurable peak current for copper. However it is irreproducible and erratic due to passivating effects, possibly attributed to the sugars, natural flavourings and colourings present. Following sono-solvent extraction, the overall copper concentration could be obtained with a detection limit of 2 microg L(-1). Biphasic sono-extraction synergistically coupled with the recognized technique sono-SWASV presents an attractive technique for copper analysis in electrode passivating media. The technique necessarily removes contaminants present in the test solution since these will prefer to remain in the initial aqueous phase, or will transfer to the organic phase but are unlikely to be doubly transferred into the 'clean' final aqueous phase.     

Novel calix[4]arene-thiacrown ether for selective and efficient extraction of Ba(II), Pb(II), and Hg(II)

A di-ionizable p-tert-butylcalix[4]arene-1,3-thiacrown-5 ether extractant was synthesized. Its cone conformation and polyether ring attachment regioselectivity were verified by NMR spectroscopy. The metal ion-complexing properties of this ligand were evaluated by solvent extractions of metal cations from aqueous solutions into chloroform. The ligand was found to be an efficient extractant with Ba²⁺ selectivity in competitive solvent extraction of alkaline earth metal cations. It also exhibits high extraction ability for Pb²⁺ and for Hg²⁺ in single species solvent extractions.     

Membrane-based solvent extraction for selective removal and recovery of metals

A membrane-based solvent extraction process was developed for selective removal and recovery of metals from aqueous solutions. The process utilizes microporous membranes as an interface between an aqueous solution and organic solvents containing liquid ion exchangers. Metal ions are transported from the aqueous solution to the organic phase at the interface created in the pores of membrane. The organic solvent, which is loaded with metal ions in the extraction module, is regenerated in contact with the stripping solution in the stripping module. One important feature of this process is the stability of the membrane system, which results from using an aqueous—organic separator to remove aqueous solution from the organic circulating line. This process was evaluated for enrichment of copper using solvents containing LIX 64N. The process is applicable to selective recovery of metals from ore leachates or metal-containing wastewater.     

Thermodynamic studies of partitioning behavior of cytochrome c in ionic liquid-based aqueous two-phase system

The ionic liquid/aqueous two-phase extraction systems (ATPSs) based on imidazolium ionic liquids were used to extract cytochrome c. Effects of the alkyl chain length of the ionic liquid cations, concentration of potassium citrate, temperature and pH on the extraction efficiency have been investigated. The thermodynamic parameters (ΔG(T)°, ΔH(T)° and ΔS(T)°) associated with Cyt-c partitioning in aqueous two phase systems were determined. Thermodynamic studies indicated that the partitioning of Cyt-c was driven by both hydrophobic and electrostatic interactions in the extraction process. Under the optimum conditions, experiment results showed that 94% of the cytochrome c could be extracted into the ionic liquid-rich phase in a one-step extraction. The structural characterization of Cyt-c in the IL ATPS was investigated by UV-vis and circular dichroism (CD) spectra. The results demonstrated that no direct bonding interaction observed between ionic liquid and cytochrome c, while the native properties of the cytochrome c were not altered. Compared with traditional liquid-liquid extractions based on toxic organic solvents, ionic liquid/aqueous two phase extraction offers clear advantages due to no use of volatile organic solvent and low consumption of imidazolium ionic liquids.     

Dispersive liquid-liquid microextraction based on the solidification of floating organic droplet for the determination of polychlorinated biphenyls in aqueous samples

In the proposed method, an extraction solvent with a lower toxicity and density than the solvents typically used in dispersive liquid-liquid microextraction was used to extract seven polychlorinated biphenyls (PCBs) from aqueous samples. Due to the density and melting point of the extraction solvent, the extract which forms a layer on top of aqueous sample can be collected by solidifying it at low temperatures, which form a layer on top of the aqueous sample. Furthermore, the solidified phase can be easily removed from the aqueous phase. Based on preliminary studies, 1-undecanol was selected as the extraction solvent, and a series of parameters that affect the extraction efficiency were systematically investigated. Under the optimized conditions, enrichment factors for PCBs ranged between 494 and 606. Based on a signal-to-noise ratio of 3, the limit of detection for the method ranged between 3.3 and 5.4 ng L⁻¹. Good linearity, reproducibility and recovery were also obtained.     

A dispersive liquid-liquid microextraction using a switchable polarity dispersive solvent. Automated HPLC-FLD determination of ofloxacin in chicken meat

In this article, dispersive liquid-liquid microextraction (DLLME), based on the use of so-called switchable polarity dispersive solvent (SPDS) for microextraction, is presented for the first time. The new extraction technique makes use of a mixture of extraction solvent (dichloromethane) and the SPDS (acrylic acid). This mixture is injected into the aqueous sample solution, which was previously fortified with the alkaline agent (NaOH). The SPDS is dissolved in aqueous phase and a cloudy solution consisting of fine droplets of extraction solvent fully dispersed in the aqueous phase is observed. Simultaneously, as a consequence of the fast neutralization reaction, the SPDS investigated is converted into water-soluble salt and phase separation is achieved because the SPDS switches its polarity. Conversion of the SPDS excludes the negative influence of the conventional dispersive solvents used in DLLME on the solubility of target analytes in aqueous phase and, as a result, increases the DLLME efficiency.     

Studies on Liquid/liquid Extraction of Copper Ion with Room Temperature Ionic Liquid

Room temperature ionic liquids are regarded as “Green solvents” for their nonvolatile and thermally stable properties. They are employed to replace traditional volatile organic solvents in organic synthesis, solvent extraction, and electrochemistry. In this work, a water immiscible room temperature ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate [C₄mim][PF₆], was used as an alternative solvent for liquid/liquid extraction of copper ions. Metal chelators, including dithizone, 8‐hydroxyquinoline, and 1‐(2‐pyridylazo)‐2‐naphthol, were employed to form neutral metal‐chelate complexes with copper ions so that copper ions were extracted from aqueous solution into [C₄mim][PF₆]. The parameters that affect the extraction of copper ions with this biphasic system were investigated. The extraction behavior in this novel biphasic system is shown to be consistent with that of traditional solvents. For example, the extraction with this biphasic system is strongly pH dependent. So, the extraction efficiency of coppers ion from an aqueous phase can be manipulated by tailoring the pH value of the extraction system. Hence, the extraction, separation and preconcentraction of copper ions can be accomplished by controlling the pH value of the extraction system. It appears that the use of ionic liquid as an alternate solvent system in liquid/liquid extraction of copper ions is very promising.     

Selective separation of copper with Lix 864 in a hollow fiber module

The transfer and separation of Cu(II), Co(II), Ni(II) and Zn(II) ions across a hollow fiber supported liquid membrane containing LIX 864 as the mobile carrier dissolved in kerosene solvent has been investigated. The flux and selectivity for copper has been studied as a function of the feed flow, the carrier concentration in the liquid membrane and the extraction solution acidity. A maximum copper recovery at 30% of LIX (v/v) in the diluent was obtained. The permeation experiments showed that at pH 2 in the extraction solution a highly selective separation of Cu over the other cations can be achieved. Increasing the acidity of the extraction solution copper selectivity decrease and the grade of recuperation sequence is Cu>Co>Ni>Zn. These results suggest that in selected situations, this membrane system can be competitive with the conventional liquid-liquid extraction process, in particular in leaching solutions with low metal concentration.     

Microwave-assisted extraction combined with dispersive liquid-liquid microextraction as a new approach to determination of chlorophenols in soil and sediments

A new method was applied for extraction of five chlorophenols from soil and marine sediment samples. Microwave-assisted extraction coupled with dispersive liquid-liquid microextraction followed by semi-automated in-syringe back-extraction technique was used as an extraction technique. Microwave-assisted extraction was performed by using 2.0 mL of alkaline water at pH 10.0. After extraction, the pH of extraction solution was adjusted at 6.0 and dispersive liquid-liquid microextraction procedure was done using 1.0 mL of acetone as a disperser solvent and 37.0 μL of chlorobenzene as extraction solvent. About 20.0 ± 0.5 μL sedimented phase was collected after centrifugation step. Then, chlorophenols were back extracted into 20 μL of alkaline water at pH 12.0 within the microsyringe. Finally, 20.0 μL of aqueous solution was injected into high performance liquid chromatography with ultra violet detection for analysis. The obtained recovery and preconcentration factors for the analytes were in the range of 68.0-82.0% and 25-30, respectively, with relative standard deviations ≤7.6%. The limits of the detection were found in the range of 0.0005-0.002 mg/kg. The method provides a simple and fast procedure for the extraction and determination of chlorophenols in soil and marine sediment samples.     

Pressurised hot water extraction-microporous membrane liquid-liquid extraction coupled on-line with gas chromatography-mass spectrometry in the analysis of pesticides in grapes

Pressurised hot water extraction-microporous membrane liquid-liquid extraction was coupled on-line with gas chromatography-mass spectrometry (PHWE-MMLLE-GC-MS) for the analysis of pesticides in grapes. MMLLE serves as a trapping step after 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. The role of MMLLE is to clean and concentrate the extract before on-line transfer to the GC via a sample loop and an on-column interface using partially concurrent solvent evaporation. The extraction conditions were investigated, and then the quantitative features such as linearity, limit of quantification (LOQ), extraction yield and enrichment factors. LOQs in the range 0.3-1.8 microg kg(-1) were achieved. Procymidone and tetradifon were found in the skins of the grapes. The results were in good agreement with those obtained by liquid-solid and ultrasonic extractions.     

On-line coupling of subcritical water extraction with high-performance liquid chromatography via solid-phase trapping

Although ambient water is very polar and cannot dissolve many organic species, water at elevated temperatures behaves like a polar organic solvent. Thus, subcritical water has been proven to be an effective extraction fluid for several classes of organic compounds. While solvent trapping was used to collect the extracted analytes in most of previous subcritical water extractions, sorbent trapping has also been developed for subcritical water extraction. In this study, an on-line system for subcritical water extraction and high-performance liquid chromatography (HPLC) was built and tested. A sorbent trap was used as the interface between subcritical water extraction and HPLC. Several shut-off valves have been utilized to switch the system from one mode to another (e.g., from the extraction mode to HPLC mode). The coupling technique of subcritical water extraction and HPLC eliminates the liquid-liquid extraction used in solvent trapping subcritical water extraction and provides higher sensitivity. Compared to the off-line system reported in an earlier work, the operation of this on-line system is even easier. Some peak broadening occurred after the coupling the water extraction with HPLC for the analytes studied. The performance of this on-line system was evaluated by the extraction and determination of caffeine, nitrotoluenes, polychlorinated biphenyls, chlorophenols and anilines.     

Simultaneous derivatization and extraction of anilines in waste water with dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometric detection

The one-step derivatization and extraction technique for the determination of anilines in river water by dispersive liquid-liquid microextraction (DLLME) is presented. In this method the anilines are extracted by DLLME and derivatized with pentafluorobenzaldehyde (PFBAY) in aqueous solution simultaneously. In this derivatization/extraction method, 0.5 ml acetone (disperser solvent) containing 10 microl chlorobenzene (extraction solvent) and 30 g/l pentafluorobenzaldehyde (PFBAY) dissolved in methanol was rapidly injected by syringe into 5 ml aqueous sample (pH 4.6). Within 20 min the analytes extracted and derivatized were almost finished. After centrifugation, 2 microl sedimented phase containing enriched analytes was determined by GC-MS. The effects of extraction and disperser solvent type and their volume, pH value of sample solution, derivatization and extraction time, derivatization and extraction temperature were investigated. Linearity in this developed method was ranging from 0.25 to 70 microg/l, and the correlation coefficients (R2) were between 0.9955 and 0.9989, and reasonable reproducibility ranging from 5.8 to 11.8% (n=5). Method detection limits (MDLs) ranged from 0.04 to 0.09 microg/l (n=5).     

Modified superheated water extraction of pesticides from spiked sediment and soil

In this study a laboratory-made superheated water system was applied in order to extract some pesticides from sand, sediment and soil samples. Extraction efficiencies were investigated at different time intervals with regard to temperature, type and amount of organic modifier. Pesticides were removed from the aqueous extract using dichloromethane as a trapping solvent. The optimal extraction temperature from sand specimens for malathion, heptachlor, aldrin, dieldrin, butachlor, metalaxyl and propiconazole was found to be 160 °C, while those for chlordane and thiobencarb were 120 °C and 180 °C, respectively. The static extraction time for heptachlor, aldrin, dieldrin, butachlor and metalaxyl was found to be 15 min, whereas for malathion and thiobencarb it was 5 min, and for chlordane and propiconazole it was 10 and 20 min, respectively. Recoveries for the extractions of the pesticides from sand under optimized extraction conditions ranged between 96 and 101%. Those obtained from sediment under such conditions were unsatisfactory, and were consequently improved by adding an organic modifier to the superheated water, and sodium chloride to the extract during liquid-liquid extraction. These procedures were optimized further for the parameters described and recoveries exceeded 91%, with the exception of butachlor. The extraction technique was also applied to soil samples at a reduced water flow rate of 0.5 mL min⁻¹, yielding recoveries of 82–105%, and 76% for dieldrin. The reproducibilities, expressed as relative standard deviations (RSDs), ranged between 2 and 13%.     

Determination of medroxyprogesterone in water samples using dispersive liquid-liquid microextraction with low solvent consumption

A simple, rapid and efficient extraction procedure, dispersive liquid-liquid microextraction with low solvent consumption, has been developed in combination with high-performance liquid chromatography-ultraviolet detection for the extraction and determination of medroxyprogesterone from aqueous samples. For this technique, 120 μL of the mixture of extraction solvent and dispersive solvent at a ratio of 3:7 was injected into the aqueous sample with a syringe. Then a cloudy solution forms while manually shaking the conical centrifuge tube. After centrifuging, the extractant settled at the bottom of the conical centrifuge tube and part of it was introduced into the HPLC system. Some key parameters, including the type and volume of extraction solvent and dispersive solvent, extraction time and salt effect were investigated. Under optimum conditions, good linear behavior (R?>?0.9982) over the investigated concentration ranges were obtained. The method was successfully applied to tap water, farm water and river water samples.     

Evaluation of methods for the determination of chlorophenols in surface water

Three methods for the determination of chlorophenols in surface water have been evaluated. Two of them utilize solid phase extraction followed by derivatization either in aqueous phase or in organic solvent. The third method is based on liquid-liquid extraction with simultaneous in-situ derivatization. This method was found to be not applicable for samples of surface water. The surfactants present in the samples prevent the separation of the hexane layer at a ratio of 1 : 20 or higher. Both methods using solid phase extraction gave acceptable results; however, the derivatization in aqueous phase proved its priority.     

Evaluation of methods for the determination of chlorophenols in surface water

Three methods for the determination of chlorophenols in surface water have been evaluated. Two of them utilize solid phase extraction followed by derivatization either in aqueous phase or in organic solvent. The third method is based on liquid-liquid extraction with simultaneous in-situ derivatization. This method was found to be not applicable for samples of surface water. The surfactants present in the samples prevent the separation of the hexane layer at a ratio of 1 : 20 or higher. Both methods using solid phase extraction gave acceptable results; however, the derivatization in aqueous phase proved its priority.     

Solvent extraction of U(VI) by trioctylphosphine oxide using a room-temperature ionic liquid

The unique physical and chemical properties of room-temperature ionic liquids(RTILs) have recently received increasing attention as solvent alternatives for possible application in the field of nuclear industry, particularly in liquid-liquid separations of radioactive nuclides. We investigated solvent extraction of U(VI) from aqueous solutions into a commonly used ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([C4mim][NTf2]) using trioctylphosphine oxide(TOPO) as an extractant. The effects of contact time, TOPO concentration, acidity, and nitrate ions on the U(VI) extraction are discussed in detail. The extraction mechanism was proposed based on slope analysis and UV-Vis measurement. The results clearly show that TOPO/[C4mim][NTf2] provides a highly efficient extraction of U(VI) from aqueous solution under near-neutral conditions. When the TOPO concentration was 10 mmol/L, the extraction of 1 mmol/L U(VI) was almost complete( 97%). Both the extraction efficiency and distribution coefficient were much larger than in conventional organic solvents such as dichloromethane. Slope analysis confirmed that three TOPO molecules in [C4mim][NTf2] bound with one U(VI) ion and one nitrate ion was also involved in the complexation and formed the final extracted species of [UO2(NO3)(TOPO)3]+. Such a complex suggests that extraction occurs by a cation-exchange mode, which was subsequently evidenced by the fact that the concentration of C4mim+ in the aqueous phase increased linearly with the extraction percent of U(VI) recorded by UV-Vis measurement.     

Electrochemical solid-phase microextraction of anions and cations using polypyrrole coatings and an integrated three-electrode device

A method for the extraction, transfer and desorption of anions and cations under controlled potential conditions employing a new integrated three-electrode device is described. The device, containing working, reference and counter electrodes, was prepared from tubes that could be moved vertically with respect to each other. In this way, a small amount of solvent, held by capillary force, remained between the electrodes when the device was lifted out of a solution after an extraction. This design allowed the potential control to be maintained at all times. With the new integrated device, it was possible to perform potential controlled desorption into vials containing as little as 200 microl of solution. The required ion exchange capacity was obtained by electrodeposition of a polypyrrole coating on the surface of the glassy carbon working electrode. Solid-phase microextractions of several cations or anions were performed simultaneously under potentiostatic control by doping the polypyrrole coating with different anions such as perchlorate and p-toluenesulfonate. The efficiency of the extractions, which could be altered by varying the potential of the working electrode, could be increased by 150 to 200% compared to extractions using normal solid-phase microextraction conditions under open circuit conditions. A constant potential of +1.0 V and -0.5 V with respect to the silver pseudo reference electrode, was found to be well-suited for the extraction of samples containing ppm concentrations of anions (chloride, nitrite, bromide, nitrate, sulfate and phosphate) and cations (cadmium, cobalt and zinc), respectively.     

Ion-pair liquid-liquid-liquid microextraction of nerve agent degradation products followed by capillary electrophoresis with contactless conductivity detection

The four nerve agent degradation products methylphosphonic acid (MPA), ethyl methylphosphonic acid (EMPA), isopropyl methylphosphonic acid (IMPA) and cyclohexyl methylphosphonic acid (CMPA) have been successfully extracted from aqueous sample solution by ion-pair liquid-liquid-liquid microextraction. In this procedure, the target analytes in the sample solution were converted into their ion-pair complexes with tri-n-butyl amine and then extracted by an organic solvent (1-octanol) layer on top of the sample solution. Simultaneously, the analytes were back-extracted into a drop of an aqueous acceptor solution which was suspended in the organic phase at a microsyringe needle tip. The factors influential to extraction: type of organic solvent, type of ion-pair reagent and its concentration, pH values of sample solution and acceptor aqueous phase, stirring rate and extraction time were investigated in detail. After extraction, the drop of the acceptor solution was withdrawn into the syringe and injected into a capillary electrophoresis system for analysis. Using contactless conductivity detection, direct quantification of these compounds is possible. Moreover, large-volume sample injection was employed for further preconcentration. Improvements in the limits of detection between 2.5 and 4 orders of magnitude could be achieved and concentrations at the ng/mL level can be determined. This newly established approach was successfully applied to a spiked river water sample.