Determination of phenytoin at trace levels in domestic wastewater and synthetic urine samples by gas chromatography-mass spectrometry after its preconcentration by simple liquid-phase microextraction.

This work presents a sensitive and accurate analytical method for the determination of phenytoin at trace levels in domestic wastewater and synthetic urine samples by gas chromatography-mass spectrometry (GC-MS) after the metal sieve-linked double syringe liquid-phase microextraction (MSLDS-LPME) method. A metal sieve was produced in our laboratory in order to disperse water-immiscible extraction solvents into aqueous media. Univariate optimization studies for the selection of proper extraction solvent, extraction solvent volume, mixing cycle, and initial sample volume were carried out. Under the optimum MSLDS-LPME conditions, mass-based dynamic range, limit of quantitation (LOQ), limit of detection (LOD), and percent relative standard deviation (%RSD) for the lowest concentration in calibration plot were figured out to be 100.5-10964.2 µg kg-1, 150.6 µg kg-1, 45.2 µg kg-1, and 9.4%, respectively. Detection power was improved as 187.7-folds by the developed MSLDS-LPME-GC-MS system while enhancement in calibration sensitivity was recorded as 188.0-folds. In the final step of this study, the accuracy and applicability of the proposed system were tested by matrix matching calibration strategy. Percent recovery results for domestic wastewater and synthetic urine samples were calculated as 95.6-110.3% and 91.7-106.6%, respectively. These results proved the accuracy and applicability of the proposed preconcentration method, and the obtained analytical results showed the efficiency of the lab-made metal sieve apparatus.

Novel data on genotoxic assessment of bismuth sulfide nanoflowers in common carp Cyprinus carpio.

The environmental impacts and risks of nanomaterials that are commonly used in different technologies are of great concern as their toxic effects on the aquatic ecosystem remain unclear. In this study, bismuth sulfide (Bi2S3) nanoflowers (nfs) were synthesized using a microwave-based hydrothermal process, and their genotoxic effects were investigated in the common carp, Cyprinus carpio. Bi2S3 nanoflowers were applied to common carp for 96 h. LC50 value (LC50 = 350 mg/L-1) was determined for acute toxicity with probit analysis, and three sublethal concentrations (35, 87, and 175 mg/L-1) were selected accordingly for genotoxicity tests. Such LC50 value - 350 mg L-1 for the common carp makes these nanoflowers non-toxic to aquatic organisms according to the EU-Directive 93/67/EEC classification scheme. Toxicological evaluations of the sublethal concentrations of Bi2S3 nanoflowers demonstrated that the 35 and 87 mg L-1 Bi2S3nfs groups were generally harmless and similar to the control group. Only the 175 mg L-1 Bi2S3nfs group had significant DNA damage frequency and nuclear abnormalities than the control and other Bi2S3nfs groups. To the best of our knowledge, this is a novel data on genotoxicity reported for fish species exposed to Bi2S3 nanoflowers; however, further systematic studies need to be performed to fully estimate the effects of Bi2S3 nanoflowers on aquatic life.

Determination of trace cobalt ions in bottled drinking water samples from Fiji Island by spray-assisted fine droplet formation-liquid phase microextraction based on simultaneous complexation and extraction before flame atomic absorption spectrometer measurement.

In this study, a green, simple and effective preconcentration method named as spray-assisted fine droplet formation-liquid phase microextraction (SAFDF-LPME) before the flame atomic absorption spectrophotometry (FAAS) measurement for cobalt determination was developed. The method reduces the external dispersive solvent usage by using a simple spraying apparatus to obtain fine droplets of the extraction solvent. SAFDF-LPME method also consists of simultaneous complexation and extraction which indicates the environmental benevolence of the developed method. This method minimized the relative errors with high repeatability and accuracy by reducing the experimental steps. The influential parameters such as buffer type, buffer solution volume, extraction solvent/ligand solution volume (spraying cycle), and mixing period were systematically optimized by the univariate optimization procedure. With the optimum parameters applied, the detection power of the FAAS system was enhanced to about 110-folds with respect to 2.2 ng mL-1 detection limit calculated for the proposed method. Bottled drinking water samples from Fiji Islands were used to demonstrate the applicability of the developed method for the accurate determination of trace cobalt in real sample matrices. Percent recovery results obtained between 95.5 and 88.5% showed the suitability of the developed method in the determination of cobalt at trace levels even in complex sample matrices.

Deep eutectic solvent-based simultaneous complexation and preconcentration of nickel in Antarctic lake water samples for determination by flame atomic absorption spectrometry.

This study presents a simple, sensitive, and accurate method for the determination of nickel by flame atomic absorption spectrometry (FAAS). Prior to instrumental measurement, a deep eutectic solvent-based simultaneous complexation and preconcentration (DES-SCP) method was used to preconcentrate nickel from aqueous solution into measurable quantities. The efficiency of the extraction method was enhanced by forming a non-ionic complex of nickel using dithizone as ligand. By mixing the ligand with the DES extractant, simultaneous complexation and preconcentration of nickel were achieved in a single step. Under optimum conditions of the extraction method, the limit of detection (LOD) and the limit of quantification (LOQ) values were found to be 2.4 and 8.0 ng/mL, respectively. With respect to direct FAAS measurement, the developed method enhanced the sensitivity of nickel determination by about 169 folds. The accuracy and applicability of the developed method were evaluated by performing spike recovery experiments with lake water sampled from Antarctica. Satisfactory recovery results in the range of 94.0-113.7% were recorded and this validated the developed method as an efficient and green alternative for nickel determination.

Analytical application of flower-shaped nickel nanomaterial for the preconcentration of manganese in domestic wastewater samples.

In this study, detection sensitivity of the conventional flame atomic absorption spectrophotometer (FAAS) for the determination of manganese (Mn2+) was enhanced by employing a preconcentration method from wastewater samples. Flower-shaped Ni(OH)2 nanomaterials were synthesized and used as sorbent material in preconcentration procedure. With the aim of attaining optimum experimental conditions, effective parameters of extraction method were optimized and these included pH of buffer solution, desorption solvent concentration and volume, mixing type and period, nanoflower amount, and sample volume. The detection limit of the optimized method was determined to be 2.2 µg L-1, and this correlated to about 41-fold enhancement in detection power relative to direct FAAS measurement. Domestic wastewater was used to test the feasibility of the proposed method to real samples by performing spike recovery experiments. The wastewater sample was spiked at four different concentrations of manganese, and the percent recoveries determined were in the range of 95-120%.

Quantification of trace fenuron in waste water samples by matrix matching calibration strategy and gas chromatography-mass spectrometry after simultaneous derivatization and preconcentration.

This study presents a highly sensitive and accurate analytical strategy for the determination of fenuron in wastewater samples using gas chromatography-mass spectrometry (GC-MS). Simultaneous derivatization and spray-based fine droplet formation-liquid phase microextraction (SFDF-LPME) method was developed and performed to achieve low detection limits. The parameters of the derivatization and SFDF-LPME method were optimized by univariate approach to improve sensitivity and selectivity. Under the optimum SFDF-LPME-GC-MS conditions, the limit of detection (LOD) and limit of quantitation (LOQ) were found to be 0.15 and 0.49 mg/kg, respectively. In addition, the linear range was calculated as 0.51-24.50 mg/kg. Recovery studies were carried out on wastewater samples to determine the accuracy of the developed method and its applicability to real sample matrix. Matrix matching calibration strategy was applied to eliminate/reduce any possible interference effects caused by the complexity of the wastewater matrix and to increase the accuracy of the analytical results. Percent recovery results varied between 85.9 and 120.9% with small percent relative standard deviation values. These results were satisfactory in terms of the accuracy and applicability of the proposed method for wastewater samples.

Trace nickel determination in seawater matrix using combination of dispersive liquid-liquid microextraction and triethylamine-assisted Mg(OH)2 method.

In order to eliminate the effects of seawater matrix on the precise/accurate determination of elements, new and efficient analytical procedure requires. In this study, co-precipitation method based on the triethylamine (TEA)-assisted Mg(OH)2 was performed to eliminate side-effects of seawater medium on the determination with flame atomic absorption spectrometry (FAAS) prior to the preconcentration of nickel by an optimized dispersive liquid-liquid microextraction (DLLME) method. Under the optimum conditions of the presented method, the limit of detection and quantification (LOD, LOQ) values obtained for nickel were found as 16.1 and 53.8 µg kg-1, respectively. Seawater samples collected from West Antarctic region were used for real sample applications to check the accuracy and applicability of developed method, and satisfying recovery results (86-97%) were obtained. In addition to this, the digital image-based colorimetric detection system and the UV-Vis system were applied to confirm the applicability of the developed DLLME-FAAS method in other analytical systems.

Removal of two antidepressant active pharmaceutical ingredients from hospital wastewater by polystyrene-coated magnetite nanoparticles-assisted batch adsorption process.

This study employed simple polystyrene-coated magnetite nanoparticles (PS@MNPs)-assisted batch adsorption process for the removal of two antidepressant active ingredients (amitriptyline HCl and sertraline HCl) from hospital wastewater. Dominant parameters of the adsorption process including pH, adsorbent amount, and contact period were optimized through the univariate approach to enhance the adsorption efficiency. Upon reaching optimum adsorption conditions, equilibrium experiments were performed by spiking the adsorbates in hospital wastewater in the concentration range of 100-2000 µg/L. The concentrations of the adsorbates in the effluent were calculated using the matrix-matching calibration strategy to enhance the accuracy of quantification. A validated switchable solvent-based liquid phase microextraction (SS-LPME) method was employed to enrich the two active pharmaceutical ingredients (APIs) prior to sensitive determination with GC-MS (gas chromatography-mass spectrometry). The equilibrium data were mathematically modeled employing the Langmuir and Freundlich adsorption isotherm models. The isotherm constants were calculated, and the results showed that both the isotherm models fitted well with the experimental data. The efficient and simple batch adsorption strategy reported in this study was successfully employed to remove amitriptyline HCl and sertraline HCl from hospital wastewater at low concentrations.

A simple and efficient derivatization strategy combined with switchable solvent liquid-liquid microextraction hydroxychloroquine methyl acetate-d3 -based quadruple isotope dilution gas chromatography mass spectrometry for the determination of hydroxychloroquine sulfate in biological fluids.

RATIONALE: A derivatization switchable solvent liquid-liquid microextraction quadruple isotope dilution gas chromatography mass spectrometry (D-SS-LLME-ID4 -GC/MS) method is presented for the determination of hydroxychloroquine sulfate in human biofluids. METHODS: While mixing type/period and concentration of NaOH were optimized via a univariate optimization approach, a multivariate optimization approach was used to determine optimum values for relatively more important parameters such as volumes of derivatization agent (acetic anhydride), NaOH and switchable solvent. RESULTS: Under the optimum experimental conditions, limit of detection and limit of quantification were calculated as 0.03 and 0.09 mg/kg (mass based), respectively. An isotopically labelled material (hydroxychloroquine methyl acetate-d3 ) was firstly synthesized to be used in ID4 experiments which give highly accurate and precise recovery results. After the application of D-SS-LLME-ID4 , superior percent recovery results were recorded as 99.9 ± 1.6-101.3 ± 1.2 for human serum, 99.9 ± 1.7-99.8 ± 1.8 for urine and 99.6 ± 1.5-101.0 ± 1.1 for saliva samples. CONCLUSIONS: The developed D-SS-LLME-ID4 -GC/MS method compensates the complicated matrix effects of human biofluids and provides highly accurate quantification of an analyte with precise results.

Removal of selected pesticides, alkylphenols, hormones and bisphenol A from domestic wastewater by electrooxidation process.

In this study, seven compounds of environmental and health concern were treated by electrooxidation to determine their removal efficiencies from domestic wastewater. A batch type lab-scale reactor was used for the treatment process, and the analytes studied included two obsolete pesticides, two alkylphenols, two hormones, and bisphenol A. Titanium oxide and graphite electrodes were used as anode and cathode, respectively. Parameters of the electrooxidation process including pH of wastewater, ionic strength, applied current and treatment period were optimized by the univariate approach to maximize the removal efficiency of the analytes from wastewater. The optimum conditions were determined as nonadjusted pH of wastewater, 1.5 A current, 15 min treatment period and 5.0 g/L sodium chloride. Dispersive liquid-liquid microextraction was used to preconcentrate analytes before and after treatment in order to calculate the removal efficiency of analytes. The removal efficiency obtained under the optimum conditions was satisfactory for all seven analytes at different influent concentrations.

Chromium speciation by the combination of high-performance liquid chromatography and inductively coupled plasma-optical emission spectrometry.

A hyphenated instrumental method high-performance liquid chromatography-inductively coupled plasma-optical emission spectrometry (HPLC-ICP-OES) was used for the separation and determination of Cr(III) and Cr(VI). After the chromatographic separation of chromium species by anion exchange column, their spectrophotometric detection was carried out by ICP-OES system. Important instrumental and chromatographic parameters were investigated via univariate optimization approach to obtain high signal to noise ratio and good resolution for chromium species. Under the optimum HPLC-ICP-OES conditions, limit of detection (LOD) values for Cr(III) and Cr(VI) were found to be 0.27 and 0.05 mg/kg, respectively. In addition, accuracy and applicability of developed method were checked by recovery experiments performed with the spiked soil, grass, and water samples. High percent recovery results (88-104%) were achieved by utilizing matrix matching calibration strategy for the selected samples. The results showed that this method was accurate and applicable to soil, grass, and water samples.

Determination of diflufenican and azaconazole pesticides in wastewater samples by GC-MS after preconcentration with stearic acid functionalized magnetic nanoparticles-based dispersive solid-phase extraction.

This study presents the preconcentration of diflufenican and azaconazole from domestic wastewater samples by using dispersive solid-phase extraction (dSPE) for determination by gas chromatography-mass spectrometry (GC-MS). Stearic acid-coated magnetic nanoparticles were used as adsorbents for dSPE method. In order to maximize the efficiency of the extraction process, parameters such as magnetic nanoparticle (MNP) type and amount, eluent type and volume, mixing type, and mixing period were all optimized. The linear range obtained for azaconazole and diflufenican was 7.50-500 ng/mL and 7.50-750 ng/mL, and their limits of detection/quantification (LOD/LOQ) were calculated as 1.3/4.3 ng/mL and 1.4/4.7 ng/mL, respectively. By comparing the LOD values of direct GC-MS and the developed dSPE method, azaconazole and diflufenican recorded approximately 35 and 38 folds enhancement in detection power. Recovery experiments with domestic wastewater were carried out to certify the proposed method's accuracy and applicability. By using the matrix matching calibration strategy, the good percent recovery results between 98 and 105% were obtained.

Development of a double monitoring system for the determination of Cr(VI) in different water matrices by HPLC-UV and digital image-based colorimetric detection method with the help of a metal sieve-linked double syringe system in complexation.

This study reports a cheap, efficient, sensitive, and simple double monitoring analytical method for trace determination of Cr(VI), which is toxic and harmful even at very low concentrations. A metal sieve-linked double syringe (MSLDS) system was used to help the formation of chromium complex (Cr-diphenyl carbazide, DPC) subsequently determined by high-performance liquid chromatography-ultraviolet (HPLC-UV) and digital image-based colorimetry (DIC) systems. The metal complex was eluted through a Phenomenex-Aqua C18 with a mobile phase comprising of 50 mM ammonium formate solution (pH 4.0):acetonitrile (78:22, v/v) and detected by the UV detector at the wavelength of 581 nm. Under their optimum conditions, the HPLC-UV and DIC systems exhibited good linearity in ranges of 10-500 µg L-1 and 100-1000 µg L-1, respectively. The percent relative standard deviations (RSD%s) calculated for the lowest concentrations of both systems fell below 10%, and this confirmed good repeatability for replicate measurements. The accuracy of the proposed methods was evaluated by performing spike recovery experiments on wastewater, river water, and tap water samples. The calculated recovery results were in the range of 81.5-105.5% for HPLC-UV system and 93.8-111.1% for the DIC system. These results indicate that the proposed methods are suitable for routine Cr(VI) determination in terms of their rapidness, simplicity, good repeatability, and low cost.

Trace level determination of eleven nervous system-active pharmaceutical ingredients by switchable solvent-based liquid-phase microextraction and gas chromatography-mass spectrometry with matrix matching calibration strategy.

This study utilized switchable solvent liquid-phase microextraction (SS-LPME) to enrich eleven nervous system active pharmaceutical ingredients (APIs) from aqueous samples for their determination at trace levels by gas chromatography mass spectrometry. The analytes selected for the study included APIs utilized in antidepressant, antipsychotic, antiepileptic, and anti-dementia drugs. Parameters of the microextraction method including switchable solvent volume, concentration and volume of the trigger agent (sodium hydroxide), and sample agitation period were optimized univariately to boost extraction efficiency. Under the optimum conditions, the detection limits calculated for the analytes were in the range of 0.20-8.0 ng/mL, and repeatability for six replicate measurements as indicated by percent relative standard deviation values were below 10%. Matrix matching calibration strategy was used to enhance quantification accuracy for the analytes. The percent recovery results calculated for the eleven analytes ranged between 86 and 117%.

Nickel hydroxide nanoflower-based dispersive solid-phase extraction of copper from water matrix.

In this work, a dispersive solid-phase extraction method based on Ni(OH)2 nanoflowers (Ni(OH)2-NFs-DSPE) was developed to separate and preconcentrate copper ions from tap water samples for determination by flame atomic absorption spectrometry (FAAS). Ni(OH)2-NFs was synthesized using a homogeneous precipitation technique and used as sorbent for copper preconcentration. X-ray diffraction, scanning electron microscopy, and Fourier-transform infrared spectroscopy were used to characterize the synthesized sorbent. All experimental variables were carefully optimized to achieve a high enhancement factor of 107.5-folds with respect to the detection sensitivity of the conventional FAAS. The proposed method's analytical parameters including LOD, LOQ, and linear range were determined as 1.33 µg/L, 4.42 µg/L, and 3.0-40 µg/L, respectively. To assess the applicability and reliability of the developed method, optimal conditions were applied to tap water samples and satisfactory percent recoveries (94-103%) were obtained for the samples spiked at 20 and 30 µg/L. This validated the accuracy and feasibility of the developed method to real samples. The developed method can be described as a simple, efficient, and rapid analytical approach for the accurate determination of trace copper ions in water samples.

Development and validation of dispersive liquid-liquid microextraction method for the determination of 15 polycyclic aromatic hydrocarbons in 200 Antarctica samples by gas chromatography mass spectrometry.

Antarctica has seen an increase in scientific research and tourism, and anthropogenic activities such as incineration of waste products and fuel combustion for energy and transportation are potential contamination sources to the ecosystem. Polycyclic aromatic hydrocarbons are common products of incomplete combustion of organic compounds and could be among accumulating contaminants in Antarctica. Thus, this study sought to develop a sensitive dispersive liquid-liquid microextraction method for the determination of 15 polycyclic aromatic hydrocarbons by gas chromatography mass spectrometry. Parameters that were relevant to the extraction method were carefully optimized and validated using aqueous standard solutions. The optimum method recorded detection limits in the range of 0.20-6.1 µg/L for the analytes. Spike recovery experiments were carried out on artificial seawater, rock-soil, and moss samples, using matrix matching calibration to mitigate effects of the sample matrices. The samples analyzed included seawater, lake, rock-soil, moss, seaweed, and feces samples all collected from the Horseshoe and Faure Islands in Antarctica. The percent recovery results obtained for the samples spiked at different concentrations ranged between 86 and 115%.

Zirconium Nanoparticles Based Vortex Assisted Ligandless Dispersive Solid Phase Extraction for Trace Determination of Lead in Domestic Wastewater using Flame Atomic Absorption Spectrophotometry.

In this paper, a sensitive and simple zirconium nanoparticles (Zr-NPs) based vortex assisted ligandless dispersive solid phase extraction (VA-LDSPE) method was developed for the preconcentration of lead from wastewater samples for the determination by slotted quartz tube-flame atomic absorption spectrometry (SQT-FAAS). Zr-NPs were synthesized using zirconium (IV) chloride salt as a starting material through a simple reduction process with sodium borohydride, and used as selective adsorbent for the extraction of lead ions from aqueous medium. Single variant experiments were carried out for all optimizations of sorption/desorption steps including pH of solution, amount of nanoparticles, mixing type/period and eluent type. An SQT with five round slots was placed onto the burner of FAAS to increase the interaction between lead atoms and light from radiation source to enhance the absorbance signals. Under the determined optimum conditions, analytical figures of merit were evaluated and the limit of detection and quantification (LOD/LOQ) values were calculated as 5.2 and 17.3 µg L- 1, respectively. The developed method showed a linear calibration range between 25 and 250 µg L- 1 with a good regression coefficient value (0.9995). Recovery studies were also performed with domestic wastewater samples spiked at three concentrations and percent recovery values obtained in the range of 97%-102% validated the developed method's applicability and accuracy.

Surface modified iron magnetic nanoparticles assisted Fenton digestion and extraction method for cadmium determination.

This study presents a Fenton digestion method for milk samples based on UV irradiation for cadmium determination using flame atomic absorption spectrometry. The method was developed as an alternative to microwave digesters, using very basic apparatus and easy to acquire chemicals. Fenton digestion process was performed by the help of citric acid coated magnetic nanoparticles. Optimum conditions of the digestion process were applied to milk samples to evaluate analytical performance of the method. Limit of detection and limit of quantification values calculated for cadmium in milk were 0.53 and 1.8 mg/L, respectively. The method was applied to three different milk samples to validate the method's suitability and accuracy. Percent recovery values calculated for the samples spiked at two different concentrations ranged between 86 and 111%. Due to differences in the content of the spiked and control/standard milk samples, exact matrix matching calibration strategy using the same brand of milk sample in the preparation of calibration standard was employed and the accuracy of cadmium quantification was greatly enhanced (≈100%).

A miniaturized spray-assisted fine-droplet-formation-based liquid-phase microextraction method for the simultaneous determination of fenpiclonil, nitrofen and fenoxaprop-ethyl as pesticides in soil samples.

RATIONALE: Pesticides are a group of micropollutants that persist for a long time in the environment and pose threats to life. Much effort has been devoted to developing pre-concentration methods capable of producing samples suitable for the detection of pesticides. However, better methods are still required to detect these compounds when they are present in trace concentrations in soils. METHOD: Spray-assisted fine-droplet-formation-based liquid-phase microextraction was used to prepare soil samples containing three different pesticides, fenpiclonil, nitrofen and fenoxaprop-ethyl, for subsequent analysis by gas chromatography/mass spectrometry (GC/MS). A spraying apparatus was used for the dispersion of the extraction solvent into the sample/standard solution to improve the extraction efficiency. Optimization studies were performed to lower the detection limits of these analytes and the results obtained by the application of the newly developed system were compared with those obtained using the conventional GC/MS method. RESULTS: A calibration curve over the range 5.0-100 µg L-1 was obtained under the optimal conditions. The limits of detection and quantification were 1.56-1.80 µg L-1 and 5.21-5.98 µg L-1 , respectively. The enhancements in detection ability over the conventional method for the three tested pesticides were 188.01, 176.96 and 517.14 for fenpiclonil, nitrofen and fenoxaprop-ethyl, respectively Recovery studies performed in soil samples were satisfactory reflecting accurate applicability of the developed method. CONCLUSIONS: The developed microextraction method is a time-saving and simple version of the traditional dispersive liquid-liquid microextraction method that also reduces the use of dispersive solvents.

Determination of selenite and selenomethionine in kefir grains by reversed-phase high-performance liquid chromatography-inductively coupled plasma-optical emission spectrometry.

A new and efficient reversed-phase high-performance liquid chromatography-inductively coupled plasma-optical emission spectrometry method was developed for the simultaneous separation and determination of SeO3 2- and seleno-dl-methionine in kefir grains. For the system, limits of detection and quantitation values for SeO3 2- and seleno-dl-methionine were calculated as 0.52/1.73 mg/kg (as Se) and 0.26/0.87 mg/kg (as Se), respectively. After performing the system analytical performance, recovery experiment was done for kefir grains and percent recovery results for SeO3 2- and seleno-dl-methionine were calculated as 98.4 ± 0.8% and 93.6 ± 1.0%, respectively. It followed by the feeding studies that the kefir grains were exposed to three different concentrations of SeO3 2- (20, 30, and 50 mg/kg) for approximately 4 days at room temperature to investigate the conversion/non-conversion of SeO3 2- to seleno-dl-methionine. Next, the fed grains were extracted with tetramethylammonium hydroxide pentahydrate solution (20%, w/w) and then sent to the developed system. There was no detectable seleno-dl-methionine found in fed kefir grains at different concentrations of SeO3 2- while inorganic or elemental selenium in the fed kefir grains was determined between 1579.5 - 3116.0 mg/kg (as Se). Selenium species in the kefir grains samples was found in the form of SeO3 2- proved by using an anion exchange column.