Implementation of simple and effective fine droplet formation-based spray-assisted liquid phase microextraction for the simultaneous determination of twenty-nine endocrine disruptor compounds and pesticides in rock, soil, water, moss, and feces samples from antarctica using gas chromatography-mass spectrometry.

This study established the simultaneous determination of the selected endocrine-disrupting compounds (EDCs) and pesticides in rock, soil, water, moss, and feces samples collected from the Antarctic region. The spray-assisted droplet formation-based liquid phase microextraction (SADF-LPME) coupled to GC-MS system was developed and validated for the screening and monitoring of 29 selected EDCs and pesticides. Binary solvent system, 1:1 (v/v) dichlormethane: 1,2-dichloroethane mixture was employed as an extraction solvent and sprayed onto sample or standard solutions using a straightforward and practical spray apparatus. The factors affecting the extraction process such as extraction solvent type and ratio, extraction solvent volume (spray repetition), vortexing period, and sample pH were properly optimized. Analytical figures of the merit of the method were recorded under the optimal extraction/chromatographic conditions. The LOD, LOQ, and enhancement factor were in the range of 1.0 to 6.6 ng/g, 3.2 to 22.1 ng/g, and 3.7 to 158.9, respectively. The method demonstrated a good linear working range for all the selected analytes with proper coefficients of determination. The usability and reliability of the microextraction strategy was confirmed using seawater, moss, and soil samples, and the %recoveries were within an acceptable range (> 70%) for all examined samples. The environmental samples collected from the Horseshoe and Faure Islands of the Antarctica region were analyzed to assess the potential pollution of EDCs and pesticides. This method has the potential to be employed for the analysis of EDCs in routine analytical laboratories and for controlling and screening the organic pollutant content of different environmental samples.

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.

Biogenic synthesis of novel nanomaterials and their applications.

Despite the many benefits derived from the unique features and practicality of nanoparticles, the release of their toxic by-products or products from the synthesis stage into the environment could negatively impact natural resources and organisms. The physical and chemical methods for nanoparticle synthesis involve high energy consumption and the use of hazardous chemicals, respectively, going against the principles of green chemistry. Biological methods of synthesis that rely on extracts from a broad range of natural plants, and microorganisms, such as fungi, bacteria, algae, and yeast, have emerged as viable alternatives to the physical and chemical methods. Nanoparticles synthesized through biogenic pathways are particularly useful for biological applications that have high concerns about contamination. Herein, we review the physical and chemical methods of nanoparticle synthesis and present a detailed overview of the biogenic methods used for the synthesis of different nanoparticles. The major points discussed in this study are the following: (1) the fundamentals of the physical and chemical methods of nanoparticle syntheses, (2) the use of different biological precursors (microorganisms and plant extracts) to synthesize gold, silver, selenium, iron, and other metal nanoparticles, and (3) the applications of biogenic nanoparticles in diverse fields of study, including the environment, health, material science, and analytical chemistry.

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.

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.

Combination of quadrupole isotope dilution mass spectrometry with simultaneous derivatization and spray assisted droplet formation-liquid phase microextraction for the determination of methamphetamine in human urine and serum samples by gas chromatography mass spectrometry.

In this study, an analytical method with high accuracy and precision was developed for the determination of methamphetamine in human urine and serum samples by gas chromatography-mass spectrometry (GC-MS). A simultaneous derivatization and spray assisted droplet formation-liquid phase microextraction (SADF-LPME) method was proposed to derivatize and preconcentrate target analyte. Quadruple isotope dilution (ID4) was used to provide high accuracy and precision for methamphetamine determination in the samples. After the optimization studies for the derivatization and microextraction parameters, limit of detection (LOD) and limit of quantitation (LOQ) for the developed SADF-LPME method were found to be 48.0 and 159.9 µg/kg, respectively. Recovery studies were implemented to verify the applicability and accuracy of the developed method for human urine and serum samples. The SADF-LPME method gave low percent recovery results (30.5-61.0%) for the spiked urine and serum samples showing that it failed to minimize or eliminate matrix effects for the analyte. Hence, methamphetamine acetamide-d3 was synthesized and purified in our research laboratory to be used as methamphetamine isotopic analogue in the ID4 method. When the SADF-LPME method was combined with ID4, the percent recovery values for urine and serum samples were calculated as 99.7-100.0% and 99.4-100.2%, respectively. These results demonstrated the applicability and accuracy of the proposed method for urine and serum samples.

Combination of smartphone digital image colorimetry and UV-Vis spectrophotometry as detection systems with solidified floating organic drop microextraction as preconcentration method for the quantification of methyl red in wastewater samples.

In this study, a portable smartphone-based digital image colorimetric system (SDIC) was designed and integrated with a solidified floating organic drop microextraction method (SFODME) for the quantification of methyl red in textile wastewater samples. The RGB (red, green, and blue) data were evaluated for each captured image, and the green channel was selected for quantification due to its linear response for the analyte. Under optimal conditions, an acceptable linear range was recorded for the analyte. The proposed method recorded a limit of detection (LOD) value of 0.046 mg/L. The developed microextraction method was also combined with UV-Vis spectrophotometry, which recorded an LOD value of 0.012 mg/L. Real sample analysis was carried out with textile wastewater samples to check the applicability/accuracy of the developed method, using a matrix matching calibration strategy to enhance quantification accuracy. Satisfactory percent recoveries in the range of 93.3%-114.3% and 92%-92.7% were recorded for the SFODME-SDIC and SFODME-UV methods, respectively.

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.

Polystyrene-coated magnetic nanoparticles based dispersive solid phase extraction for the determination of cadmium in cigarette ash prior to slotted quartz tube flame atomic absorption spectrometry system.

A sensitive, accurate and simple analytical method was developed to determine cadmium by slotted quartz tube-flame atomic absorption spectrometry after preconcentration/extraction with polystyrene coated magnetic nanoparticles based dispersive solid phase extraction. The surface of Fe3O4 based magnetic nanoparticles was modified with polystyrene to yield higher selectivity and sensitivity in adsorption efficiency of cadmium. The nanoparticles were dispersed into the aqueous solution to extract/separate cadmium. Significant parameters of the method including magnetic nanoparticle amount, mixing effect, effect of ionic strength, eluent concentration and sonication period were optimized to achieve optimal conditions for the analyte. The limit of detection and quantification values of the developed method were found to be 0.62 and 2.1 ng/mL, respectively. Under the optimum conditions, enhancement of the detection power for cadmium were calculated as 102 folds for the developed method. The developed method was then applied to cigarette ash to test its accuracy and applicability. Total cadmium was found to be between 402 and 450 ng/g in the ashes of different cigarette brands commercially available in Turkey. The accuracy of quantifying cadmium in the complex ash samples was enhanced by using the matrix matching calibration strategy. The developed method provides sensitive and selective determination of cadmium at ng/mL levels even at complex cigarette ash samples. High percent recovery results (90-102%) were obtained from spiked real samples.

Development of a metal sieve-linked double syringe liquid phase microextraction method for the determination of copper in olive leaf extract samples by flame atomic absorption spectrometry.

This work reports the development of a simple, sensitive and low-cost analytical method for the trace determination of copper. A metal sieve-linked double syringe liquid phase microextraction method was used to preconcentrate copper into measurable quantities for FAAS system. The pressurized mixing offered by the automated syringe system and the sieve connector enhanced surface area for analyte and extraction solvent interaction, this significantly increased the extraction efficiency for copper. There was therefore no need for auxiliary organic solvents as disperser solvents for the extractant dichloromethane. The limits of detection and quantification, linear dynamic range and percent relative standard deviation values calculated for copper under optimum conditions of the method were 1.5 and 5.1 µg L-1, 5.0-500 µg L-1 and 8.4%, respectively. The developed method was successfully employed to determine copper (0.75-8.06 mg kg-1) in unspiked olive leaf samples.

Determination of trace cadmium in saliva samples using spray assisted droplet formation-liquid phase microextraction prior to the measurement by slotted quartz tube-flame atomic absorption spectrophotometry.

BACKGROUND: An effective, green and rapid analytical strategy namely the simultaneous spray assisted droplet formation-liquid phase microextraction (S-SADF-LPME) method was developed for the determination of trace quantity of cadmium in saliva samples by using the slotted quartz tube-flame atomic absorption spectrophotometry (SQT-FAAS). By the developed method, external dispersive solvent usage for droplet formation was reduced to obtain a more environmental-friendly method. METHODS: Method consists of a simultaneous complexing and extraction step, which was based on spraying an extraction solvent containing a solid ligand into the aqueous sample solution, forming fine droplets without the use of dispersive solvent. The procedure was implemented using a customized, cost effective and portable spray apparatus to minimize the consumption of reagent, analysis time and operation steps. Thus, this methodology ensures better repeatability and accuracy while minimizing the relative errors caused by the experimental steps. Parameters including the buffer amount, extractant/ligand concentration, extraction solvent type, extraction/ligand solution volume, spraying number and vortex period were systemically optimized to lower the detection limit. RESULTS: Under the optimal extraction conditions, 96.9-folds enhancement in the detection power of the traditional FAAS was achieved. The limit of detection and limit of quantification values of presented method were calculated to be 0.65 and 2.17 ng mL-1, respectively. Accuracy and applicability of the optimized method was investigated by collecting saliva samples from smokers. Satisfactory percent recovery values wereachieved for cadmium with a low standard deviation in the acceptable range of 84.9-109.6 %. CONCLUSION: The developed dispersive solvent-free S-SADF-LPME technique presents a fast, simple, cost-effective and eco-friendly microextraction method based on the use of an easily accessible and functional spray apparatus.

A basic and effective liquid phase microextraction with a novel automated mixing system for the determination of cobalt in quince samples by flame atomic absorption spectrometry.

A new, green, and simple liquid-phase microextraction method namely sieve conducted two syringe-based pressurized liquid-phase microextraction methods was combined with flame atomic absorption spectrometry for the preconcentration and determination of cobalt. For this aim, a novel automated syringe mixing system was developed to be used in the developed extraction procedure. Two syringes were connected to each other by an apparatus having six holes to produce efficient dispersion of the extractant. The pressure created between the two syringes by the forward and backward movements of the syringe plungers created an efficient dispersion of the extractant. In the present study, ligand as complexing agent was synthesized in our laboratory. Limits of detection and quantification were determined to be 1.8 and 6.0 µg L-1, respectively. A 33.7-fold enhancement in detection power was obtained with the developed method. Method was effectively applied for the determination of cobalt in quince samples.

An accurate and sensitive effervescence-assisted liquid phase microextraction method for the determination of cobalt after a Schiff base complexation by slotted quartz tube-flame atomic absorption spectrophotometry in urine samples.

In this study, an accurate analytical method development for cobalt determination in urine samples was described. The method is based on the mass transfer of the target analytes to the organic phase from the aqueous phase by the dispersing extractant throughout the solution with the aid of CO2 bubbles prior to sample measurement by using a slotted quartz tube flame atomic absorption spectrophotometer. An extractor (1-decanol) dropped effervescent tablet (anhydrous sodium carbonate and sodium dihydrogen phosphate dihydrate mixture) was used in order to separate/preconcentrate cobalt after complexation of cobalt ions in aqueous solution with the Schiff base ligand. The parameters affecting the extraction output such as complexing conditions (pH, ligand concentration, and volume) and extraction conditions (extraction solvent type and volume, extraction temperature, and heating duration, NaOH volume and mixing period) were optimized to lower the detection limit. The limit of detection and quantification values under optimized experimental and instrumental conditions were determined as 3.7 µg L-1 and 12 µg L-1, respectively with high linearity with respect to the dynamic range between 15 and 300 µg L-1. The enhancement factor obtained with the developed method was calculated as 83 fold. The pretreatment process was applied to urine samples in order to test the convenience of the developed method in urine samples for the determination of cobalt at low levels. The high percentage recovery results of 96-97% for four different concentrations of spiked urine samples indicated the proposed method's sufficient sensitivity for analyte determination in such a complex matrix.

Combination of stearic acid coated magnetic nanoparticle based sonication assisted dispersive solid phase extraction and slotted quartz tube-flame atomic absorption spectrophotometry for the accurate and sensitive determination of lead in red pepper samples and assessment of green profile.

This study describes the determination of lead at trace levels by slotted quartz tube flame atomic absorption spectrophotometry (SQT-FAAS) after preconcentration by the help of stearic acid coated magnetic nanoparticle (SAC-MNPs) based sonication assisted dispersive solid phase extraction (SA-DSPE). SAC-MNPs were used due to their easy separation advantages by the application of external magnetic field. All extraction parameters were optimized by response surface methodology based experimental design. The experimented data was evaluated by the analysis of variance. Under the optimum conditions, about 31 folds enhancement in detection power was obtained over the conventional FAAS. The recovery results obtained for samples spiked at 60 and 120 ng mL-1 were 106.6 and 102.6%, respectively, validating the method as accurate and applicable to the red pepper matrix. The percent relative standard deviations of the results were under 5.0% even at low concentrations that established high precision for replicate extractions and instrumental readings.

A new combination for the determination of ultratrace cadmium: solid-phase microextraction by stearic acid-coated magnetic nanoparticles prior to batch-type hydride generation atomic absorption spectrometry.

Solid-phase microextraction method based on stearic acid-coated magnetic nanoparticle has been combined with batch-type hydride generation atomic absorption spectrometry (BT-HGAAS) system to determine cadmium at ultratrace levels. After the adsorption of cadmium ions onto stearic acid-coated magnetic nanoparticles, they were easily separated from the aqueous phase by means of a magnet. All the instrumental and experimental parameters such as pH of buffer solution, interaction period, concentration, and volume of NaBH4 were optimized. Under the optimal conditions, limit of quantification (LOQ) and limit of detection (LOD) for the solid-phase microextraction (SPME) based on stearic acid-coated magnetic nanoparticles-BT-HGAAS (SACMNP-BT-HGAAS) method were obtained as 270.8 ng/L and 81.7 ng/L, respectively. The matrix-matching calibration method was performed in order to improve the accuracy of cadmium quantification in tap water and the recovery results obtained were as follows: 88.56 ± 8.92 and 97.43 ± 9.76, for 6.0 and 8.0 ng/mL of cadmium-spiked tap water samples, respectively. Graphical abstract ᅟ.

Development of an efficient and sensitive analytical method for the determination of copper at trace levels by slotted quartz tube atomic absorption spectrometry after vortex-assisted dispersive liquid-liquid microextraction in biota and water samples using a novel ligand.

This study describes the determination of trace levels of copper by slotted quartz tube atomic absorption spectrometry after dispersive liquid-liquid microextraction. A ligand synthesized from the reaction of salicylaldehyde and 1-naphthylamine was used to form coordinate copper complex prior to extraction. All parameters that influence the output of complex formation, extraction, and instrumental measurement were optimized to enhance the absorbance signal of copper. Under the optimum conditions, about 104-fold enhancement in sensitivity was recorded over the conventional flame atomic absorption spectrometer, corresponding to a 0.51 ng/mL detection limit. The percent relative standard deviation calculated for the lowest concentration (4.8%) indicated high precision for the experimental procedure. Accuracy and applicability of the optimum method were determined by performing spiked recovery tests on urine, lake water, and mineral water samples. Satisfactory recovery results were obtained between 82.2 and 106.3% at four different concentrations. Matrix matching method was also performed to increase the accuracy of quantification, and the percent recovery calculated for 175 ng/mL was 105.14%.