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.

A simple microwave-assisted synthesis of cobalt ferrite nanoparticles and its application for the determination of lead ions in rooibos (Aspalathus linearis) tea.

In this study, a magnetic sorbent assisted dispersive solid phase extraction (DSPE) method was used to preconcentrate lead ions from rooibos tea samples for determination by slotted quartz tube-flame atomic absorption spectrometry (SQT-FAAS). Cobalt ferrite magnetic nanoparticles (CoFe2O4 MNPs) were synthesized by microwave assisted digestion. Limits of detection and quantification were calculated as 5.3 and 17.6 µg/L, respectively, in a linear dynamic range of 20-800 µg/L. The enhancement factor of the developed method was found to be 80-folds when compared to the detection limit of the regular FAAS system. The percent recoveries obtained for rooibos tea samples spiked at different concentrations were in the range of 77 - 125%, with high repeatability as indicated by low standard deviations. The findings of the study demonstrated that the CoFe2O4 MNPs-based extraction method is a straightforward, fast, affordable, safe, and eco-friendly approach to qualifying/quantifying lead with high precision in the selected beverage sample.

Validation and green profile assessment of a binary solvent liquid phase microextraction method for the determination of chlorbenside and fenobucarb in lake and wastewater samples by GC-MS.

This study reports a liquid phase microextraction method based on binary extraction solvents, which were used to preconcentrate chlorbenside and fenobucarb from aqueous samples for determination by gas chromatography mass spectrometry. Parameters including the type, ratio, and volume of binary solvents, disperser solvent type and volume, and vortex period were optimized systematically to achieve high enrichment for the analytes. The optimum conditions obtained were used to validate the method, and the detection limits calculated for chlorbenside (0.71 ng/mL) and fenobucarb (0.33 ng/mL) correlated to enrichment factors of 399- and 912-folds, respectively. The optimum method was applied to lake water and wastewater samples in spike recovery experiments, and the results obtained (96-104%) verified the method as accurate and applicable to the aqueous sample matrices. Matrix matching calibration method was used to boost the accuracy of quantifying the two analytes in the wastewater sample, which presented interference effects. Assessment of the method's green profile based on penalty points confirmed the method's compliance with green analytical chemistry.

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.

Performance evaluation of ceramic membrane bioreactor: effect of operational parameters on micropollutant removal and membrane fouling.

This paper presents the removal of nine potential endocrine disruptors including pesticides, pharmaceuticals and industrial chemicals using a submerged membrane bioreactor (MBR) system. Two lab-scale submerged MBRs having ceramic membranes were operated at three different sludge retention times (SRT: 15, 45, 90 days) and two hydraulic retention times (HRT: 12, 6 h) and the effects of SRT and HRT on both micropollutant removal and membrane fouling were investigated. While the effect of SRT and HRT change was observed on the removal of atrazine, fluoxetine, penconazole, no significant change was detected for the other micropollutants studied. It was determined that physicochemical properties such as distribution coefficient (LogD) and hydrophobicity of micropollutants are also effective on the removal efficiency of micropollutants. High removal efficiencies ([Formula: see text] 97.5%) were observed for hydrophobic pollutants (logD > 3.2) except for penconazole (72.1%) and for hydrophilic pollutants (logD < 3.2) except for atrazine (42.5%). Membrane fouling was significantly affected by different operational parameters applied, with the slowest fouling occurring at 45 days of SRT and 12 h of HRT. However, micropollutant addition did not have a significant effect on membrane fouling. It has been shown that the simultaneous and effective treatment performance for micropollutants makes the membrane bioreactor system a promising wastewater treatment process.

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%.

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.

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.

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%.

Determination of levetiracetam by GC-MS and effects of storage conditions and gastric digestive systems on drug samples.

Background: Epilepsy is a neurologic condition that is occurs globally and is associated with various degrees of seizures. Levetiracetam is an approved drug that is commonly used to treat seizures in juvenile epileptic patients. Accurate quantification of the drug's active compound and determining its stability in the stomach after oral administration are important tasks that must be performed. Results & methodology: Levetiracetam was extracted from drug samples and quantified by gas chromatography mass spectrometry using calibration standards. Stability of levetiracetam was studied under various storage conditions and in simulated gastric conditions. The calibration plot determined for levetiracetam showed good linearity with a coefficient of determination value of 0.9991. The limits of detection and quantification were found to be 0.004 and 0.014 µg·ml-1, respectively. The structural integrity of levetiracetam did not change within a 4-h period under the simulated gastric conditions, and no significant degradation was observed for the different storage temperatures tested. Discussion & conclusion: An accurate and sensitive quantitative method was developed for the determination of levetiracetam in drug samples. The stability of the drug active compound was monitored under various storage and gastric conditions. The levetiracetam content determined in the drug samples were within ±10% of the value stated on the drug labels.

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%).

Arsenic speciation in rice samples for trace level determination by high performance liquid chromatography-inductively coupled plasma-mass spectrometry.

Six arsenic species, namely arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB) and arsenocholine (AsC) were speciated using a combination of high-performance liquid chromatography and inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Under optimum chromatographic conditions, six arsenic species were well separated, and the performance of the combined system (HPLC-ICP-MS) for the species was determined. The limits of detection were calculated in the range of 0.14-0.29 ng/mL, and the corresponding quantification limits ranged between 0.45 and 0.97 ng mL-1 for the species. Spike recovery experiments performed on rice samples were used to validate the method's applicability to complex matrices. The recovery results calculated ranged between 93 and 109%, validating the method's applicability. Triplicate measurements for all spiked samples recorded percent relative standard deviation values below 10%.

Dispersive Liquid-Liquid Microextraction Based Preconcentration of Selected Pesticides and Escitalopram Oxalate, Haloperidol, and Olanzapine from Wastewater Samples Prior to Determination by GC-MS.

BACKGROUND: Determination of emerging pollutants including pharmaceuticals, pesticides, industrial chemicals and hormones in different environmental samples is very important for human health. OBJECTIVE: Experimental design enabled parameters to be evaluated for their effects onextraction output as well as their interactive effects. METHOD: A multivariate experimental design was used to attain optimum conditions of a dispersive liquid-liquid microextraction method for preconcentration of pesticides and pharmaceuticals for determination by GC-MS. RESULTS: The optimum parameters suggested by the design model were 200 µL of chloroform, 1.96 mL of ethanol, and 40 s vortexing period. LOD and LOQ were calculated using linear calibration plots of the analytes developed in the standard concentration range of 2.0 µg/L-2.0 mg/L. CONCLUSIONS: Enhancement in detection power of the analytes recorded by the optimized method with respect to direct GC-MS determination (based on LOD values) was in the range of 3.6 and 539 folds. Spiked recovery experiments for municipal, medical, and synthetic wastewater samples yielded low recovery results when calculated against aqueous standard solutions. Matrix matched calibration standards were used to mitigate interferences from the waste samples and the percent recoveries obtained were close to 100%. This established accuracy and applicability of the developed method. HIGHLIGHTS: The detection limits were found between 0.50 ng/mL and 37 ng/mL. An accurate, simple and sensitive analytical method was developed for the analytes.

Determination of copper in traditional coffee pot water samples by flame atomic absorption spectrometry and matrix matching calibration strategy after switchable solvent based liquid-phase microextraction.

Traditional copper coffee pots are widely used in these modern times and daily consumption of coffee brewed in overused/old pots increases the risk of copper ingestion. This study employed a green switchable solvent-based liquid-phase microextraction (SS-LPME) method to isolate and preconcentrate copper from water boiled in coffee pots. Copper was determined by a flame atomic absorption spectrometry (FAAS) system coupled with a slotted quartz tube (SQT). 1,5-Diphenylcarbazone was added to aqueous samples to form a complex with copper before the extraction step. Box-Behnken experimental design was applied to select optimum conditions of the extraction method that were used to validate the analytical method. The limits of quantification and detection of the optimized SS-LPME-SQT-FAAS method were determined as 9.1 and 2.7 µg/L, respectively. Water samples boiled in traditional coffee pots were spiked at different concentrations and analyzed to ascertain the method's accuracy and applicability to real samples. Satisfactory recovery results obtained in the range of 92-107% established good accuracy, and percent relative standard deviations lower than 8.0% also proved high precision.

Experimental Design of Vortex Assisted Switchable Solvent Homogeneous Liquid-Liquid Microextraction for Simultaneous Determination of Four Pesticides in Wastewater.

BACKGROUND: Pesticides are chemicals used mainly to protect plant crops in order to increase their production efficiency and quality. OBJECTIVE: Switchable-solvent homogeneous liquid-liquid microextraction was optimized using a Box-Behnken experimental design and validated on a gas chromatography mass spectrometry system for the determination of analytes. METHOD: The significance of independent variables (switchable solvent volume, sodium hydroxide volume, and vortex period) and their interactions were evaluated by analysis of variance at 95% confidence limits (α = 0.05). RESULTS: The LOD and LOQ ranges of the analytes were found to be 0.42-1.90 µg/L and 1.36-6.33 µg/L, respectively. Percentage recovery results were found to be in the range of 87-113% in spiking experiments. CONCLUSIONS: A simple, efficient, and accurate analytical method was developed for the simultaneous determination of the selected pesticides. Highlights: Matrix matching was used to enhance quantification accuracy for real samples. HIGHLIGHTS: Matrix matching was used to enhance quantification accuracy for real samples.

Accurate and simple determination of oxcarbazepine in human plasma and urine samples using switchable-hydrophilicity solvent in GC-MS.

This work presents a sensitive and rapid analytical method for the determination of oxcarbazepine in human plasma and urine samples. A vortex-assisted switchable hydrophilicity solvent-based liquid phase microextraction (VA-SHS-LPME) was used to preconcentrate oxcarbazepine from the samples before the determination by gas chromatography mass spectrometry. The switchable hydrophilicity solvent was synthesized by protonating N,N-dimethylbenzylamine with carbon dioxide to make it totally miscible with an equivalent volume of water. Parameters of the VA-SHS-LPME method including volume of switchable hydrophilicity solvent, concentration/volume of sodium hydroxide and vortex period were systematically optimized. Under the optimum conditions, good linearity ranging from 27.03 to 353.47 µg/kg was obtained for the analyte. Limit of detection and quantitation values were found to be 6.2 and 21 µg/kg (mass base), respectively. The relative standard deviation was calculated as 6.9% for six replicate measurements of the lowest concentration of the calibration plot. Satisfactory recovery results were calculated in the range of 97-100% for human plasma and urine samples spiked at five different concentrations.

Development of a sensitive and accurate method for the simultaneous determination of selected insecticides and herbicide in tap water and wastewater samples using vortex-assisted switchable solvent-based liquid-phase microextraction prior to determination by gas chromatography-mass spectrometry.

In this study, a switchable solvent-based liquid-phase microextraction method was developed to preconcentrate selected pesticides from tap water and wastewater matrices for determination by gas chromatography-mass spectrometry. A thorough optimization process was performed for prominent extraction parameters such as switchable solvent amount, concentration/amount of sodium hydroxide, salt type and mixing period. Optimum parameters obtained at the end of the optimization process were applied to aqueous standard solutions to validate the method. The linear dynamic ranges of all four analytes were appreciably wide with coefficient of determination values greater than 0.9997. The limits of detection and quantification (LOD and LOQ) were calculated for the analytes in the ranges of 0.38-2.0 ng/mL and 1.3-6.5 ng/mL, respectively. Spiked recovery experiments were used to validate the accuracy of the developed method and to determine the performance of the method in different sample matrices. Tap water, municipal wastewater and medical wastewater were spiked at three different concentrations and analyzed under the method's optimum conditions. The percent recovery results calculated for the samples were in the range of 79-107%, and this validated the method's accuracy and applicability to complex matrices such as municipal and medical wastewater samples.

Combination of vortex assisted binary solvent microextraction and QuEChERS for the determination of prothiofos, oxadiargyl, and gamma-cyhalothrin in water and pineapple samples by gas chromatography mass spectrometry.

An accurate and sensitive dispersive liquid-liquid microextraction method based on binary solvents was used to enrich prothiofos, oxadiargyl, and gamma-cyhalothrin for quantification by GC-MS. The combination of two extraction solvents (binary mixture) resulted in higher extraction efficiencies compared to the single solvent extraction systems. Parameters of the binary extraction method where optimized to enhance the extraction output of the analytes. The limits of detection calculated for the analytes ranged between 0.59 and 1.6 ng/mL. Linear calibration plots of the analytes covered wide concentration ranges with R2 values greater than 0.9996 and percent relative standard deviation lower than 10%. Spiked recovery experiments were performed well and wastewater at two different concentrations and satisfactory results (89-104%) were obtained. The binary solvent microextraction method was combined with QuEChERS to quantify the analytes in pineapple matrix, using matrix matching method to enhance the accuracy of the method to almost 100%.

A new derivatization method for the determination of propineb in black tea and infant formula samples using dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

A novel derivatization method for the determination of propineb by gas chromatography-mass spectrometry (GC-MS) was developed in this study. This was achieved by isothiocyanate derivatization of the analyte by potassium persulfate and potassium carbonate in water medium. Dispersive liquid-liquid microextraction (DLLME) was employed to isolate and preconcentrate the derivatized analyte into an organic phase. All method parameters including concentration/volume of potassium persulfate and potassium carbonate salts, type/period of mixing for derivatization reaction and microextraction process were systematically optimized to lower the detection limit. Under the optimum experimental conditions, the limit of detection (LOD) and limit of quantitation (LOQ) values were calculated as 0.15 mg/kg and 0.52 mg/kg, respectively. The developed method was checked for its accuracy and applicability by spiking black tea and infant formula samples, and the respective percent recovery results were found to be in the range of 99-102% and 98-103%, respectively.