Air-assisted liquid-liquid microextraction of total 3-monochloropropane-1,2-diol from refined edible oils based on a natural deep eutectic solvent and its determination by gas chromatography-mass spectrometry.

In this paper, a fast, sensitive, and selective sample preparation procedure was presented for the determination of 3-monochloropropane-1,2-diol (3-MCPD) in refined edible oils using gas chromatography-mass spectrometry. In this method, firstly, the sample lipids and analyte fatty esters are saponified by sodium hydroxide under sonication. After that the analyte was derivatized using phenylboronic acid (as the derivatization agent) and the obtained derivative was extracted during an air-assisted liquid-liquid microextraction procedure (AALLME). Six different deep eutectic solvents (DESs) were prepared as the extraction solvents and the most effective extraction for 3-MCPD was obtained in the presence of a natural DES (NDES) consisting of choline chloride (ChCl)-acetic acid (AcOH). Important variables such as sodium hydroxide concentration and volume, sonication time, temperature, extraction solvent type and volume, and phenylboronic acid concentration and volume have been optimized. Using the optimum conditions, broad linear range (0.88-1000 ng g-1), suitable coefficient of determination (0.995), and low limits of detection (0.26 ng g-1) and quantification (0.88 ng g-1) were obtained. Relative standard deviations for intra- (n=8) and inter-day (n=6) precisions at a concentration of 5 ng g-1 were 2.6 and 3.2%, respectively. The developed method has been successfully applied to 3-MCPD determination in refined edible oil samples including sunflower, corn, and canola oils.

Application of magnetic carbon nano-onions in dispersive solid-phase extraction combined with DLLME for extraction of pesticide residues from water and vegetable samples.

A dispersive solid-phase microextraction method based on magnetic carbon nano-onions (MCNOs) was developed for the extraction and preconcentration of some pesticides from water and vegetable samples. For more cleanup and preconcentration, a dispersive liquid-liquid microextraction (DLLME) method was employed after performing the first step. In this method, firstly, MCNOs were prepared and then used for adsorption of the analytes from the sample solution. After that, the adsorbed analytes were eluted with an appropriate water-miscible organic solvent and used as a dispersive solvent in the following DLLME procedure. The extracted analytes were quantified by gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. Various factors affecting the method efficiency such as sorbent weight, salt effect, pH, temperature, and type and volume of eluent and extraction solvent were optimized. This method showed wide linear ranges with a coefficient of determination ≥ 0.994, and low limits of detection (0.001-0.005 ng mL-1) and quantification (0.003-0.019 ng mL-1) under optimal conditions. Also, a good precision (relative standard deviation ≤ 8.6%) for five replicates and a satisfactory accuracy (mean relative recoveries between 82 and 99%) were obtained. It can be considered as an efficient and environment friendly method for the extraction of analytes from vegetable and fruit juices and water samples.

A simple and green ultrasound liquid-liquid microextraction method based on low viscous hydrophobic deep eutectic solvent for the preconcentration and separation of selenium in water and food samples prior to HG-AAS detection.

A simple and green ultrasound liquid-liquid microextraction method based on low viscous hydrophobic deep eutectic solvent (ULLME-LV-HDES) was proposed for the preconcentration and separation of selenium prior to HG-AAS detection. Six different DESs were prepared for the extraction of selenium. Quercetin was used complexing agent for Se(IV) ions. Various analytical parameters such as pH, quercetin amount, DES type and its volume, sonication time, sample volume were optimized. Tolerance limits of anion, cation and transition metal ions were studied. Preconcentration and enhancement factor were found 62.5 and 121. Under the optimum conditions, limit of detection was found 0.25 ng L-1 with calibration range of 0.8-120 ng L-1. Relative standard deviation was found 3.2%. The accuracy of the method was confirmed with certified reference materials (NIST 1567a Wheat flour and NIST 1548a Typical diet). Finally, the developed method was successfully applied to food and water samples.

Determination of trace levels of selenium in natural water, agriculture soil and food samples by vortex assisted liquid-liquid microextraction method: Multivariate techniques.

A green vortex assisted based liquid-liquid microextraction (VA-LLME) method was developed for preconcentration of selenium. Ammonium pyrrolidine dithiocarbamate (APDC) was used to form a hydrophobic complex with selenium in natural water, agricultural soil and food samples by GFAAS. Whereas Triton X-114, a nonionic surfactant and 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid were used for Se extraction as a dispersing medium. The conical flasks contents were shack on a vortex mixer to increase the extraction efficiency. Multivariate techniques were used to evaluate extraction parameters; pH, vortex time, APDC amount, volume of ionic liquid and Triton X-114 and centrifugation rate on the recovery of Se. The central composite design (CCD) was used for further optimization of the essential extraction parameters. The enhancement factor and limit of detection were obtained as 98.7 and 0.07 µg L-1. The certified reference materials was used for accuracy of method and the related standard deviation was found to be 3.51%. The resulted data indicated that concentrations of Se in all types of water samples were below the permissible limit recommended by WHO.

Pyrocatechol violet impregnated magnetic graphene oxide for magnetic solid phase microextraction of copper in water, black tea and diet supplements.

Pyrocatechol violet impregnated magnetic graphene oxide hybrid material (PV-MGO) was prepared as magnetic solid phase microextraction for separation and preconcentration of copper before its determination by flame atomic absorption spectrometry. PV-MGO hybrid material was characterized using field emission scanning electron microscope (FE-SEM, SEM-Mapping), scanning transmission electron microscopy (STEM), energy dispersive X-ray (EDX), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and Raman spectroscopy. Effects of various parameters such as pH, eluent type, vortex time, amount of magnetic adsorbent were investigated. Under the optimized conditions the MSPE-FAAS procedure presents limit of detection (LOD) of 4.0 µg L-1, limit of quantification (LOQ) of 13.3 µg L-1, preconcentration factor of 20 and relative standard deviation (RSD) 4.93%. The accuracy of the method was confirmed by the analysis of the certified reference materials (NCS ZC73032 Celery, CRM025-050 metals on soil, TMDA-64.2 fortified water) and addition-recovery tests. The present method was successfully applied to water, black tea and diet supplements.

Multi-element determination in some foods and beverages using silica gel modified with 1-phenylthiosemicarbazide.

1-Phenylthiosemicarbazide bonded modified silica gel (PTC-SG) was synthesised and characterised by FTIR, SEM and elemental analysis for a novel separation/preconcentration of multiple elements based on solid phase extraction. The analytical parameters including pH of solutions, amounts of PTC-SG, flow rates of sample, eluent type and sample volume were optimised. The adsorption capacities of PTC-SG were found to be 7.9, 6.4, 6.3, 8.3, 7.2, 8.9 and 6.6 mg/g for Cu(II), Cd(II), Pb(II), Co(II), Cr(III), Ni(II) and Mn(II), respectively. The limit of detection (LOD) was calculated as 3x the standard deviation(s) of the reagent blank (k = 3, N = 21) and the LOD values were obtained to be 0.98 µg L-1 (Cu), 0.65 µg L-1 (Cd), 0.57 µg L-1 (Pb), 1.12 µg L-1 (Co), 1.82 µL-1 (Cr), 1.67 µg L-1 (Ni) and 0.55 µg L-1 (Mn). Certified reference materials were used to test the validation of the present method. The new solid phase extraction method was successfully applied to determination of the amount of multiple elements in food and beverage samples.

A newly synthesized graft copolymer for magnetic solid phase microextraction of total selenium and its electrothermal atomic absorption spectrometric determination in food and water samples.

A newly synthesized polystyrene-g-polyoleic acid-g-polyethylene glycol graft copolymer (PoleS-PEG) was used as adsorbent in the solid phase microextraction of selenium ions by using electrothermal atomic absorption spectrometry (ETAAS). Neodymium magnet was used for separation of analyte ions. Various analytical parameters such as pH, adsorbent amount, mixing time, eluent solution, sample volume, etc. were optimized. The matrix effects of some cations and anions were also studied. The capacity of the adsorbent was found 11.5 mg g-1. The preconcentration factor was found to be 50. The detection limit (LOD) and quantification limit (LOQ) were found 6.06 ng L-1 and 20 ng L-1, respectively. The calibration curve was linear in the range of 0.02-4.0 µg L-1. Relative standard deviation was found 3.2%. The accuracy of the method was provided by using standard reference materials. The optimized method was successfully applied to natural water and food samples.

Choline Chloride-Oxalic Acid as a Deep Eutectic Solvent-Based Innovative Digestion Method for the Determination of Selenium and Arsenic in Fish Samples.

An innovative and effective digestion method based on choline chloride (ChCl)-oxalic acid (Ox) deep eutectic solvent (DES) was proposed for the determination of Se and As in fish samples via electrothermal atomic absorption spectrometry (ETAAS). The impacts of different variables, including the composition and volume of ChCl-Ox, temperature, and acid addition, on analyte recovery were studied for optimization. In this procedure, an 80 mg sample was dissolved in a 1:2 molar ratio of ChCl-Ox at 105°C for 40 min, with the subsequent addition of 4.0 mL HNO3 (1.0 M) and further heating at the same temperature for about 5 min. Next, centrifugation was applied, and the supernatant solution was filtered, diluted to a known volume, and measured by ETAAS. The accuracy of the developed method was tested using a Standard Reference Material (NIST SRM 1946 Lake Superior Fish Tissue). The proposed DES-based digestion method was successfully applied to the simultaneous extraction of Se and As from fish samples.

Determination of Selenium and Arsenic Ions in Edible Mushroom Samples by Novel Chloride-Oxalic Acid Deep Eutectic Solvent Extraction Using Graphite Furnace-Atomic Absorption Spectrometry.

In present study, we proposed the application of a deep eutectic solvent (DES) made up of choline chloride (ChCl) and oxalic acid (Ox) for the dissolution of different edible mushroom samples for the determination of selenium (Se) and arsenic (As) ions. Therefore, an innovative, green, novel, and inexpensive method based on ChCl-Ox as the DES was developed for the determination of Se and As ions in mushroom species by graphite furnace-atomic absorption spectrometry. The important analytical parameters were also optimized. The LODs for Se and As ions were found to be 0.32 and 0.50 µg/L, respectively. The LOQs for Se and As ions were found to be 1.06 and 1.65 µg/L, respectively. The RSD was observed to be less than 5% for both analyte ions. The accuracy of the developed method was confirmed by analyzing mushroom powder Certified Reference Material CS-M-3 (Boletus edulis). The developed technique was effectively useful for the determination of Se and As ions in different species of mushroom samples from Turkey.

Simple and Rapid Dual-Dispersive Liquid-Liquid Microextraction as an Innovative Extraction Method for Uranium in Real Water Samples Prior to the Determination of Uranium by a Spectrophotometric Technique.

An innovative, rapid, and simple dual-dispersive liquid-liquid microextraction (DDLL-ME) approach was used to extract uranium from real samples for the first time. The main objective of this study was to disperse extraction solvent by using an air-agitated syringe system to overcome matrix effects and avoid dispersion of hazardous dispersive organic solvents by using heat. The DDLL-ME method consisted of two dispersive liquid-liquid extraction steps with chloroform as the extracting solvent. Uranium formed complexes with 4-(2-thiazolylazo) resorcinol in the aqueous phase and was extracted in extracting solvent (chloroform) after the first dispersive liquid-liquid process. Uranium was then back-extracted in the acidic aqueous phase in a second dispersive liquid-liquid process. Finally, uranium was determined by a spectrophotometric detection technique. The variables that played a key role in the proposed method were studied and optimized. The LOD and sensitivity enhancement factor for uranium were found to be 0.60 µg/L and 45, respectively, under optimized conditions. Calibration graphs were found to be linear in the range of 5.0-600 µg/L. The RSD was 2.5%. Reliability of the proposed method was verified by analyzing certified reference material TM-28.3.

A simple and sensitive vortex-assisted ionic liquid-dispersive microextraction and spectrophotometric determination of selenium in food samples.

In the present study, a novel and eco-friendly vortex-assisted ionic liquid-based microextraction method was developed for the determination of selenium in food. The microextraction method is based on the liberation of iodine in the presence of selenium; the liberated iodine reacts with I- to form I3-. Anionic I3- reacts with cationic crystal violet dye, and the product is extracted into 1-hexyl-3-methylimidazolium hexafluorophosphate phase in the presence of Triton X-114. The proposed method is linear in the range of 2.0-70µgL-1 and has a detection limit of 9.8×10-2µgL-1. Relative standard deviations were 3.67% and 2.89% for the five replicate measurements of 14 and 35µgL-1 Se(IV), respectively. The proposed method was successfully applied to different food samples (NIST SRM 2976 mussel tissue, pepper, ginger, wheat flour, red lentil, traditional soup, cornflour, cornstarch, and garlic) after microwave digestion.

Equilibrium, thermodynamic and kinetic investigations for biosorption of uranium with green algae (Cladophora hutchinsiae).

Removal of toxic chemicals from environmental samples with low-cost methods and materials are very useful approach for especially large-scale applications. Green algae are highly abundant biomaterials which are employed as useful biosorbents in many studies. In the present study, an interesting type of green algae, Cladophora hutchinsiae (C. hutchinsiae) was used for removal of highly toxic chemical such as uranium. The pH, biosorbent concentration, contact time and temperature were optimized as 5.0, 12 g/L, 60 min and 20 °C, respectively. For the equilibrium calculations, three well known isotherm models (Langmuir, Freundlich and Dubinin-Radushkevich) were employed. The maximum biosorption capacity of the biosorbent was calculated as about 152 mg/g under the optimum batch conditions. The mean energy of biosorption was calculated as 8.39 kJ/mol from the D-R biosorption isotherm. The thermodynamic and kinetic characteristics of biosorption were also investigated to explain the nature of the process. The kinetic data best fits the pseudo-second-order kinetic model with a regression coefficient of >0.99 for all studied temperatures. The calculated ΔH° and ΔG° values showed that the biosorption process is exothermic and spontaneous for temperatures between 293 and 333 K. Furthermore, after seven cycling process, the sorption and desorption efficiencies of the biosorbent were found to be 70, and 58%, respectively meaning that the biosorbent had sufficiently high reusability performance as a clean-up tool.

A new separation and preconcentration method for selenium in some foods using modified silica gel with 2,6-diamino-4-phenil-1,3,5-triazine.

A novel and simple solid phase extraction method was improved and recommended for selenium. Silica gel was modified with 2,6-diamino-4-phenil-1,3,5-triazine and characterized by FTIR, SEM and elemental analysis and used adsorbent for column solid phase extraction of selenium ions. The experimental parameters (pH, flow rates, amounts of the modified silica gel, concentration and type of eluent, volume of sample, etc.) on the recoveries of selenium were optimized. Standard reference materials were analyzed for validation of method. The present method was successfully applied to the detection of total selenium in water and microwave digested some food samples with quantitative recoveries (> 95%). The relative standard deviations were<8%. Matrix influences were not observed. The adsorption capacity of modified silica gel was 5.90mgg-1. The LOD was 0.015µgL-1. Enrichment factor was obtained as 50 for the introduced method.

Polyhydroxybutyrate-b-polyethyleneglycol block copolymer for the solid phase extraction of lead and copper in water, baby foods, tea and coffee samples.

A new adsorbent, polyhydroxybutyrate-b-polyethyleneglycol, was used for the separation and preconcentration of copper(II) and lead(II) ions prior to their flame atomic absorption spectrometric detections. The influences of parameters such as pH, amount of adsorbent, flow rates and sample volumes were investigated. The polymer does not interact with alkaline, alkaline-earth metals and transition metals. The enrichment factor was 50. The detection limits were 0.32 µg L(-1) and 1.82 µg L(-1) for copper and lead, respectively. The recovery values were found >95%. The relative standard deviations were found to be less than 6%. The validation of the procedure was performed by analysing certified reference materials; NIST SRM 1515 Apple leaves, IAEA-336 Lichen and GBW-07605 Tea. The method was successfully applied for the analysis of analytes in water and food samples.

Graphite furnace atomic absorption spectrometric detection of vanadium in water and food samples after solid phase extraction on multiwalled carbon nanotubes.

Vanadium(V) ions as 8-hydroxyquinoline chelates were loaded on multiwalled carbon nanotubes (MWNTs) in a mini chromatographic column. Vanadium was determined by graphite furnace atomic absorption spectrometry (GFAAS). Various analytical parameters including pH of the working solutions, amounts of 8-hydroxyquinoline, eluent type, sample volume, and flow rates were investigated. The effects of matrix ions and some transition metals were also studied. The column can be reused 250 times without any loss in its sorption properties. The preconcentration factor was found as 100. Detection limit (3 s) and limit of quantification (10 s) for the vanadium in the optimal conditions were observed to be 0.012 µg L(-1) and 0.040 µg L(-1), respectively. The capacity of adsorption was 9.6 mg g(-1). Relative standard deviation (RSD) was found to be 5%. The validation of the method was confirmed by using NIST SRM 1515 Apple leaves, NIST SRM 1570a Spinach leaves and GBW 07605 Tea certified reference materials. The procedure was applied to the determination of vanadium in tap water and bottled drinking water samples. The procedure was also successfully applied to microwave digested food samples including black tea, coffee, tomato, cabbage, zucchini, apple and chicken samples.

Selective speciation of inorganic antimony on tetraethylenepentamine bonded silica gel column and its determination by graphite furnace atomic absorption spectrometry.

A speciation system for antimony (III) and antimony (V) ions that based on solid phase extraction on tetraethylenepentamine bonded silica gel has been established. Antimony was determined by graphite furnace atomic absorption spectrometry (GF-AAS). Analytical conditions including pH, sample volume, etc., were studied for the quantitative recoveries of Sb (III) and Sb (V). Matrix effects on the recovery were also investigated. The recovery values and detection limit for antimony (III) at optimal conditions were found as >95% and 0.020 µg L(-1), respectively. Preconcentration factor was calculated as 50. The capacity of adsorption for the tetraethylenepentamine bonded silica gel was 7.9 mg g(-1). The validation was checked by analysis of NIST SRM 1573a Tomato laves and GBW 07605 Tea certified reference materials. The procedure was successfully applied to speciation of antimony in tap water, mineral water and spring water samples. Total antimony was determined in refined salt, unrefined salt, black tea, rice, tuna fish and soil samples after microwave digestion and presented enrichment method combination.

Simultaneous coprecipitation of lead, cobalt, copper, cadmium, iron and nickel in food samples with zirconium(IV) hydroxide prior to their flame atomic absorption spectrometric determination.

A simple and new coprecipitation procedure is developed for the determination of trace quantities of heavy metals (lead, cobalt, copper, cadmium, iron and nickel) in natural water and food samples. Analyte ions were coprecipitated by using zirconium(IV) hydroxide. The determination of metal levels was performed by flame atomic absorption spectrometry (FAAS). The influences of analytical parameters including pH, amount of zirconium(IV), sample volume, etc. were investigated on the recoveries of analyte ions. The effects of possible matrix ions were also examined. The recoveries of the analyte ions were in the range of 95-100%. Preconcentration factor was calculated as 25. The detection limits for the analyte ions based on 3 sigma (n=21) were in the range of 0.27-2.50 microgL(-1). Relative standard deviation was found to be lower than 8%. The validation of the presented coprecipitation procedure was performed by the analysis certified reference materials (GBW 07605 Tea and LGC 6010 Hard drinking water). The procedure was successfully applied to natural waters and food samples like coffee, fish, tobacco, black and green tea.

Investigation of the levels of some element in edible oil samples produced in Turkey by atomic absorption spectrometry.

The element contents (Fe, Mn, Zn, Cu, Pb, Co, Cd, Na, K, Ca and Mg) in edible oils (olive oil, hazelnut oil, sunflower oil, margarine, butter and corn oil) from Turkey were determined using atomic absorption spectrometry after microwave digestion. The concentrations of trace element in the samples were found to be 291.0-52.0, 1.64-0.04, 3.08-1.03, 0.71-0.05, 0.03-0.01, 1.30-0.50, 84.0-0.90, 50.1-1.30, 174.2-20.8 and 20.8-0.60 microg/g for iron, manganese, zinc, copper, lead, cobalt, sodium, potassium, calcium, and magnesium, respectively. Cadmium was found to be 4.57-0.09 microg/kg. The high heavy metal and minerals accumulation levels in the samples were found in olive oil for Cu, Pb, Co, margarine for Fe, K, corn oil for Zn, Mn, butter for Na, Mg, sunflower oil for Ca and hazelnut oil for Cd, respectively.

Optimization of microwave assisted digestion procedure for the determination of zinc, copper and nickel in tea samples employing flame atomic absorption spectrometry.

The present paper describes the development of a microwave assisted digestion procedure for the determination of zinc, copper and nickel in tea samples employing flame atomic absorption spectrometry (FAAS). The optimization step was performed using a full factorial design (2(3)) involving the factors: composition of the acid mixture (CMA), microwave power (MP) and radiation time (RT). The experiments of this factorial were carried out using a certified reference material of tea GBW 07605 furnished by National Research Centre for Certified Reference Materials, China, being the metal recoveries considered as response. The relative standard deviations of the method were found below 8% for the three elements. The procedure proposed was used for the determination of copper, zinc and nickel in several samples of tea from Turkey. For 10 tea samples analyzed, the concentration achieved for copper, zinc and nickel varied at 6.4-13.1, 7.0-16.5 and 3.1-5.7 (microg g(-1)), respectively.

Adsorption characteristics of Cu(II) and Pb(II) onto expanded perlite from aqueous solution.

The adsorption characteristics of Cu(II) and Pb(II) onto expanded perlite (EP) from aqueous solution were investigated with respect to the changes in pH of solution, adsorbent dosage, contact time and temperature of solution. For the adsorption of both metal ions, the Langmuir isotherm model fitted to equilibrium data better than the Freundlich isotherm model. Using the Langmuir model equation, the monolayer adsorption capacity of EP was found to be 8.62 and 13.39 mg/g for Cu(II) and Pb(II) ions, respectively. Dubinin-Radushkevich (D-R) isotherm model was also applied to the equilibrium data and the mean free energies of adsorption were found as 10.82 kJ/mol for Cu(II) and 9.12 kJ/mol for Pb(II) indicating that the adsorption of both metal ions onto EP was taken place by chemical ion-exchange. Thermodynamic functions, the change of free energy (DeltaG degrees ), enthalpy (DeltaH degrees ) and entropy (DeltaS degrees ) of adsorption were also calculated for each metal ions. These parameters showed that the adsorption of Cu(II) and Pb(II) ions onto EP was feasible, spontaneous and exothermic at 20-50 degrees C. Experimental data were also evaluated in terms of kinetic characteristics of adsorption and it was found that adsorption process for both metal ions followed well pseudo-second-order kinetics.