Ionic Liquid-Dispersive Micro-Extraction and Detection by High Performance Liquid Chromatography-Mass Spectrometry for Antifouling Biocides in Water.

A simple analytical method was developed and evaluated for the determination of two antifouling biocides using an ionic liquid-dispersive liquid-liquid micro-extraction (IL-DLLME) and a high-performance liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) analysis. Irgarol 1051 and Sea-Nine 211 were extracted from deionized water, lake water, and seawater using IL 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIm][PF6]) and ethyl acetate as the extraction solvent and the dispersion solvent. Several factors were considered, including the type and volume of extraction and dispersive solvent, IL amount, sample pH, salt effect, and cooling temperature. The developed method resulted in a recovery range of 78.7-90.3%, with a relative standard deviation (RSD, n = 3) less than 7.5%. The analytes were enriched greater than 40-fold, and the limits of detection (LOD) for two antifouling biocides were 0.01-0.1 µg L-1. The method was effectively applied for the analysis of real samples of freshwater as well as samples of seawater.

Magnetic dispersive solid-phase extraction of some pesticides from fruit juices using monodisperse nanosorbent combined with dispersive liquid-liquid micro-extraction.

In this study, the new synthesized magnetic nanoparticles based on amorphous carbon have been used as a sorbent in magnetic dispersive solid-phase extraction prior to dispersive liquid-liquid micro-extraction. The developed method was applied for analysis of ten pesticides from different fruit juice samples by gas chromatography-flame ionization detection. In this work, a few mg of the sorbent is added into an aqueous solution containing the analytes. Adsorption and desorption of the compounds of interest are accelerated by vortexing and sonication, respectively. To achieve high enrichment factors, a suitable organic solvent (iso-propanol) is used to elute the target analytes from the nanosorbent. The obtained iso-propanol is phased and 1,1,2-trichloroethane are employed as the disperser and extraction solvents, respectively, in the following micro-extraction procedure. The synthesized magnetic nanoparticles were characterized by scanning electron microscope, X-ray diffraction, vibrating sample magnetometer, and Fourier-transform infrared spectrophotometer. To achieve the high extraction efficiency and optimum conditions, all parameters that could affect the extraction yield were investigated. Under optimum conditions, the method had broad linear ranges with a proper linearity (r2 ≥ 0.9987). Limits of detection and quantification for analysis of the selected pesticides were found in the ranges of 0.5-1.0 and 1.7-3.3 µg L-1, respectively. High enrichment factors and extraction recoveries were obtained in the ranges of 321-438 and 64-88%, respectively. To evaluate repeatability of the method, it was performed on two sets of standard solutions at the concentrations of 10 and 50 µg L-1 (each analyte). Relative standard deviations varied in the ranges of 2-6% and 4-7% for intra- (n = 6) and inter-day (n = 5) precisions, respectively.

Flow-based determination of lead exploiting in-syringe dispersive liquid-liquid micro-extraction in xylene and integrated spectrophotometric detection.

A lab-in-syringe flow system exploiting dispersive liquid-liquid micro-extraction in a solvent lighter than water is proposed for the spectrophotometric determination of lead in industrial residual waters. The steps inherent to both liquid-liquid extraction and monitoring of the formed compound are in-syringe carried out. The classical carbon tetrachloride is not used as the extracting solvent, as it does not present the friendly characteristics inherent to the Green Analytical Chemistry. Aiming at a cleaner alternative for this determination, xylene is selected. Enrichment factor, linear dynamic range, detection limit, sample throughput and residue volume inherent to the proposed procedure were estimated as 36, 50.0-250 µg L-1, 9.0 µg L-1, 13 h-1, and 2.0 mL, respectively.

Deep eutectic solvent-based dispersive liquid-liquid micro-extraction of pesticides in food samples.

Deep eutectic solvents are versatile, green and new generation solvents that can be used during dispersive liquid-liquid micro-extraction techniques for pesticides. They have tunable physico-chemical properties that can be easily changed by varying the ratios of hydrogen bond donors and hydrogen bond acceptors in their structures. Deep eutectic solvents are non-flammable, chemically and thermally stable solvents with low vapour pressure. Thus, they have characteristics that are similar to those of ionic liquids. However, they have simpler synthetic procedures, less expensive and are more biodegradable than ionic liquids. One of the limitations of deep eutectic solvents is their toxicity to the environment but they are less toxic than ionic liquids. This paper gives a focused and comprehensive recent review on the applications of deep eutectic solvents during dispersive liquid-liquid micro-extraction of pesticides in food samples for the period starting from 2016 to 2020. Emphasis was placed on the modifications done to the deep eutectic solvent-based dispersive liquid-liquid micro-extraction techniques in order to enhance their greenness during pesticide pre-concentration in food samples. In addition, hyphenated dispersive liquid-liquid micro-extraction techniques were also reviewed and lastly, the paper outlined the challenges associated with the use of DESs during the DLLME techniques.

A Simple Method for the Determination of Triazines from Seawater in Accordance with the Directive 2013/39/EU.

Since the Directive 2013/39/EU included terbutryn to the list of priority substances of all water bodies, a previous method based on dispersive liquid-liquid micro-extraction (DLLME) for the determination of triazines in seawater has been modified. The main change consisted on the use of tandem mass spectrometry instead of diode array as detection technique. Due to the higher sensitivity of mass detector, sample volume was reduced and extraction solvent volume was optimized. The optimum extraction conditions were 5 mL of sample, 50 µL of 1-octanol and an agitation step instead of disperser solvent. The obtained analytical recoveries (73%-101% with relative standard deviations below 4%) meeting the requirements. The limits of quantification (between 0.016 and 0.021 µg L-1) were more than 10 times lower than the limit set by the European Directive 2013/39/EU for terbutryn (0.34 µg L-1). The proposed method was applied to the determination of the target compounds in seawater samples from A Coruña (Galicia, NW of Spain).

dLLME-µSPE extraction coupled to HPLC-ESI-MS/MS for the determination of F2α-IsoPs in human urine.

Oxidative stress is a pathological condition characterized by an imbalance between body's antioxidant defenses and oxidizing agents, resulting in damage of endogenous molecules. These products can be used as markers of oxidative conditions; in particular, isoprostanes (IsoPs) come from the reaction of arachidonic acid with reactive oxygen species (ROS) and are currently defined as gold markers of oxidative stress in urine. Our main goal was the development of a reliable analytical method for the determination and quantification of the IsoPs in human urine by dispersive Liquid-Liquid Micro Extraction (dLLME) coupled with micro Solid Phase Extraction (µSPE) clean-up and HPLC-MS/MS analysis. The selected compounds are present in very small concentration in urine, furthermore, due to relevant matrix effect, they are challenging for ESI-MS/MS analysis. This approach provided selectivity and sensitivity for 8-isoprotaglandine F2α (8-iso-PGF2α), the "gold" OS marker, together with the main isomers. dLLME extraction allowed a significant enrichment factor and µSPE clean-up provided the removal of ion-suppressing compounds from the sample resulting in low matrix effect. The chromatographic separation was also challenging as the target compounds possess very similar chemical characteristics, so experimental conditions were carefully tuned. The reported method represents a useful tool for the detection of IsoPs in urine taking advantage of the combination of dLLME extraction and µSPE clean-up; overall recoveries were above 50 % and matrix effects were ≤15 %, with LOQs ranging between 0.020 and 0.060 ng mL-1. The procedure is easy to use and rapid allowing the removal of interfering compounds and matrix effect maintaining a highly sensitive determination.

Rapid analysis of short- and medium-chain chlorinated paraffins in wine by dispersive liquid-liquid micro-extraction coupled with high performance liquid chromatography-electrospray ionization quadrupole time-of-flight mass spectrometry.

This study established a simple and rapid method for determination of short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) by dispersive liquid-liquid micro-extraction coupled with high performance liquid chromatography-electrospray ionization quadrupole time-of-flight mass spectrometry (HPLC-ESI-Q-TOF/MS) in white and red wines. Affecting variables, including extraction solvent, salt concentration, ultrasound-vortex conditions and ethanol content, were evaluated. Under optimized conditions, the limit of detection (LODs) for SCCPs and MCCPs were in the range of 0.15-3.00 ng mL-1 and 0.08-2.50 ng mL-1, respectively. The spiked recoveries of SCCPs and MCCPs from white and red wine ranged from 63.2% to 127%. The method is precise with intra- and inter-day variations within 14.0% and 17.0%, respectively. SCCPs and MCCPs in wines from china varied widely, from

Detection of C60 in environmental water using dispersive liquid-liquid micro-extraction followed by high-performance liquid chromatography.

The wide application of fullerene C60 nanoparticles would inevitably lead to their release into the environment. In order to evaluate the environment risks of C60 and the subsequent effects on ecosystem health, a reliable quantitative methodology of C60 should be established. In this study, a rapid pretreatment method called low-density solvent-based dispersive liquid-liquid micro-extraction (DLLME) combined high-performance liquid chromatography-UV detector (HPLC-UV) was developed to detect C60 in environmental water. In this proposed method, toluene and methanol were chosen as the extraction solvent and the dispersive solvent, respectively. The optimized volume of extraction solvent and dispersive solvent were 100 µL and 10 µL, respectively. And the best shaking time was chosen as 10 min at room temperature for the optimal homogenization procedure for the extraction of C60 in water samples. The enrichment factor of 50 was obtained with 100 µL toluene, and the recoveries of C60 from various environmental samples were in the range of 81.4 ± 5.0-101.4 ± 6.2% at 1.25-5.00 µg/L spiked levels. The detection limits of C60 in tap water, surface water, living sewage and mining waste water were 0.19, 0.29, 0.34 and 0.22 µg/L, respectively. The low detection limit, good linear range and high recoveries of C60 in environmental water indicated that the proposed method could provide an efficient approach for the analysis and tracking of C60 in the environment.

One step rapid dispersive liquid-liquid micro-extraction with in-situ derivatization for determination of aflatoxins in vegetable oils based on high performance liquid chromatography fluorescence detection.

A rapid dispersive liquid-liquid micro-extraction (DLLME) with in-situ derivatization method for extraction and purification of aflatoxins (AFs) in vegetable oils was developed and evaluated. Oil extract, dichloromethane and trifluoroacetic acid were mixed and injected into water to form a cloudy solution. AFs in the oil were extracted into the numerous liquid droplets (with diameters from a few microns to dozens of microns) of extractant, where derivatization was carried out in situ. The proposed sample preparation method was coupled with high performance liquid chromatography with fluorescence detection (HPLC-FLD) for determination of four AFs in vegetable oils. The method showed excellent linearity in three orders of magnitude, good relative recoveries, good repeatability and high sensitivity with limits of detection in range of 0.005-0.03 ng/mL. The accuracy of the method was also verified by certified reference sample. Finally, different kinds of vegetable oils from the local supermarket were analyzed.

Study of the repartition of phthalate esters during distillation of wine for spirit production.

Due to health concerns and legal matters, an investigation to limit phthalates esters (PEAs) in spirits is necessary. A lab still was used to perform pilot distillations according to the official method for brandy production in order to explore the repartition into the distilled fractions of each PAE. The process was divided in two steps: a première chauffe and a bonne chauffe. The former step included the cut into heads, heart and tails, while the latter into heads, brandy, secondes, and tails. The behaviour of each PAE during distillation was affected by its own chemical nature. Dibutyl phthalate (DBP) was entirely carried over into the distillate, while bis(2-ethylhexyl) phthalate (DEHP) only partially, and diisononyl phthalate (DINP) accumulated in the stillage. During the bonne chauffe, DBP and DEHP accumulated in the secondes more than in the brandy. A rectification step of the secondes was demonstrated to considerably reduce PAEs concentration.

Determination of benzimidazoles in meat samples by capillary zone electrophoresis tandem mass spectrometry following dispersive liquid-liquid microextraction.

A novel method based on capillary zone electrophoresis-tandem mass spectrometry has been proposed and validated for the identification and simultaneous quantification of twelve benzimidazoles in meat samples. Electrophoretic separation was carried out using 500mM formic acid (pH 2.2) as background electrolyte and applying a voltage of 25kV at 25°C. In order to improve the sensitivity, stacking mode injection was applied, using as injection solvent a mixture of 30:70 acetonitrile/water at 50mbar for 75s. Sensitivity enhancement factors from 74 to 317 were obtained under these conditions. Detection using an ion trap as analyzer, operating in multiple reactions monitoring mode was employed. The main MS/MS parameters as well as the composition of the sheath liquid and other electrospray variables were optimized in order to obtain the highest sensitivity and precision in conjunction with an unequivocal identification. The method was applied to poultry and pork muscle samples. The deproteinization of samples and extraction of benzimidazoles was carried out with acetonitrile. MgSO4 and NaCl were added as salting-out agents. Subsequently, dispersive liquid-liquid microextraction was applied as clean up procedure. The organic layer (acetonitrile, used as dispersant) containing the benzimidazoles was mixed with the extractant (chloroform) and both were injected in water, producing a cloudy solution. Recoveries for fortified samples were higher than 70%, with relative standard deviations lower than 16% were obtained in all cases. The limits of detection were below 3µgkg-1, demonstrating the applicability of this fast, simple, and environmentally friendly method.

Determination of phthalate esters in distillates by ultrasound-vortex-assisted dispersive liquid-liquid micro-extraction (USVADLLME) coupled with gas chromatography/mass spectrometry.

A method for the extraction of phthalate esters (PAEs) by Ultrasound-Vortex-Assisted Dispersive Liquid-Liquid Micro-Extraction (USVADLLME) approach was optimised and applied for the first time to a historical series of brandies. These contaminants are widely spread in the environment as a consequence of about half century of use in different fields of applications. The concern about these substances and the recent legal restrictions of China in distillates import need a quick and sensitive method for their quantification. The proposed method, moreover, is environmentally oriented due to the disposal of micro-quantities of solvent required. In fact, sub-ppm-limits of detection were achieved with a solvent volume as low as 160µL. The analysed samples were within the legal limits, except for some very ancient brandies whose contamination was probably due to a PAEs concentration effect as a consequence of long ageing and for the use of plastic pipelines no more operative.

Salting-out homogenous extraction followed by ionic liquid/ionic liquid liquid-liquid micro-extraction for determination of sulfonamides in blood by high performance liquid chromatography.

Salting-out homogenous extraction followed by ionic liquid/ionic liquid dispersive liquid-liquid micro-extraction system was developed and applied to the extraction of sulfonamides in blood. High-performance liquid chromatography was applied to the determination of the analytes. The blood sample was centrifuged to obtain the serum. After the proteins in the serum were removed in the presence of acetonitrile, ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, dipotassium hydrogen phosphate, ionic liquid 1-Hexyl-3-methylimidazolium hexafluorophosphate were added into the resulting solution. After the resulting mixture was ultrasonically shaken and centrifuged, the precipitate was separated. The acetonitrile was added in the precipitate and the analytes were extracted into the acetonitrile phase. The parameters affecting the extraction efficiency, such as volume of ionic liquid, amount of dipotassium hydrogen phosphate, volume of dispersant, extraction time and temperature were investigated. The limits of detection of sulfamethizole (STZ), sulfachlorpyridazine (SCP), sulfamethoxazole (SMX) and Sulfisoxazole (SSZ) were 4.78, 3.99, 5.21 and 3.77µgL-1, respectively. When the present method was applied to the analysis of real blood samples, the recoveries of analytes ranged from 90.0% to 113.0% and relative standard deviations were lower than 7.2%.

Ultrasound-assisted extraction combined with reverse phase-dispersive liquid-liquid micro extraction as a new approach for preconcentration and spectrophotometric determination of total phenol in marine sediments of Chabahar Bay.

In this study, Reverse phase dispersive liquid-liquid micro extraction (RP-DLLME) technique have been successfully developed to preconcentrate trace amount of phenol from sediment samples as a prior step to its derivatization with 4-aminoantipyrine and enhanced determination by UV-Vis spectrophotometry after primary ultrasonic extraction. In this procedure, 50µL 0.7M NaOH solution was chosen as extraction solvent and other factors including pH, extraction time, concentration of 4-aminoantipyrine, type and volume of dispersive solvents were optimized. Under selected conditions, the limit of detection, the linearity range, relative standard deviation and enrichment factor of method were obtained 15µg·kg(-1), 50-1800µg·kg(-1), 4.8% (n=10) and 33, respectively. Finally, using the high sensitivity, low organic solvent consumption and waste generation method, total phenol content in marine sediments from several locations in Chabahar Bay (southeast Iran) was estimated at 55.8-73.2µg·kg(-1).

Sensitive spectrophotometric determination of Co(II) using dispersive liquid-liquid micro-extraction method in soil samples.

Analytical performance of conventional spectrophotometer was developed by coupling of effective dispersive liquid-liquid micro-extraction method with spectrophotometric determination for ultra-trace determination of cobalt. The method was based on the formation of Co(II)-alpha-benzoin oxime complex and its extraction using a dispersive liquid-liquid micro-extraction technique. During the present work, several important variables such as pH, ligand concentration, amount and type of dispersive, and extracting solvent were optimized. It was found that the crucial factor for the Co(II)-alpha benzoin oxime complex formation is the pH of the alkaline alcoholic medium. Under the optimized condition, the calibration graph was linear in the ranges of 1.0-110 µg L(-1) with the detection limit (S/N = 3) of 0.5 µg L(-1). The preconcentration operation of 25 mL of sample gave enhancement factor of 75. The proposed method was applied for determination of Co(II) in soil samples.

Assessment of strobilurin fungicides' content in soya-based drinks by liquid micro-extraction and liquid chromatography with tandem mass spectrometry.

Seven strobilurin fungicides were pre-concentrated from soya-based drinks using dispersive liquid-liquid micro-extraction (DLLME) with a prior protein precipitation step in acid medium. The enriched phase was analysed by liquid chromatography (LC) with dual detection, using diode array detection (DAD) and electrospray-ion trap tandem mass spectrometry (ESI-IT-MS/MS). After selecting 1-undecanol and methanol as the extractant and disperser solvents, respectively, for DLLME, the Taguchi experimental method, an orthogonal array design, was applied to select the optimal solvent volumes and salt concentration in the aqueous phase. The matrix effect was evaluated and quantification was carried out using external aqueous calibration for DAD and matrix-matched calibration method for MS/MS. Detection limits in the 4-130 and 0.8-4.5 ng g(-1) ranges were obtained for DAD and MS/MS, respectively. The DLLME-LC-DAD-MS method was applied to the analysis of 10 different samples, none of which was found to contain residues of the studied fungicides.

Speciation of inorganic arsenic species and total inorganic arsenic in rice using microwave-assisted dispersive liquid-liquid micro-extraction and electrothermal atomic absorption spectrometry.

Human exposure to inorganic arsenic (iAs) via rice consumption is of increasing concern. In the present study, microwave-assisted dispersive liquid-liquid micro-extraction (MADLLME) and electrothermal atomic absorption spectrometry (ETAAS) were developed for the speciation of iAs in rice samples. After microwave-assisted digestion, the As(III) ion reacted with diethyldithiophosphoric acid (DDTP) to form an As-DDTP complex and was extracted at the same time. Some parameters affecting digestion, complex formation, and extraction were studied and optimised. Under the optimised conditions, a detection limit of 0.2 µg kg(-1) with a correlation coefficient of 0.9901 were obtained with a calibration curve in the range of 0.5-200 µg kg(-1). Total iAs was determined after reduction of As(V) to As(III) with sodium thiosulfate and potassium iodide, and As(V) was calculated by difference. The proposed extraction procedure was successfully applied for the determination of iAs ions in certified reference materials (NIST CRM 1568a and NMIJ CRM 7503a) and 10 rice samples produced in Iran and other Asian countries.

Simultaneous Determination of Toxic Alkaloids and Rat Poisons in Toxic Samples by Dispersive Liquid-liquid Micro-extraction Combined with Gas Chromatography-Mass Spectrometry / 分析化学

A novel method for simultaneous determination of 3 rat poisons ( tetramine, bromadiolone, brodifacoum) and 5 toxic alkaloids ( hyoscyamine, scopolamine, gelsemine, strychnine, brucine ) in toxic samples by dispersive liquid-liquid micro-extraction ( DLLME ) coupled with gas chromatography-mass spectrometry was established. A mixture extractant containing 100 μL trichloromethane and 600 μL methanol was injected into the prepared sample to form an emulsion and the extraction process was accomplished. After centrifuged at 8000 r/min for 5 min, the settled drop of trichloromethane solvent was transferred to a conical insert within a GC autosampler vessel, and analyzed by GC-MS. Factors affecting extraction efficiency such as the type and volume of extractant, dispersive agent, extraction time, pH value and salt concentration of extraction system were studied. The limits of detection(LODs) were from 0. 003 to 1 μg/L in water sample, urine sample and rice wine sample. LODs were from 0. 002 to 0. 2 μg/kg in rice sample. The recoveries of toxic samples were in the range of 81. 0%-110%. The relative standard deviations( RSDs) were lower than 7%. The proposed method was sensitive, effective, and suitable for the simultaneous determination of toxic alkaloids and rat poisons in food poisoning sample.

Method for the determination of cadmium, lead, nickel, cobalt and copper in seafood after dispersive liquid-liquid micro-extraction.

A method using dispersive liquid-liquid micro-extraction (DLLME) and detection by inductively coupled plasma optical emission spectroscopy (ICP-OES) was developed for the determination of trace elements in seafood samples. The procedure allowed the simultaneous determination of Cd(II), Pb(II), Ni(II) Cu(II) and Co(II) after pre-concentration using sodium diethyldithiocarbamate (DDTC) as a chelating agent. Under optimised conditions, the method had a limit of detection (LOD) of 0.03, 0.11, 0.12, 0.18 and 0.12 µg l(-1) for Cd(II), Pb(II), Ni(II) Cu(II) and Co(II), respectively. The following enrichment factors were obtained: 16 (Cd), 34 (Pb), 20 (Ni) 34 (Cu) and 12 (Co). The procedure was applied for the determination of these elements in seafood (shrimp, mussel, bass and mullet) samples. The method is simple, efficient and easy to perform for the simultaneous determination of elements in seafood samples by ICP-OES.

A dispersive liquid-liquid microextraction method based on the solidification of a floating organic drop combined with HPLC for the determination of lovastatin and simvastatin in rat urine.

A dispersive liquid-liquid microextraction method based on solidification of floating organic drop combined with HPLC was developed for the determination of lovastatin and simvastatin in rat urine for the first time. 1-Dodecanol and methanol were used as the extraction and disperser solvents, respectively. Several important parameters influencing the micro-extraction efficiency were studied and systematically optimized, including the type and volume of extraction solvent and disperser solvent, extraction time, pH and salt concentration. The analytes were separated on a Kromasil C18 column at 30°C with a mobile phase of methanol and 0.2% acetic acid in water (83:17, v/v) and detected at 238 nm. Under the optimal conditions, the maximum number of enrichment factors for both analytes was 27. The linear ranges were 20.08-1004 and 20.00-1000 µg/L with the correlation coefficients ranging from 0.9990 to 0.9994 for lovastatin and simvastatin, respectively. The volume of organic solvent consumed in extraction was <0.3 mL, and the extraction time was 10 min. The newly developed environment-friendly sample pretreatment method will be a good alternative to conventional techniques, such as solid-phase extraction, liquid-liquid extraction and protein precipitation, for the HPLC determination of lovastatin and simvastatin in biological samples.