Development of a green miniaturized quick, easy, cheap, effective, rugged, and safe approach in tandem with temperature-assisted solidification of floating menthol droplet for analysis of multiclass pesticide residues in milk.

A new green miniaturized quick, easy, cheap, effective, rugged, and safe approach was developed and used for the extraction of multiclass 16 pesticides in milk before gas chromatography analysis. The miniaturization of method reduced the consumption of chemical reagents and samples. Magnetic three-dimensional graphene was used as sorbent in the clean-up step. Choline chloride:lactic acid (1:2) natural deep eutectic solvent was used as desorption solvent. Temperature-assisted solidification of floating menthol drop was executed for preconcentration of analytes. The method parameters including sorbent, desorption solvent, sorption and desorption times, menthol amount, pH, and ionic strength were optimized. The limit of quantification and linear range were 0.03-0.38 and 0.03-250 µg/kg, respectively. The accuracy was assessed by recovery evaluation at the spike levels of 50 and 100 µg/kg, in the range of 61-119%, with relative standard deviations within 2.1-18.2%. The method was applied to the analysis of pasteurized low and high-fat bovine milk, and various pesticide residues were detected in the concentrations range of 1.24-4.68 µg/kg. Finally, the greenness of the procedure was evaluated using the Analytical Eco-Scale. This work represents the first application of hybrid miniaturized extraction/preconcentration using a natural deep eutectic solvent and menthol to analyze pesticides.

Natural thymol-based ternary deep eutectic solvents: Application in air-bubble assisted-dispersive liquid-liquid microextraction for the analysis of tetracyclines in water.

Four new thymol-based ternary deep eutectic solvents were prepared and evaluated as the extractive phase in air-bubbles assisted dispersive liquid-liquid microextraction for extraction of tetracycline, doxycycline, and oxytetracycline from the water before high-performance liquid chromatography. The maximum extraction efficiencies were obtained using 400 µL of [choline chloride]:[thymol]:[nonanoic acid] in the molar ratio of 1:2:2 at pH = 5. The solvent was characterized by FTIR and NMR spectroscopy. The hydrophobicity of the deep eutectic solvent and its effect on the pH of water samples after mixing was also studied. Besides, the extraction efficiency of the ternary deep eutectic solvent was compared with that of two binary thymol-based deep eutectic solvents, including [choline chloride]:[thymol] and [thymol]:[nonanoic acid] at the same conditions. Under optimal conditions, limits of detection and quantification were 1.2-8.0 and 3.8-26.6 µg/L, respectively. The linear ranges were 18.2-500 µg/L for oxytetracycline, 26.6-500 µg/L for tetracycline, and 3.8-500 µg/L for doxycycline with the determination coefficients > 0.9912. Intra- and inter-day relative standard deviations were 1.2-3.8 and 7.7-11.2%, respectively. The developed method was applied to the analysis of tetracyclines in unspiked and spiked environmental water samples, and the obtained recoveries were 74.5-95.4% with relative standard deviations of 1.2-4.0%.

Deep eutectic solvent-based clean-up/vortex-assisted emulsification liquid-liquid microextraction: Application for multi-residue analysis of 16 pesticides in olive oils.

A new hydrophobic deep eutectic solvent (DES) composed of thymol and vanillin (1:1) was prepared and used as the extraction solvent in vortex-assisted emulsification liquid-liquid microextraction of 16 pesticides in olive oil before GC-µECD analysis. Due to the complexity of oil samples, a DES-based liquid-liquid solvent system (n-hexane/acetonitrile/DES) was developed to achieve an effective clean-up. Among the four examined hydrophilic DESs, [choline chloride]:[urea] led to improved sensitivity, and clean chromatograms with low noise and drift from the sample matrix. Besides, the effect of the significant factors such as extraction solvent volume, pH, ionic strength, and vortex time was investigated. At the optimized conditions, the validation parameters such as linear range 0.04-250 µg kg-1, the limits of detection of 0.01-0.08 µg kg-1, intra-day, and inter-day relative standard deviations (RSDs) < 6.8 and < 9.7%, were obtained. This method was followed by GC-µECD and applied to determine pesticides in five olive oil samples. The relative recoveries were in the range of 63.1-119.4%.

Electrochemically controlled solid phase microextraction based on a conductive polyaniline-graphene oxide nanocomposite for extraction of tetracyclines in milk and water.

BACKGROUND: Tetracycline antibiotics are employed for human and animal health and for speeding up growth rates. However, their presence in food products and environmental waters has been a concern for some years. Therefore, a variety of sample preparation methods have been developed for the analysis of tetracycline residues in these matrices. RESULTS: An electrochemically controlled solid phase microextraction based on a modified copper electrode with polyaniline/graphene oxide (PANI/GO) conductive nanocomposite was developed for the extraction of oxytetracycline, tetracycline and doxycycline before high-performance liquid chromatography-UV analysis. PANI/GO was synthesized by in situ chemical oxidative polymerization, characterized by scanning electron microscopy and Fourier-transform infrared spectroscopy, and bound on the electrode using high purity conductive double-sided adhesive carbon glue. The significant factors affecting the performance of microextraction were investigated and optimized. Under the optimized conditions [sample, 15 mL; sorbent, 10 mg; pH, 3.0; electroextraction voltage, -0.9 V; electroextraction time, 20 min; eluent (MeOH/NH3 ), 500 µL; and desorption time, 5 min], the limits of detection for target analytes were in the ranges 0.32-1.01 and 2.42-7.59 µg L-1 in water and milk samples, respectively. The linear ranges were 1.06-750 µg L-1 for water and 8.05-750 µg L-1 for milk samples. The intra-day and inter-day precisions were 2.32-3.80 and 3.29-4.25, respectively. The method was applied to the determination of analytes in milk and water samples with different fat contents, and the recoveries were obtained in the range 71-104%. CONCLUSION: The developed electro-microextraction method provides a facile, rapid, cost-effective, sensitive and efficient promising procedure for the extraction of antibiotics in complex matrices. © 2020 Society of Chemical Industry.

Nanosorbent-based solid phase microextraction techniques for the monitoring of emerging organic contaminants in water and wastewater samples.

This review (including 127 refs) summarizes applications of nanosorbent-based solid phase microextraction (SPME) for the cleanup, extraction, and quantification of Emerging Organic Contaminants (EOCs). SPME is the most widely used technique for the analysis of EOCs from water samples. The selection of sorbent material plays a key role in SPME applications. Here, we have collected information about recent developments in the application of nanosorbents in the SPME technique used for the extraction of EOCs from water and wastewater samples. In this review, the preparation, properties, advantages, and limitations of nanosorbents used in SPME applications are evaluated and discussed. Besides, the applications of these nanosorbents in SPME-based extraction techniques and their analytical characteristics for the determination of EOCs are reviewed. Graphical abstract.

Hyphenated dispersive solid- and liquid-phase microextraction technique based on a hydrophobic deep eutectic solvent: application for trace analysis of pesticides in fruit juices.

BACKGROUND: Pesticides are extensively used worldwide to control plant pathogens and prevent agricultural product damage. However, they can pollute the environment and endanger human health. So far, a variety of sample preparation methods have been developed for the analysis of pesticide residues. RESULTS: A hyphenated solid-liquid microextraction method based on a new adsorbent of magnetic graphene oxide functionalized by (3-glycidyloxypropyl)trimethoxysilane and a deep eutectic solvent (choline chloride/4-chlorophenol (1:2)) was developed for extraction/preconcentration of trace levels of pesticides. The sorbent was characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, and vibrating sample magnetometry. In-syringe magnetic dispersive solid-phase extraction in tandem with dispersive liquid-liquid microextraction followed by gas chromatography was applied for the analysis of the selected pesticides. The main parameters governing sample preparation efficiency, including adsorbent dosage, desorption conditions, pH, extraction time, deep eutectic solvent volume, and salt concentration, were investigated. The linear ranges were 0.024-500 µg L-1 with 0.9971-0.9999 linearity factor (R2 ). The limits of detection and quantification were 0.006-0.038 and 0.024-0.126 µg L-1 , respectively. The relative standard deviations were 0.5-4.2% for intra-day analysis and 2.7-4.6% for inter-day analysis. Enrichment factors were in the range 210-540. CONCLUSIONS: The method was successfully applied for the determination of malathion, heptachlor epoxide, endrin, dichlorodiphenyltrichloroethane, azinphos ethyl, cypermethrin, and deltamethrin in fruit juice samples (apple, pineapple, cherry, peach, and red and green grape juices) and the recoveries were within the range 71-115%. © 2020 Society of Chemical Industry.

Integrated in-syringe magnetic sheet solid-phase extraction and dispersive liquid-liquid microextraction for determination of aflatoxins in fresh and moldy breads.

BACKGROUND: Magnetic three-dimensional graphene-based nanoadsorbents have unique characteristics such as large surface area, good thermal and chemical stability, and high adsorption capacity that make them efficient materials in sorbent-based extraction techniques. In this study, four aflatoxins (AFs) were analyzed in bread samples using magnetic three-dimensional graphene as the adsorbent phase in dispersive micro solid-phase extraction. RESULTS AND CONCLUSIONS: In-syringe magnetic sheet solid-phase extraction based on magnetic three-dimensional graphene in tandem with dispersive liquid-liquid microextraction was used for the extraction and preconcentration of the target AFs. The effect of significant parameters of the method was investigated and the optimum conditions were determined as follows: adsorbent dosage, 20 mg; desorption/disperser solvent (methanol) volume, 700 µL; desorption solvent flow rate, 0.7 mL min-1 ; pH, neutral; salt (NaCl) concentration, 10% (w/v); extraction solvent (chloroform) volume, 250 µL; and centrifugation rate (and time), 4000 rpm (5 min). The limits of detection and quantification were in the ranges 0.043-0.083 and 0.14-0.28 µg kg-1 , respectively. The extraction method was followed by the HPLC technique with fluorescence detection and applied to the determination of the AFs in four different Iranian fresh and moldy bread samples. The relative recoveries were in the range 84-107% with relative standard deviations of 3.9-8.6%. © 2019 Society of Chemical Industry.

Electrospun polymer composite nanofiber-based in-syringe solid phase extraction in tandem with dispersive liquid-liquid microextraction coupled with HPLC-FD for determination of aflatoxins in soybean.

A fast method based on in-syringe solid phase extraction combined with dispersive liquid-liquid microextraction was developed for extraction of aflatoxins prior to HPLC-FD. Electrospun polyurethane nanofibers doped with graphene oxide were collected on a thin metal net sheet without using a binder, placed into a filter holder between filter papers on a syringe tip and used as an efficient adsorbent for the first time. The major parameters affecting whole extraction efficiency were investigated and optimized. Under the optimum conditions, the limits of detection and the limits of quantification were in the range of 0.09-0.15 and 0.3-0.5 µg kg-1, respectively. The linear dynamic range was 0.3-1000 µg kg-1 with determination coefficients of 0.9946-0.9965. The inter- and intra-day precisions were lower than 4.3 and 7.2%, respectively. The method was successfully applied for the determination of aflatoxins B1, B2, G1, and G2 in soybeans and satisfactory relative recoveries of 76-101% were achieved.

Applications of three-dimensional graphenes for preconcentration, extraction, and sorption of chemical species: a review.

This review (with 115 refs) summarizes applications of 3-dimensional graphene (3DGs) and its derivatives in the fields of preconcentration, extraction, and sorption. Following an introduction into the field (including a definition of the materials treated here), the properties and synthetic strategies for 3DGs are described. The next section covers applications of 3DG-based adsorbents in solid phase extraction of organic species including drugs, phthalate esters, chlorophenols, aflatoxins, insecticides, and pesticides. Another section treats applications of 3DGs in solid phase microextraction of species such as polycyclic aromatic hydrocarbons, alcohols, and pesticides. We also describe how the efficiency of assays may be improved by using these materials as a sorbent. A final section covers conclusions and perspectives. Graphical abstract Graphical abstract contains poor quality and small text inside the artwork. Please do not re-use the file that we have rejected or attempt to increase its resolution and re-save. It is originally poor, therefore, increasing the resolution will not solve the quality problem. We suggest that you provide us the original format. We prefer replacement figures containing vector/editable objects rather than embedded images. Preferred file formats are eps, ai, tiff and pdf.Tiff file of graphical abstract was attached. Schematic presentation of synthesis of three-dimensional graphene (3DG) from two-dimensional graphene (2DG) with self-assembly, template-assisted and direct deposition methods. Application of 3DG-based nanoadsorbents in direct immersion-solid phase microextraction (DI-SPME), headspace-SPME (HS-SPME), magnetic-solid phase extraction (Magnetic-SPE), dispersive-SPE, and magnetic sheet-SPE.

Graphene-coated magnetic-sheet solid-phase extraction followed by high-performance liquid chromatography with fluorescence detection for the determination of aflatoxins B1 , B2 , G1 , and G2 in soy-based samples.

A new method named graphene-coated magnetic-sheet solid-phase extraction based on a magnetic three-dimensional graphene sorbent was developed for the extraction of aflatoxins prior to high-performance liquid chromatography with fluorescence detection. The use of a perforated magnetic-sheet for fixing the magnetic nanoparticles is a new feature of the method. Hence, the adsorbent particles can be separated from sample solution without using an external magnetic field. This made the procedure very simple and easy to operate so that all steps of the extraction process (sample loading, washing, and desorption) were carried out continuously using two lab-made syringe pumps. The factors affecting the performance of extraction procedure such as the extraction solvent, adsorbent dose, sample loading flow rate, ionic strength, pH, and desorption parameters were investigated and optimized. Under the optimal conditions, the obtained enrichment factors and limits of detection were in the range of 205-236 and 0.09-0.15 µg/kg, respectively. The relative standard deviations were <3.4 and 7.5% for the intraday (n = 6) and interday (n = 4) precisions, respectively. The developed method was successfully applied to determine aflatoxins B1 , B2 , G1 , and G2 in different soy-based food samples.

Enhanced removal of phosphate and nitrate ions from aqueous media using nanosized lanthanum hydrous doped on magnetic graphene nanocomposite.

A novel nanocomposite adsorbent based on nanosized lanthanum hydroxide doped onto magnetic reduced graphene oxide (MG@La) was synthesized and used for removal of phosphate and nitrate ions from river and sewage media. The composition, surface properties and morphology of the as prepared adsorbent were studied using Fourier transform-infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and field emission scanning electron microscopy (FE-SEM). The influence of main parameters on the efficiency of removal process including adsorbent dosage, salt addition, solution pH, contact time, and concentration of the analytes were thoroughly investigated. The validity of the experimental process was checked by the adsorption isotherm and adsorption kinetics models. The obtained data were well fitted to Langmuir isotherm and pseudo-second-order kinetic models. The developed adsorbent showed high adsorption capacities of 116.28 mg g-1 and 138.88 mg g-1 for phosphate and nitrate ions, respectively. Additionally, Langmuir isotherm and free energy were suggested monolayer pattern and physisorption mechanism for adsorption process, respectively. Finally, the field application of newly synthesized MG@La provided high removal efficiencies (74%-90%) for phosphate and nitrate ions in real river and sewage water samples.

Application of elevated temperature-dispersive liquid-liquid microextraction for determination of organophosphorus pesticides residues in aqueous samples followed by gas chromatography-flame ionization detection.

In the present study, an elevated temperature, dispersive, liquid-liquid microextraction/gas chromatography-flame ionization detection was investigated for the determination, pre-concentration, and extraction of six organophosphorus pesticides (malathion, phosalone, dichlorvos, diazinon, profenofos, and chlorpyrifos) residues in fruit juice and aqueous samples. A mixture of 1,2-dibromoethane (extraction solvent) and dimethyl sulfoxide (disperser solvent) was injected rapidly into the sample solution heated at an elevated temperature. Analytical parameters, including enrichment factors (1600-2075), linearity (r>0.994), limits of detection (0.82-2.72ngmL(-1)) and quantification (2.60-7.36ngmL(-1)), relative standard deviations (<7%) and extraction recoveries (64-83%), showed the high efficiency of the method developed for analysis of the target analytes. The proposed procedure was used effectively to analyse selected analytes in river water and fruit juice, and diazinon was found at ngmL(-1) concentrations in apple juice.

Determination of three antidepressants in urine using simultaneous derivatization and temperature-assisted dispersive liquid-liquid microextraction followed by gas chromatography-flame ionization detection.

This paper presents a fast and simple method for the extraction, preconcentration and determination of fluvoxamine, nortriptyline and maprotiline in urine using simultaneous derivatization and temperature-assisted dispersive liquid-liquid microextraction (TA-DLLME) followed by gas chromatography-flame ionization detection (GC-FID). An appropriate mixture of dimethylformamide (disperser solvent), 1,1,2,2-tetrachloroethane (extraction solvent) and acetic anhydride (derivatization agent) was rapidly injected into the heated sample. Then the solution was cooled to room temperature and cloudy solution formed was centrifuged. Finally a portion of the sedimented phase was injected into the GC-FID. The effect of several factors affecting the performance of the method, including the selection of suitable extraction and disperser solvents and their volumes, volume of derivatization agent, temperature, salt addition, pH and centrifugation time and speed were investigated and optimized. Figures of merit of the proposed method, such as linearity (r(2) > 0.993), enrichment factors (820-1070), limits of detection (2-4 ng mL(-1)) and quantification (8-12 ng mL(-1)), and relative standard deviations (3-6%) for both intraday and interday precisions (concentration = 50 ng mL(-1)) were satisfactory for determination of the selected antidepressants. Finally the method was successfully applied to determine the target pharmaceuticals in urine.

Determination of amantadine in biological fluids using simultaneous derivatization and dispersive liquid-liquid microextraction followed by gas chromatography-flame ionization detection.

A one-step derivatization and microextraction technique for the determination of amantadine in the human plasma and urine samples is presented. An appropriate mixture of methanol (disperser solvent), 1,2-dibromoethane (extraction solvent), and butylchloroformate (derivatization agent) is rapidly injected into samples. After centrifuging, the sedimented phase is analyzed by gas chromatography-flame ionization detection (GC-FID). The kind of extraction and disperser solvents and their volumes, amount of derivatization agent and reaction/extraction time which are effective in derivatization/dispersive liquid-liquid microextraction (DLLME) procedure are optimized. Under the optimal conditions, the enrichment factor (EF) of the target analyte was obtained to be 408 and 420, and limit of detection (LOD) 4.2 and 2.7ngmL(-1), in plasma and urine respectively. The linear range is 14-5000 and 8.7-5000ng/mL for plasma and urine, respectively (squared correlation coefficient≥0.990). The relative recoveries obtained for the spiked plasma and urine samples are between 72% and 93%. Moreover, the inter- and intra-day precisions are acceptable at all spiked concentrations (relative standard deviation <7%). Finally the method was successfully applied to determine amantadine in biological samples.

Simultaneous derivatization and air-assisted liquid-liquid microextraction of some aliphatic amines in different aqueous samples followed by gas chromatography-flame ionization detection.

The paper presents a new method based on simultaneous derivatization and air-assisted liquid-liquid microextraction (AALLME) for the extraction and preconcentration of some aliphatic amines prior to gas chromatography-flame ionization detection (GC-FID). Primary aliphatic amines are derivatized and extracted simultaneously by a fast reaction with butylchloroformate (derivatization agent/extraction solvent) under mild conditions. The mixture of butylchloroformate and aqueous sample solution is rapidly sucked into a 10-mL glass syringe and then is injected into a test tube with conical bottom and the procedure is repeated seven times. After centrifuging the resulted cloudy solution, the derivatized analytes in the sedimented phase are determined by GC-FID. The influence of main factors on the efficiency of derivatization/extraction procedure is studied. Under the optimal conditions, the enrichment factors (EFs) for aliphatic amines are obtained in the range of 248-360 and limits of detection (LODs) are between 0.30 and 2.6 µg L(-1). The obtained extraction recoveries ranged from 50 to 72% and the relative standard deviation (RSD) was less than 4.8% for intra-day (n=6) and inter-days (n=4) precision. The method is successfully applied to determine some aliphatic amines in environmental water samples.

Simultaneous derivatization and dispersive liquid-liquid microextraction of anilines in different samples followed by gas chromatography-flame ionization detection.

A new method based on simultaneous derivatization and dispersive liquid-liquid microextraction in one step is developed for determination of five anilines in different aqueous samples. In this method, acetonitrile containing microlitre-level of butylchloroformate was rapidly injected into aqueous sample by a syringe. After centrifugation of the cloudy solution, the fine droplets of the butylchloroformate containing the derivatized analytes were sedimented in the bottom of the conical test tube. Then, 0.5 µL of the settled phase was injected into gas chromatography-flame ionization detector. Under optimum conditions the enrichment factors, extraction recoveries and enhancement factors were high and ranged between 197 and 298, 47 and 69%, and 4.7 and 6.2, respectively. Linearity was observed in the range of 10-10,000 µg L(-1) (except for 4-chloroaniline), and the relative standard deviations (RSD %) were lower than 5.2% (n=6). The limits of detection of the six anilines ranged from 1 to 3 µg L(-1). Different aqueous samples including tap, river and well waters as well as wastewaters were successfully analyzed. In this method the extraction solvent and derivatization agent are the same and the derivatization reaction was carried out under mild conditions. This method has several advantages over other reported techniques, being very simple, rapid and less hazardous for the environment.

Coupling stir bar sorptive extraction-dispersive liquid-liquid microextraction for preconcentration of triazole pesticides from aqueous samples followed by GC-FID and GC-MS determinations.

Stir bar sorptive extraction (SBSE) combined with dispersive liquid-liquid microextraction (DLLME) has been developed as a new approach for the extraction of six triazole pesticides (penconazole, hexaconazole, diniconazole, tebuconazole, triticonazole and difenconazole) in aqueous samples prior to GC-flame ionization detection (GC-FID). A series of parameters that affect the performance of both steps were thoroughly investigated. Under optimized conditions, aqueous sample was stirred using a stir bar coated with octadecylsilane (ODS) and then target compounds on the sorbent (stir bar) were desorbed with methanol. The extract was mixed with 25 microL of 1,1,2,2-tetrachloroethane and the mixture was rapidly injected into sodium chloride solution 30% w/v. After centrifugation, an aliquot of the settled organic phase was analyzed by GC-FID. The methodology showed broad linear ranges for the six triazole pesticides studied, with correlation coefficients higher than 0.993, lower LODs and LOQs between 0.53-24.0 and 1.08-80.0 ng/mL, respectively, and suitable precision (RSD < 5.2%). Moreover, the developed methodology was applied for the determination of target analytes in several samples, including tap, river and well waters, wastewater (before and after purification), and grape and apple juices. Also, the presented SBSE-DLLME procedure followed by GC-MS determination was performed on purified wastewater. Penconazole, hexaconazole and diniconazole were detected in the purified wastewater that confirmed the obtained results by GC-FID determination. In short, by coupling SBSE with DLLME, advantages of two methods are combined to enhance the selectivity and sensitivity of the method. This method showed higher enrichment factors (282-1792) when compared with conventional methods of sample preparation to screen pesticides in aqueous samples.