Extraction and separation of zirconium from hafnium by using nano-structured supramolecular solvent microextraction method

In the present study, a simple versatile extraction method based on supramolecular solvent microextraction followed by inductively coupled plasma atomic emission spectrometry was developed for the extraction, separation and determination of zirconium (Zr) from hafnium (Hf). Zr and Hf were complexed with bis(2,4,4-trimethylpentyl) phosphinic acid, to obtain hydrophobic complex, and extracted into supramolecular solvent phase. The effective parameters on the supramolecular solvent microextraction efficiency were studied and optimized by using two different optimization methods: one variable at a time and central composite design. Under the optimum conditions, the linear range of 0.3–200.0 and 2.0–200.0 µg L^?1, detection limits (S/N = 3) of 0.1 and 0.6 µg L^?1, and precisions (n = 5) of 3.2–4.9% and 3.0–5.1% were obtained for Zr and Hf, respectively. Finally, the proposed method has been successfully applied for the extraction and separation of these cations in zirconium ore sample.     

Simultaneous Determination of Deltamethrin and Permethrin in Water Samples Using Homogeneous Liquid–Liquid Microextraction via Flotation Assistance and GC-FID

A new method was developed for the simultaneous determination of deltamethrin and permethrin in water samples with homogeneous liquid–liquid microextraction via flotation assistance and gas chromatography–flame ionization detection. A special extraction cell was designed to facilitate collection of the low density solvent extracts. The sample solution was added into the extraction cell, which contained an appropriate mixture of n-hexane (as an extraction solvent) and acetone (as a homogeneous solvent). Air flotation allowed the extraction solvent to be collected from the top of the solution. Under the optimum conditions, good linearity was observed in the range of 1.0–200 μg L^?1 with a correlation coefficient (r ²) greater than 0.9980 for both of the analytes. The limits of detection were 0.2 and 0.3 μg L^?1 for deltamethrin and permethrin, respectively (S/N = 3). The developed method was successfully applied to determine the two pesticides in three different water samples.     

Trace determination of cadmium in rice samples using solidified floating organic drop microextraction based on vesicular supramolecular solvent followed by flow-injection analysis–flame atomic absorption spectrometry

In this work, a solidified floating organic drop microextraction was developed based on a vesicular supramolecular solvent consisting of decanoic acid and quaternary ammonium. The method was used for preconcentration of trace amount of cadmium in different rice samples followed by flow-injection analysis–flame atomic absorption spectrometry. Several parameters affecting the extraction efficiency including pH, concentration of 1-(2-pyridylazo)-2-naphthol as the chelating agent, sample and extraction solvent volume, stirring rate, extraction time, salt effect, and interfering ions were investigated and optimized. Under the optimum conditions, a preconcentration factor of 84 was achieved. LOD and LOQ were found to be 0.09 and 0.31 µg L^?1, respectively. The calibration curve was linear within the range of 5.0–700 µg L^?1 (r²?>?0.9978). Intra- and inter-day precisions (RSD% n?=?3) were estimated 2.7 and 3.9% at the concentration of 20 µg L^?1, respectively. The accuracy of the method was successfully validated by analysis of an SRM-1643f standard reference material. Relative recoveries were achieved within the range of 93–107% elucidating suitability of the method for determination of cadmium in rice samples.     

Rapid Determination of DDT and Its Metabolites in Environmental Water Samples with Mixed Ionic Liquids Dispersive Liquid–Liquid Microextraction Prior to HPLC-UV

In this paper, a novel mixed ionic liquids-dispersive liquid–liquid microextraction method was developed for rapid enrichment and determination of environmental pollutants in water samples. In this method, two kinds of ionic liquids, hydrophobic ionic liquid and hydrophilic ionic liquid, were used as extraction solvent and disperser solvent, respectively. DDT and its metabolites were used as model analytes and high-performance liquid chromatography with ultraviolet detector for the analysis. Factors that may affect the extraction recoveries, such as type and volume of extraction solvent (hydrophobic ionic liquid) and disperser solvent (hydrophilic ionic liquid), extraction time, sample pH and ionic strength, were investigated and optimized. Under the optimum conditions, the linear range was 1–100 μg L⁻¹, limits of detection could reach 0.21–0.49 μg L⁻¹, and relative standard deviation was 6.01–8.48 % (n = 7) for the analytes. Satisfactory results were achieved when the method was applied to analyze the target pollutants in environmental water samples with spiked recoveries over the range of 85.7–106.8 %.

     

Liquid–Liquid Microextraction of Nitrophenols Using Supramolecular Solvent and Their Determination by HPLC with UV Detection

A novel, efficient, and environmentally friendly method—supramolecular solvent liquid–liquid microextraction (SMS-LLME) combined with high-performance liquid chromatography (HPLC)—was first established for the determination of p-nitrophenol and o-nitrophenol in water samples. Several important parameters influencing extraction efficiency, such as the type and volume of extraction solvent, pH of sample, temperature, salt effect, extraction time, and stirring rate, were optimized in detail. Under the optimal conditions, the enrichment factor was 166 for p-nitrophenol and 160 for o-nitrophenol, and the limits of detection by HPLC were 0.26 and 0.58 μg L^?1, respectively. Excellent linearity with coefficients of correlation from 0.9996 to 0.9997 was observed in the concentration range of 2–1,000 μg L^?1. The ranges of intra- and interday precision (n = 5) at 100 μg L^?1 of nitrophenols were 5.85–7.76 and 10.2–11.9 %, respectively. The SMS-LLME method was successfully applied for preconcentration of nitrophenols in environmental water samples.     

Application of vortex-assisted supramolecular solvent liquid–liquid microextraction for trace determination of nitroaniline isomers

A novel, fast and efficient method for the analysis of nitroaniline isomers as model compounds was developed using vortex-assisted supramolecular solvent liquid–liquid microextraction (VA-SMS-LLME). A vortex mixer was used as the mixer in supramolecular solvent liquid–liquid microextraction, and it decreased the extraction time greatly. Several important parameters influencing extraction efficiency, such as the type and volume of extraction solvent, pH of sample, salt effect and extraction time, were optimised in detail. Under the optimal conditions, the enrichment factor was 133 for p-nitroaniline, 98 for m-nitroaniline and 115 for o-nitroaniline, and the limits of detection by HPLC were 0.3, 1.0 and 0.5 μg L^?1, respectively. Linearity with determination coefficient from 0.9981 to 0.9993 was evaluated using water samples spiked with the nitroanilines at fourteen different concentration ranging from 4 to 1000 μg L^?1. The ranges of intra-day and inter-day precision (n = 5) at 10 μg L^?1 of nitroanilines were 1.67–7.05% and 9.4–11.6%, respectively. The VA-SMS-LLME method was successfully applied for preconcentration of nitroanilines in environmental water samples.     

Supramolecular solvent-based hollow fiber liquid phase microextraction of benzodiazepines

A new, efficient, and environmental friendly hollow fiber liquid phase microextraction (HF-LPME) method based on supramolecular solvents was developed for extraction of five benzodiazepine drugs. The supramolecular solvent was produced from coacervation of decanoic acid aqueous vesicles in the presence of tetrabutylammonium (Bu₄N⁺). In this work, benzodiazepines were extracted from aqueous samples into a supramolecular solvent impregnated in the wall pores and also filled inside the porous polypropylene hollow fiber membrane. The driving forces for the extraction were hydrophobic, hydrogen bonding, and π-cation interactions between the analytes and the vesicular aggregates. High-performance liquid chromatography with photodiode array detection (HPLC-DAD) was applied for separation and determination of the drugs. Several parameters affecting the extraction efficiency including pH, hollow fiber length, ionic strength, stirring rate, and extraction time were investigated and optimized. Under the optimal conditions, the preconcentration factors were obtained in the range of 112–198. Linearity of the method was determined to be in the range of 1.0–200.0 μg L⁻¹ for diazepam and 2.0–200.0 μg L⁻¹ for other analytes with coefficient of determination (R²) ranging from 0.9954 to 0.9993. The limits of detection for the target benzodiazepines were in the range of 0.5–0.7 μg L⁻¹. The method was successfully applied for extraction and determination of the drugs in water, fruit juice, plasma and urine samples and relative recoveries of the compounds studied were in the range of 90.0–98.8%.     

Rapid Ultrasound-Assisted Emulsification Microextraction Combined with COU-2 Dispersive Micro-solid Phase Extraction for the Determination of Azole Antifungals in Milk Samples by HPLC-DAD

A rapid, simple, and efficient method using ultrasound-assisted emulsification microextraction combined with dispersive micro-solid phase extraction (USAE-D-µ-SPE) was developed for detection and quantification of three azole antifungals in milk samples by high-performance liquid chromatography diode array detector. In this study, mesoporous carbon, COU-2, was used as sorbent in USAE-D-µ-SPE for the extraction and preconcentration of analytes. Several important experimental parameters, including type of deproteinized solvents, desorption time, type of extraction solvents, volume of extraction solvent, extraction time, emulsification time, sample pH, salt addition, and mass of COU-2 sorbent, were optimized using spiked milk samples. Under the optimum extraction and detection conditions, three azole antifungals, namely ketoconazole, clotrimazole, and miconazole, were determined within 20 min, with good linearity of matrix-matched calibration in the range of 0.5–5000.0 µg L^?1 with coefficient of determination, r ² ≥ 0.9943. The method showed limits of detection and limits of quantification of all analytes in the range of 0.15–3.0 and 0.5–10.0 µg L^?1, respectively. Good repeatability with RSDs <15% (n = 3) and satisfactory relative recoveries (83.3–111.1%) were obtained for spiked azole antifungal drugs in milk. The results reveal that the developed USAE-D-µ-SPE method was a simple, rapid, efficient, environmentally friendly, and practicable method for the determination of azole antifungals in milk samples.     

Optimization of parameters for the alcoholic-assisted dispersive liquid–liquid microextraction of estrogens in water

Extraction and determination of estrogens in water samples were performed using alcoholic-assisted dispersive liquid–liquid microextraction (AA-DLLME) and high-performance liquid chromatography (UV/Vis detection). A Plackett–Burman design and a central composite design were applied to evaluate the AA-DLLME procedure. The effect of six parameters on extraction efficiency was investigated. The factors studied were volume of extraction and dispersive solvents, extraction time, pH, amount of salt and agitation rate. According to Plackett–Burman design results, the effective parameters were volume of extraction solvent and pH. Next, a central composite design was applied to obtain optimal condition. The optimized conditions were obtained at 220 μL 1-octanol as extraction solvent, 700 μL ethanol as dispersive solvent, pH 6 and 200 μL sample volume. Linearity was observed in the range of 1–500 μg L^?1 for E2 and 0.1–100 μg L^?1 for E1. Limits of detection were 0.1 μg L^?1 for E2 and 0.01 μg L^?1 for E1. The enrichment factors and extraction recoveries were 42.2, 46.4 and 80.4, 86.7, respectively. The relative standard deviations for determination of estrogens in water were in the range of 3.9–7.2 % (n = 3). The developed method was successfully applied for the determination of estrogens in environmental water samples.     

Supramolecular-based solvent microextraction of carbaryl in water samples followed by high performance liquid chromatography determination

In this study, a simple, rapid, low cost, sensitive and environmentally friendly technique, supramolecular solvent microextraction (SM-SME) followed by high performance liquid chromatography-ultraviolet has been proposed to extract carbaryl from water samples. Parameters, affecting the SM-SME performance such as the weight of decanoic acid (DeA), volume of tetrahydrofuran (THF), pH and salt concentration, were studied and optimised. The effect of the pH on the extraction efficiency was evaluated by one–factor-at-a-time methodology, but the other variables were optimised by a face-centred cube central composite design methodology. Optimum extraction conditions were obtained: DeA: 70 mg; THF: 650 µL; salt concentration: 10% (w/v) NaCl and pH = 2–4), and the performance of the proposed method was evaluated. Under the optimum conditions, good linearity (1.0–500 µg L^?1, r² = 0.9994) was obtained. Limit of detection and limit of quantification were 0.3–1.0 µg L^?1, respectively. Also, the recoveries of the carbaryl were obtained in the ranged from 96% to 105%. Finally, proposed method was successfully applied for the determination of the carbaryl in the water samples of farms run-off and rivers and satisfactory results were obtained.     

Determination of BTEX Compounds by Dispersive Liquid–Liquid Microextraction with GC–FID

Rapid, inexpensive, and efficient sample-preparation by dispersive liquid–liquid microextraction (DLLME) then gas chromatography with flame ionization detection (GC–FID) have been used for extraction and analysis of BTEX compounds (benzene, toluene, ethylbenzene, and xylenes) in water samples. In this extraction method, a mixture of 25.0 μL carbon disulfide (extraction solvent) and 1.00 mL acetonitrile (disperser solvent) is rapidly injected, by means of a syringe, into a 5.00-mL water sample in a conical test tube. A cloudy solution is formed by dispersion of fine droplets of carbon disulfide in the sample solution. During subsequent centrifugation (5,000 rpm for 2.0 min) the fine droplets of carbon disulfide settle at the bottom of the tube. The effect of several conditions (type and volume of disperser solvent, type of extraction solvent, extraction time, etc.) on the performance of the sample-preparation step was carefully evaluated. Under the optimum conditions the enrichment factors and extraction recoveries were high, and ranged from 122–311 to 24.5–66.7%, respectively. A good linear range (0.2–100 μg L⁻¹, i.e., three orders of magnitude; r ² = 0.9991–0.9999) and good limits of detection (0.1–0.2 μg L⁻¹) were obtained for most of the analytes. Relative standard deviations (RSD, %) for analysis of 5.0 μg L⁻¹ BTEX compounds in water were in the range 0.9–6.4% (n = 5). Relative recovery from well and wastewater at spiked levels of 5.0 μg L⁻¹ was 89–101% and 76–98%, respectively. Finally, the method was successfully used for preconcentration and analysis of BTEX compounds in different real water samples.

     

Liquid–Liquid Microextraction of Nitrophenols Using Supramolecular Solvent and Their Determination by HPLC with UV Detection

A novel, efficient, and environmentally friendly method—supramolecular solvent liquid–liquid microextraction (SMS-LLME) combined with high-performance liquid chromatography (HPLC)—was first established for the determination of p-nitrophenol and o-nitrophenol in water samples. Several important parameters influencing extraction efficiency, such as the type and volume of extraction solvent, pH of sample, temperature, salt effect, extraction time, and stirring rate, were optimized in detail. Under the optimal conditions, the enrichment factor was 166 for p-nitrophenol and 160 for o-nitrophenol, and the limits of detection by HPLC were 0.26 and 0.58 μg L⁻¹, respectively. Excellent linearity with coefficients of correlation from 0.9996 to 0.9997 was observed in the concentration range of 2–1,000 μg L⁻¹. The ranges of intra- and interday precision (n = 5) at 100 μg L⁻¹ of nitrophenols were 5.85–7.76 and 10.2–11.9 %, respectively. The SMS-LLME method was successfully applied for preconcentration of nitrophenols in environmental water samples.

     

Analysis of PAHs in Water and Fruit Juice Samples by DLLME Combined with LC-Fluorescence Detection

A simple, rapid and efficient method termed dispersive liquid–liquid microextraction combined with liquid chromatography-fluorescence detection, has been developed for the extraction and determination of polycyclic aromatic hydrocarbons (PAHs) in water and fruit juice samples. Parameters such as the kind and volume of extraction solvent and dispersive solvent, extraction time and salt effect were optimized. Under optimum conditions, the enrichment factors ranged from 296 to 462. The linear range was 0.01–100 μg L^?1 and limits of detection were 0.001–0.01 μg L^?1. The relative standard deviations (RSDs, for 5 μg L^?1 of PAHs) varied from 1.0 to 11.5% (n = 3). The relative recoveries of PAHs from tap, river, well and sea water samples at spiking level of 5 μg L^?1 were 82.6–117.1, 74.9–113.9, 77.0–122.4 and 86.1–119.3%, respectively. The relative recoveries of PAHs from grape and apple juice samples at spiking levels of 2.5 and 5 μg L^?1 were 80.8–114.7 and 88.9–123.0%, respectively. It is concluded that the proposed method can be successfully applied for determination of PAHs in water and fruit juice samples.     

Determination of Chlorophenoxy Acid Herbicides in Water Samples by Suspended Liquid-Phase Microextraction�CLiquid Chromatography

In this study, directly suspended liquid-phase microextraction was investigated for the extraction and determination of five chlorophenoxy acid herbicides in water samples. The optimized parameters for extraction of chlorophenoxy acid herbicides were 1 M HCl concentration in sample solution, solution temperature 20 °C, 45-min extraction time, 1,000 rpm stirring rate, 25 ??L extracting solvent volume and without NaCl addition. Under the optimum conditions, the enrichment factor ranged from 192 to 390. Calibration curves yielded good linearity (R ² > 0.999) and the linear range was 5.0?C500.0 ??g L^?1, limit of detection was 0.3?C0.4 ??g L^?1 and limit of quantification was 1?C2 ??g L^?1 for analytes and the relative standard deviations were in the range of 3?C10% (n = 3). Finally, the proposed method was successfully applied to the quantification of five chlorophenoxy acid herbicides in water samples and recovery was in the range of 74?C110%.     

Supramolecular microextraction of cobalt from water samples before its microsampling flame atomic absorption spectrometric detection

The supramolecular solvent system consists of tetrahydrofuran (THF) and 1-decanol, that was used as an extraction solvent for a microextraction procedure for the preconcentration and separation of Co(II). The proposed supramolecular-based procedure was combined with microsampling flame atomic absorption spectrometry for the determination of cobalt at trace levels in water samples. N-Benzoyl-N,N-diisobutylthiourea was used to chelate Co(II) in an aqueous solution. Quantitative extraction efficiency was obtained at pH 6.5. The effects of analytical parameters including pH, amount of ligand, type, ratio and volume of supramolecular solvent, sample volume and interfering ions were investigated for optimisation of the procedure. The proposed supramolecular solvent-based microextraction procedure (Ss-ME) exhibits a limit of detection (LOD) of 1.29 µg L^?1 and a limit of quantification (LOQ) of 3.88 µg L^?1. The procedure was validated by addition/recovery tests and by applying TMDA 64.2 and TMDA 53.3 water certified reference materials. The microextraction method was successfully applied for the preconcentration and determination of cobalt in water samples.     

Simultaneous Derivatization and Dispersive Liquid–Liquid Microextraction for Fatty Acid GC Determination in Water

Simultaneous derivatization and dispersive liquid–liquid microextraction technique for gas chromatographic determination of fatty acids in water samples is presented. One hundred microlitre of ethanol:pyridine (4:1) were added to 4 mL aqueous sample. Then a solution containing 0.960 mL of acetone (disperser solvent), 10 μL of carbon tetrachloride (extraction solvent) and 30 μL of ethyl chloroformate (derivatization reagent) were rapidly injected into the aqueous sample. After centrifugation, 1 μL sedimented phase with the analytes was analyzed by gas chromatography. The effects of extraction solvent type, derivatization, extraction, and disperser solvents volume, extraction time were investigated. The calibration graphs were linear up to 10 mg L^?1 for azelaic acid (R ² = 0.998) and up to 1 mg L^?1 for palmitic and stearic acids (R ² = 0.997). The detection limits were 14.5, 0.67 and 1.06 μg L^?1 for azelaic, palmitic, and stearic acids, respectively. Repeatabilities of the results were acceptable with relative standard deviations (RSD) up to 13%. A possibility to apply the proposed method for fatty acids determination in tap, lake, sea, and river water was demonstrated.     

Application of Double-Phase Liquid Phase Microextraction in the Determination of Partition Coefficients and Analysis of Pesticides in Water Samples

A simple and solvent-minimized sample preparation technique based on two-phase hollow fiber-protected liquid-phase microextraction has been developed and used for the determination of partition coefficient and analysis of selected pesticides in environmental water samples. The analysis was performed by gas chromatography–electron capture detector. Three pesticides namely hexaconazole, quinalphos, and methidathion were considered as target analytes. Extraction conditions such as solvent identity, salt concentration, stirring speed, extraction time, length of the hollow fiber, and volume of donor phase were optimized. The analytes were extracted from a donor phase (water sample) through 3 μL of an organic solvent immobilized in the pores of a porous polypropylene hollow fiber and then into the acceptor phase present inside the hollow fiber. Excellent extractions of the analytes were achieved under the optimized conditions, with relative standard deviations of 4.6–7.9%, correlation coefficients (r ²) of 0.9954–0.9986 and limits of detection of 3–7 ng L^?1. The proposed method provided good average enrichment factors of up to 250-fold. The partition coefficients of the analytes determined were found to be directly correlated with the enrichment factor. The present methodology also confirms the robustness of microextraction for monitoring trace levels of pesticides in environmental water samples.     

Supramolecular�Cbased dispersive liquid�Cliquid microextraction: A novel sample preparation technique for determination of inorganic species

A new simple and sensitive method has been developed for the determination of trace levels of inorganic species in environmental water samples. It is based on the use of supramolecular?Cbased dispersive liquid?Cliquid microextraction (SM?CDLLME) prior to microsample introduction into FAAS. The ions are micro?Cextracted with coacervates composed of reverse micelles made from decanoic acid and dispersed in tetrahydrofuran?Cwater mixtures. Cobalt ion was used as a model ion, and 1?C (2?Cpyridylazo)?C2?Cnaphthol as the complexing agent. SM?CDLLME results from a combination of DLLME with coacervation?Cbased microextraction. It combines the advantages of DLLME with those of preconcentration based on coacervation and reverse micelles. Factors affecting the extraction efficiency of Co and its subsequent determination by FAAS were optimized. Under the optimized conditions and using 5.00?mL sample only, the enhancement factor is 58, the limit of detection is 4.2???g L^?C1, and the relative standard deviations for 100???g L^?C1 and 30???g L^?C1 of Co are 2.1% and 3.8%, respectively (n?=?6). The accuracy of the method was confirmed by parallel analyses using the ASTM reference method.

LC Determination of Trace Amounts of Phenoxyacetic Acid Herbicides in Water after Dispersive Liquid–Liquid Microextraction

Dispersive liquid–liquid microextraction (DLLME) for extraction and preconcentration of phenoxyacetic acid herbicides in water samples is described. After adjusting the pH to 1.5, the sample was extracted in the presence of 10% w/v sodium chloride by injecting 1 mL acetone as disperser solvent containing 25 μL of chlorobenzene as extraction solvent. The effect of parameters, such as the nature and amount of extraction and disperser solvents, ionic strength of the sample, pH, temperature and extraction time were optimized. DLLME was followed by LC for the determination of 2,4-dichlorophenoxyacetic acid and 4-chloro-2-methyl phenoxyacetic acid. The method had good linearity and a wide linear dynamic range (0.5–750 μg L^?1) with a detection limit of 0.16 μg L^?1 for both the PAAs, making it suitable for their determination in water samples.     

preconcentration and determination of amoxicillin and ceftriaxone in hospital sewage using vortex-assisted liquid-phase microextraction based on the solidification of the deep eutectic solvent followed by HPLC–UV

In the present study, a new method for extraction and preconcentration of amoxicillin and ceftriaxone was used in hospitalised sewage samples, called vortex-assisted liquid-phase microextraction based on the solidification of deep eutectic solvent. Samples were analysed by high-performance liquid chromatography–ultraviolet detection after preparation and extraction. In this method, the new deep eutectic solvent is used as the extraction solvent, which is obtained from the combination of 1-decyl-3-methylimidazolium chloride and n-butanoic acid. The important advantages of this novel extraction solvent include material stability, low density and good freezing point near room temperature. Under the optimum conditions, enrichment factors are in the range of 164–172. Repeatability and reproducibility of the method based on seven replicate measurements of 50.0 µg L^?1 of the target analytes in analysed samples were in the range of 2.1–3.5% and 3.8–5.2%, respectively. The limit of detections and linearity are in the range of 0.005–0.10 and 3–600 µg L^?1, respectively. The method was successfully applied for the determination of amoxicillin and ceftriaxone in the real sewage samples. The relative recoveries of sewage samples spiked with amoxicillin and ceftriaxone are 91–107%.