In-situ sorbent formation for the extraction of pesticides from honey.

An organic polymer was re-precipitated in solution to use as an adsorbent in dispersive solid-phase extraction of some pesticides from honey samples prior to their determination by high-performance liquid chromatography-tandem mass spectrometry. In this approach, different deep eutectic solvents were prepared using lysine and their ability in elution of the analytes from the adsorbent surface was tested. A diluted honey solution was transferred into a glass test tube and then a solution of polystyrene dissolved in dimethylformamide was injected into the solution. By doing this, polystyrene is re-precipitated in the solution and dispersed in whole parts of it as many tiny particles. Then the mixture was centrifuged and the adsorbed analytes on the particles were eluted using a proper hydrophilic deep eutectic solvent. The central composite design approach was used for the optimization of effective parameters. The limits of detection and quantification were in the ranges of 0.06-0.20 and 0.22-0.69 ng/g, respectively. The calibration curves obtained by matrix-matched standard solutions were linear in the range of 0.69-500 ng/g with a coefficient of determinations ≥0.9962. The method provided high extraction recoveries (70-99%) and enrichment factors (140-198), and an acceptable precision (relative standard deviations ≤7.1%).

Application of microcrystalline cellulose as an efficient and cheap sorbent for the extraction of metoprolol from plasma and wastewater before HPLC-MS/MS determination.

A dispersive solid-phase extraction method based on a new sorbent has been performed on plasma and wastewater samples to determine metoprolol by high-performance liquid chromatography-tandem mass spectrometry. In this study, the analyte was adsorbed from the samples onto microcrystalline cellulose as a green and efficient sorbent and then eluted for use in the determination step. In the mass spectrometer, the analyte was detected in the positive mode and selectivity of the analysis was increased by sequential mass analysis through multiple reaction monitoring. All of the effective parameters in the extraction of metoprolol from plasma and wastewater were optimized. Under optimal conditions the method was linear in the ranges of 1-1,000 and 0.1-1,000 ng/ml in plasma and wastewater samples, respectively. The detection limits of the method were 0.30 and 0.03 ng/ml in plasma and wastewater samples, respectively. The data showed that the method provides low detection limit, wide linear range, good precision and high extraction recovery. Finally several plasma and wastewater samples were successfully analyzed using the method. The use of a small amount of a green and inexpensive sorbent and a low volume of plasma without the need for further pretreatment steps are the main advantages of the method.

Voltammetric sensor based on bimetallic nanocomposite for determination of favipiravir as an antiviral drug.

A novel and sensitive voltammetric nanosensor was developed for the first time for trace level monitoring of favipiravir based on gold/silver core-shell nanoparticles (Au@Ag CSNPs) with conductive polymer poly (3,4-ethylene dioxythiophene) polystyrene sulfonate (PEDOT:PSS) and functionalized multi carbon nanotubes (F-MWCNTs) on a glassy carbon electrode (GCE). The formation of Au@Ag CSNPs/PEDOT:PSS/F-MWCNT composite was confirmed by various analytical techniques, including X-ray diffraction (XRD), ultraviolet-visible spectroscopy (UV-Vis), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and field-emission scanning electron microscopy (SEM). Under the optimized conditions and at a typical working potential of + 1.23 V (vs. Ag/AgCl), the Au@Ag CSNPs/PEDOT:PSS/F-MWCNT/GCE revealed linear quantitative ranges from 0.005 to 0.009 and 0.009 to 1.95 µM with a limit of detection 0.46 nM (S/N = 3) with acceptable relative standard deviations (1.1-4.9 %) for pharmaceutical formulations, urine, and human plasma samples without applying any sample pretreatment (1.12-4.93%). The interference effect of antiviral drugs, biological compounds, and amino acids was negligible, and the sensing system demonstrated outstanding reproducibility, repeatability, stability, and reusability. The findings revealed that this assay strategy has promising applications in diagnosing FAV in clinical samples, which could be attributed to the large surface area on active sites and high conductivity of bimetallic nanocomposite.

Carbon nanotubes grafted with poly(trimesoyl, m-phenylenediamine) for enhanced removal of phenol.

This work focused on the facile synthesis of carbon nanotubes grafted with a polymer of trimesoyl chloride and m-phenylenediamine (CNTs-MDP-TMC) as novel and effective adsorbent and investigation of its ability in the phenol uptake from aqueous media. The chemical and morphological characterization of the synthesized adsorbent was carried out by FT-IR, SEM, EDX, and mapping techniques. The influence of the operational parameters on the adsorption performance was inspected and optimized batch adsorption conditions by factorial design analysis. The non-linear Langmuir model was better represented the isotherm of phenol adsorption compared to the Freundlich isotherm. The CNTs-MDP-TMC had a maximum adsorption capacity as much as 261.6 mg/g. The kinetic examinations revealed that the pseudo-second-order (PSO) kinetic model depicted higher relationship with phenol adsorption than the pseudo-first-order (PFO) model. The thermodynamics findings confirmed that the phenol adsorption by the CNTs-MDP-TMC is taken place exothermically and more spontaneously with lessening temperature. The prepared adsorbent had a great adsorption/desorption performance, especially during the first four cycles. It can be drawn a conclusion form all findings that the synthesized CNTs-MDP-TMC has great prospective as a novel and influential adsorbent for phenol polluted-wastewaters.

Polyamide magnetic palygorskite for the simultaneous removal of Hg(II) and methyl mercury; with factorial design analysis.

A novel efficient adsorbent was prepared by the modification of magnetic palygorskite (MPG) by polyamide via the interfacial polymerization of trimesoyl chloride with m-phenylenediamine. The prepared magnetic palygorskite modified with polyamide (MPGP) material was appraised for its removal of the Hg(II) and CH3Hg species from aqueous solutions. The developed adsorbent was characterized using spectroscopic techniques. The adsorption ability of the MPGP sorbent was systematically investigated by using the batch method. Factorial design analysis was applied to study the effect of different batch parameters on the adsorption yield of both mercury species. These factors include mercury concentration, initial pH, sorbent amount and contact time. The equilibrium data coincided with the Langmuir adsorption isotherm indicating the maximum adsorption capacity of the MPGP was determined as 211.93 mg/g for Hg(II) and 159.73 mg/g for CH3Hg. The kinetic mechanism of the adsorption of both mercury species was well defined by the pseudo-second-order while the adsorption processes demonstrated spontaneity and an exothermic character at the studied temperatures. The cycling adsorption/desorption tests made by using a 1 mol/L HCl solution demonstrated that the MPGP had good reusable performance up to seven cycles. Based on the results it can be suggested that the synthesized MPGP sorbent can be handled for the elimination of Hg(II) and CH3Hg from wastewater effluents.

Response surface optimization, kinetic and thermodynamic studies for effective removal of rhodamine B by magnetic AC/CeO2 nanocomposite.

The activated carbon (AC) was obtained from waste scrap tires and modified by bimetallic Fe and Ce nanoparticles in order to combine both the high surface area and the active sites for enhanced adsorption of the dye. The produced nanocomposite was used as a novel cost-effective magnetic in rhodamine B (RhB) removal from aqueous solutions. The FT-IR, SEM, EDX, TEM, and surface area analysis methods were implemented to characterize the morphological, chemical, thermal and surface properties of the developed adsorbent. The optimum batch experimental conditions were found under the response surface methodology. The adsorption equilibrium data were well fitted by the Langmuir isotherm model. The adsorption capacity was 324.6 mg g-1. The kinetic and thermodynamics studies were also carried out to understand the adsorption mechanism. The study indicated that RhB adsorption by the AC/Fe/Ce magnetic adsorbent has an endothermic character and followed the pseudo-second-order kinetics model. By using ethanol solution, RhB was desorbed at high efficiency and the prepared material could be recycled for up to ten cycles. Thus, the magnetic nanocomposite is an effective and promising adsorbent for the cleaning treatment of RhB ions from wastewater by a large scale designed adsorption system.

A Novel Selective Deep Eutectic Solvent Extraction Method for Versatile Determination of Copper in Sediment Samples by ICP-OES.

In the present study, a simple, mono step deep eutectic solvent (DES) extraction was developed for selective extraction of copper from sediment samples. The optimization of all experimental parameters, e.g. DES type, sample/DES ratio, contact time and temperature were performed with using BCR-280 R (lake sediment certified reference material). The limit of detection (LOD) and the limit of quantification (LOQ) were found as 1.2 and 3.97 µg L-1, respectively. The RSD of the procedure was 7.5%. The proposed extraction method was applied to river and lake sediments sampled from Serpincik, Çeltek, Kizilirmak (Fadl and Tecer region of the river), Sivas-Turkey.

Honeybees and honey as monitors for heavy metal contamination near thermal power plants in Mugla, Turkey.

In the present work, 6 honeydew samples of known geographical and botanical origins and 11 honeybee samples were analyzed to detect possible contamination by the thermoelectric power plants in Mugla, Turkey. The contents of trace elements were determined by atomic absorption spectrometry after application of microwave digestion. The samples from the thermal power plants, which were 10-22 km away from the hives, that did not cause pollution in honeydew honeys were also analyzed. The levels of copper, cadmium (Cd), lead (Pb), zinc, manganese, iron, chromium, nickel, and aluminum were similar to the values found in other recent studies in literature. However, it was found that the contamination levels of the toxic elements such as Pb and Cd in honeybee samples measured relatively higher than that of honey samples. The study concludes that honeybees may be better bioindicators of heavy metal pollution than honey.

Separation and Enrichment of Gold in Water, Geological and Environmental Samples by Solid Phase Extraction on Multiwalled Carbon Nanotubes Prior to its Determination by Flame Atomic Absorption Spectrometry.

This study proposes the application of multi-walled carbon nanotubes as a solid sorbent for the preconcentration of gold prior to its flame atomic absorption spectrometry determination. Extraction was achieved by using a glass column (15.0 cm in length and 1.0 cm in diameter). Quantitative recoveries were obtained in the pH range of 2.5-4.0; the elution step was carried out with 5.0 ml of 1.0 mol/L HNO3 in acetone. In the ligand-free study, variables such as pH, eluent type, sample volume, flow rates, and matrix effect were examined for the optimum recovery of gold ions. The gold ions were able to be pre-concentrated by a factor of 150 and their LOD was determined to be 1.71 µg/L. In order to evaluate the accuracy of the developed method, addition-recovery tests were applied for the tap water, mineral water, and sea water samples. Gold recovery studies were implemented using a wet digestion technique for mine and soil samples taken from various media, and this method was also applied for anodic slime samples taken from the factories located in the Kayseri Industrial Zone of Turkey.

Separation and Preconcentration of Sudan Blue II Using Membrane Filtration and UV-Visible Spectrophotometric Determination in River Water and Industrial Wastewater Samples.

A new separation and preconcentration method based on adsorption on a cellulose acetate membrane filter and elution with ethanol was established for the UV-Vis spectrophotometric determination of Sudan blue II. Various analytical parameters such as pH of working media, flow rates of solutions, and sample volumes were optimized. Matrix effects of concomitants were investigated for the quantitative recovery values of Sudan blue II. The preconcentration factor was 200. LOD was calculated as 0.96 µg/L. RSD was 5.1%. The optimized procedure was applied to the spectrophotometric determination of Sudan blue II in river and industrial wastewater samples from oil and dye products.

Solid-phase extraction of iridium from soil and water samples by using activated carbon cloth prior to its spectrophotometric determination.

A solid-phase extraction method for separation and preconcentration of Ir(IV) ion by using activated carbon cloth (ACC) has been presented. Ir(IV) as their 1-(2-pyridylazo) 2-naphtol (PAN) chelate was adsorbed on ACC at pH 2.0 and was eluted from ACC with acidic dimethylformamide (DMF). The Ir(IV) concentration was determined at 536 nm as Ir(IV)-PAN complex by using UV-vis spectrophotometer. The analytical parameters including pH, sample and eluent flow rates, amount of PAN, eluent type, concentration, and sample volume were optimized. The effects of foreign ions on the recoveries of iridium were also investigated. The preconcentration factor was calculated as 60. The limit of detection (LOD) and the limit of quantification (LOQ) of the method were found as 0.039 and 0.129 µg L(-1), respectively. The method was applied to soil and water samples for iridium determination.

Ultrasound-assisted ionic liquid-based dispersive liquid-liquid microextraction for preconcentration of patent blue V and its determination in food samples by UV-visible spectrophotometry.

Ultrasound-assisted ionic liquid-based dispersive liquid-liquid microextraction procedure (UA-IL-DLLME) was developed for determination of trace levels of patent blue V prior to its determination by UV-visible spectrophotometry. Patent blue V was extracted from 25-mL sample into a 100-µL volume of ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), with the aid of sonication in an ultrasonic bath. Several variables affecting microextraction efficiency were optimized. Under the optimum experimental conditions, the detection limit (3 s) was 0.68 µg L(-1), and the preconcentration factor was 100. The relative standard deviation for six replicate determinations of patent blue V was 4.5%. The method was applied to the determination of patent blue V in food samples. The proposed procedure is effective, very simple, and fast.

Dispersive liquid-liquid microextraction of lead(II) as 5-(4-dimethylaminobenzylidene) rhodanine chelates from food and water samples.

A dispersive liquid-liquid microextraction procedure for lead(II) as its 5-(4-dimethylaminobenzylidene) rhodanine complex has been established prior to its microsampling flame atomic absorption spectrometric determination. The influences of various analytical parameters including pH, solvent type and volume, dispersive solvent type and volume, 5-(4-dimethylaminobenzylidene) rhodanine amount, salt effect, and centrifugation time and speed were investigated. The effects of certain alkali, alkaline earth, and transition metal ions on the quantitative extraction of lead(II) were also studied. Quantitative recoveries were obtained at pH 6. The enrichment factor was calculated as 125. The detection limit for lead is 1.1 µg/L. The accuracy of the method was tested with the additions recovery test and analysis of the standard reference materials (SPS-WW2 waste water, NIST SRM 1515 apple leaves, and TMDA-51.3 fortified water). Applications of the present procedure were tested by analyzing water and food samples.

Sequential extraction procedure for the determination of some trace elements in fertilizer samples.

Total concentration of metal ions at trace levels does not give sufficient information about toxicity and biological availability of these elements in fertilizer samples. In the presented work, a sequential extraction procedure modified by the European Community Bureau of Reference (BCR) was applied to fractionate Cd, Cr, Co, Cu, Fe, Pb, Mn, Ni, and Zn levels in two fertilizer samples collected from cooperative agricultural retailers. The fractions extracted were exchangeable/dilute acid soluble, reducible bound to Fe/Mn oxides, oxidizable bound to organic matter and sulfides, and residual. The determination of analyte elements was done by flame atomic absorption spectrometry. The accuracy of the procedure was validated with BCR-701 sediment certified reference material. The RSD of the procedure was less than 10%.

Solid-phase extraction of copper(II) in water and food samples using silica gel modified with bis(3-aminopropyl)amine and determination by flame atomic absorption spectrometry.

A simple and selective separation and preconcentration method was developed for the determination of Cu(ll) ions. This method is based on adsorption of Cu(ll) ions from aqueous solution on a bis(3-aminopropyl)amine modified silica gel column and flame atomic absorption spectrometric determination after desorption. Various analytical parameters such as pH, type of eluent solution and its volume, flow rate of sample and eluent, and sample volume were optimized. Effects of some cation, anion, and transition metal ions on the recoveries of Cu(ll) ions were also investigated. Cu(ll) ions were quantitatively recovered at pH 6; 5.0 mL of 2 M HCI was used as the eluent. The preconcentration factor was found to be 150. The LOD was 0.12 microg/L for Cu(ll). The accuracy of the method was confirmed by analysis of Tea Leaves (INCT-TL-1) and Fish Protein (DORM-3) certified reference materials. The optimized method was applied to various water and food samples for the determination of Cu(ll).

Assessment of trace metal concentrations in muscle tissue of certain commercially available fish species from Kayseri, Turkey.

Regular consumption of fish has been widely recommended by health authorities. However, it is known that some species accumulate high levels of contaminants including heavy metals (e.g., Hg, Cd, Pb, and As). In this study, Cu, Pb, Co, Ni, Cr, Mn, Cd, and Fe were determined in the muscle tissue of 11 commercially available fish species (Sparus auratus, Dicentrarchus labrax, Mullus barbatus, Belone belone, Psetta maxima, Epinephelus aeneus, Salmothymus, Soleidae, Pomatomus saltatrix, Engraulis encrasicolus, and Sarda sarda) supplied from retailers in Kayseri, Turkey. Determinations were carried out by flame atomic absorption spectrometry after the wet digestion method. The average metal concentrations of the 11 species were determined in the range of 0.54-1.79, 0.82-1.40, 2.38-4.54, 1.23-3.67, 5.01-5.97, 0.77-3.59, 0.48-1.06, and 5.05-122.8 µg/g wet weight for Cu, Pb, Co, Ni, Cr, Mn, Cd, and Fe, respectively. The permissible tolerable daily intake (PTDI) and calculated daily intake (CDI) values were compared, and the calculated daily intake values of the samples were found to be below the established values. Correlations between the metal contents in samples were investigated by performing correlation tests with SPSS 13.0 for windows.

Extraction and preconcentration of lead (II) in various water and food samples by orbital shaker-assisted magnetic solid phase extraction method using a new magnetic poly linoleic acid-polystyrene-PDMS block copolymer.

The aim of this study was to develop a practical orbital shaker-assisted magnetic solid phase extraction (OSA-MSPE) method for the determination of lead by FAAS. A new magnetic poly linoleic acid-polystyrene-polydimethylsiloxane (PSt-PLina-PDMS) hydrophobic graft copolymer was synthesized and characterized by NMR, FT-IR, SEM-EDX, DSC, TGA, BET and used as adsorbent for the extraction of Pb (II). This adsorbent can be used at least 50 times without any decrease of its adsorption properties for the adsorption and elution of analyte ions. Several analytical parameters including pH, adsorbent amount, sample volume, shaking time, etc. were optimized. Multivariate optimization was used for the investigation of different parameters. The linear range at optimum operating condition was 1.7-84 µg L-1. The limit of detection (LOD) and limit of quantification (LOQ) were 0.5 µg L-1, 1.7 µg L-1, respectively. Intraday and interday relative standard deviation (RSD %), enhancement factor (EF) and adsorbent capacity were found as 1.9%, 3.3%, 166.7, 50 mg g-1, respectively. OSA-MSPE method was tested with certified reference materials including LGC-6010 (Hard Drinking Water), NCS ZC73032 Celery and CS-M-3 Control Sample Microelements in Mushroom Powder for the accuracy. Experimental results for lead were confirmed with certified values. Present method was successfully applied to various liquid and solid food samples. The OSA-MSPE method has some important features such as selective, sensitive, low LOD, LOQ and RSD, pre-concentration factor (PF) and high enhancement factor (EF). High tolerance limits against matrix ions were achieved.

A sensitive determination of Brilliant Blue FCF in some food samples using hydrophillic deep eutectic solvent-assisted magnetic nano gel-based dispersive solid phase microextraction prior to spectrophotometric analysis.

A new magnetic nano gel (MNG) was prepared from choline chloride/phenol deep eutectic solvent and magnetic amberlite XAD-7 nanocomposite. The dispersive solid phase micro extraction (dSPME) method was developed for seperation and preconcentration of Brilliant Blue FCF (BB) by the prepared MNG. In this study, firstly, the optimum DES type and mole ratio of DES were investigated before response surface methodology optimization. Then, the effect of the MNG-dSPME experimental parameters were optimized by response surface methodology using central composite design. Under the optimum microextraction conditions, limit of detection (LOD), limit of quantification (LOQ), preconcentration factor (PF), enhencament factor (EF) were found to be 1.15 µg L-1,3.80 µg L-1, 70, and 88, respectively. It was seen that the recovery of real samples were obtained from 95.5 to 103.6%. The pesent method was succesfully for extraction of BB in some food, personal care samples, to the best of our knowledge, this is the first study that is presented method on determination of BB by preconcentration with magnetic nano gel. The obtained results showed that the present procedure is effective, sensitive, and has high accuracy for the quantitative detection of BB.

Determination of chromium in foodstuffs by using novel adsorbent in vortex assisted-dispersive solid phase micro-extraction method: An application of multivariate techniques.

A new graft copolymer composed of polystyrene and polylinoleic acid (PLinas) with the sodium salt of iminodiacetate (Ida) was synthesized and used as an adsorbent. The vortex-assisted dispersive solid-phase micro-extraction (VA-dSPµE) method was used for the extraction and pre-concentration of chromium. Multivariate methodologies, such as factorial design and 3D surface plots, were applied for screening and optimizing effective extraction parameters. The influence of diverse analytical parameters, such as pH, sample volume, and interfering ions, on the extraction of chromium was studied. The calibration standard curve exhibited a linear range from 0.01 to 0.50 µg L-1. The relative standard deviation and limit of detection were found to be 1.65 % and 0.003 µg L-1, respectively. Extraction recoveries were found in the range of 96 to 99 % by using certified reference materials (CRMs). The adsorbent capacity of PLinas-Ida was found to be 112 mg g-1. The VA-dSPµE method demonstrated its effectiveness in the pre-concentration and determination of chromium within samples of foodstuffs by graphite furnace-atomic absorption spectrometry (GF-AAS).

Separation and determination of copper in bottled water samples by combination of dispersive liquid--liquid microextraction and microsample introduction flame atomic absorption spectrometry.

A new and simple method for the determination of trace amounts of Cu(II) was developed by combination of dispersive liquid-liquid microextraction (DLLME) preconcentration and microsample introduction flame atomic absorption spectrometry. In this method, ethanol and chloroform were chosen as disperser and extraction solvents, respectively, and 1-nitroso-2-naphthol was used as the complexing agent. The factors affecting the extraction efficiency and determination of Cu(II), including extraction and disperser solvent nature and volume, concentration of the complexing agent, pH of the solution, extraction time, and matrix ions, were investigated. Under optimal conditions, the LOD for Cu(II) was 0.95 microg/L with a preconcentration factor of 70. The RSD was 1.9%. The accuracy of the developed DLLME method was verified by determination of Cu(II) in a certified reference material (NRCC-SLRS-4 river water). The relative error was -3.31%. The developed preconcentration procedure was successfully applied to the analysis of bottled drinking water samples.