A study of liquid-liquid extraction in a sieve plate column

The literature relating to sieve plate liquid extraction columns and relevant hydrodynamic phenomena have been surveyed. Mass transfer characteristics during drop formation, rise and coalescence, and related models were also reviewed. Important design parameters i.e. flooding, dispersed phase hold-up, drop size distribution, mean drop size, coalescence/flocculation zone height beneath a plate and jetting phenomena were investigated under non-mass transfer and mass transfer conditions in a 0.45m diameter, 2.3m high sieve plate column. This column had provision for four different plate designs, and variable plate spacing and downcomer heights, and the system used was Clairsol `350' (dispersed) - acetone - deionised water (continuous) with either direction of mass transfer. Drop size distributions were best described by the functions proposed by Gal-or, and then Mugele-Evans. Using data from this study and the literature, correlations were developed for dispersed phase hold-up, mean drop size in the preferred jetting regime and in the non-jetting regime, and coalescence zone height. A method to calculate the theoretical overall mass transfer coefficient allowing for the range of drop sizes encountered in the column gave the best fit to experimental data. This applied the drop size distribution diagram to estimate the volume percentage of stagnant, circulating and oscillating drops in the drop population. The overall coefficient Kcal was then calculated as the fractional sum of the predicted individual single drop coefficients and their proportion in the drop population. In a comparison between the experimental and calculated overall mass transfer coefficients for cases in which all the drops were in the oscillating regime (i.e. 6.35mm hole size plate), and for transfer from the dispersed(d) to continuous(c) phase, the film coefficient kd predicted from the Rose-Kintner correlation together with kc from that of Garner-Tayeban gave the best representation. Droplets from the 3.175mm hole size plate, were of a size to be mainly circulating and oscillating; a combination of kd from the Kronig-Brink (circulating) and Rose-Kintner (oscillating) correlations with the respective kc gave the best agreement. The optimum operating conditions for the SPC were identified and a procedure proposed for design from basic single drop data.

IONIC LIQUID EXTRACTION UNVEILS PREVIOUSLY OCCLUDED HUMICBOUND IRON IN PEAT POREWATER

Extracellular iron reduction has been suggested as a candidate metabolic pathway that may explain a large proportion of carbon respiration in temperate peatlands. However, the o-phenanthroline colorimetric method commonly employed to quantitate iron and partition between redox species is known to be unreliable in the presence of humic and fulvic acids, both of which represent a considerable proportion of peatland dissolved organic matter. We propose ionic liquid extraction as a more accurate iron quantitation and redox speciation method in humic-rich peat porewater. We evaluated both o-phenanthroline and ionic liquid extraction in four distinct peatland systems spanning a gradient of physico-chemical conditions to compare total iron recovery and Fe2+:Fe3+ ratios determined by each method. Ionic liquid extraction was found to provide more accurate iron quantitation and speciation in the presence of dissolved organic matter. A multivariate approach utilizing fluorescence- and UV-Vis spectroscopy was used to identify dissolved organic matter characteristics in peat porewater that lead to poor performance of the o-phenanthroline method. Where these interferences are present, we offer an empirical correction factor for total iron quantitation by o-phenanthroline, as verified by ionic liquid extraction. The written work presented in this thesis is in preparation for submission to Soil Biology and Biochemisrty by T.J. Veverica, E.S. Kane, A.M. Marcarelli, and S.A. Green.

Liquid-liquid equilibria for systems composed of rice bran oil and alcohol-rich solvents: Application to extraction and deacidification of oil

The liquid-liquid equilibria of systems composed of rice bran oil, free fatty acids, ethanol and water were investigated at temperatures ranging from 10 to 60 degrees C. The results of the present study indicated that the mutual solubility of the compounds decreased with an increase in the water content of the solvent and a decrease in the temperature of the solution. The experimental data set was correlated by applying the UNIQUAC model. The average variance between the experimental and calculated compositions was 0.35%, indicating that the model can accurately predict behavior of the compounds at different temperatures and degrees of hydration. The adjustment of interaction parameters enables both the simulation of liquid-liquid extractors for deacidification of vegetable oil and the prediction of phase compositions for the oil and alcohol-rich phases that are generated during cooling of the stream exiting the extractor (when using ethanol as the solvent). (C) 2012 Elsevier Ltd. All rights reserved.

Determination of imidacloprid in paddy water and soil by liquid chromatography electrospray ionization-tandem mass spectrometry

A method for the determination of imidacloprid in paddy water and soil was developed using liquid chromatography electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS). Separation of imidacloprid was carried out on a Shimadzu C18 column (150 mm × 4.6 mm, 4.6 μm) with an acetonitrile?water (50 : 50, v/v) mobile phase containing 0.1% of acetic acid. The flow rate was 0.3 mL/min in isocratic mode. The product ion at 209 m/z was selected for quantification in multiple-reaction monitoring scan mode. Imidacloprid residues in soil were extracted by a solid-liquid extraction method with acetonitrile. Water samples were filtered and directly injected for analysis without extraction. Detection limits of 0.5 μg/kg and 0.3 μg/L were achieved for soil and water samples, respectively. The method had recoveries of 90 ± 2% (n = 4) for soil samples and 100 ± 2% (n = 4) for water samples. A linear relationship was observed throughout the investigated range of concentrations (1-200 μg/L), with the correlation coefficients ranging from 0.999 to 1.000. © Pleiades Publishing, Ltd., 2010.

A novel recovery process for lipids from microalgæ for biodiesel production using a hydrated phosphonium ionic liquid

The use of a hydrated phosphonium ionic liquid, [P(CH<inf>2</inf>OH)<inf>4</inf>]Cl, for the extraction of microalgæ lipids for biodiesel production, was evaluated using two microalgæ species, Chlorella vulgaris and Nannochloropsis oculata. The ionic liquid extraction was compared to the conventional Soxhlet, and Bligh & Dyer, methods, giving the highest extraction efficiency in the case of C. vulgaris, at 8.1%. The extraction from N. oculata achieved the highest lipid yield for Bligh & Dyer (17.3%), while the ionic liquid extracted 12.8%. Nevertheless, the ionic liquid extraction showed high affinity to neutral/saponifiable lipids, resulting in the highest fatty acid methyl esters (FAMEs)-biodiesel yield (4.5%) for C. vulgaris. For N. oculata, the FAMEs yield of the ionic liquid and Bligh & Dyer extraction methods were similar (>8%), and much higher than for Soxhlet (<5%). The ionic liquid extraction proved especially suitable for lipid extraction from wet biomass, giving even higher extraction yields than from dry biomass, 14.9% and 12.8%, respectively (N. oculata). Remarkably, the overall yield of FAMEs was almost unchanged, 8.1% and 8.0%, for dry and wet biomass. The ionic liquid extraction process was also studied at ambient temperature, varying the extraction time, giving 75% of lipid and 93% of FAMEs recovery after thirty minutes, as compared to the extraction at 100 °C for one day. The recyclability study demonstrated that the ionic liquid was unchanged after treatment, and was successfully reused. The ionic liquid used is best described as [P(CH<inf>2</inf>OH)<inf>4</inf>]Cl·2H<inf>2</inf>O, where the water is not free, but strongly bound to the ions.

Quantification of clenbuterol at trace level in human urine by ultra-high pressure liquid chromatography-tandem mass spectrometry.

Clenbuterol is a β2 agonist agent with anabolic properties given by the increase in the muscular mass in parallel to the decrease of the body fat. For this reason, the use of clenbuterol is forbidden by the World Anti-Doping Agency (WADA) in the practice of sport. This compound is of particular interest for anti-doping authorities and WADA-accredited laboratories due to the recent reporting of risk of unintentional doping following the eating of meat contaminated with traces of clenbuterol in some countries. In this work, the development and the validation of an ultra-high pressure liquid chromatography coupled to electrospray ionization tandem mass spectrometry (UHPLC-ESI-MS/MS) method for the quantification of clenbuterol in human urine is described. The analyte was extracted from urine samples by liquid-liquid extraction (LLE) in basic conditions using tert butyl-methyl ether (TBME) and analyzed by UHPLC-MS/MS with a linear gradient of acetonitrile in 9min only. The simple and rapid method presented here was validated in compliance with authority guidelines and showed a limit of quantification at 5pg/mL and a linearity range from 5pg/mL to 300pg/mL. Good trueness (85.8-105%), repeatability (5.7-10.6% RSD) and intermediate precision (5.9-14.9% RSD) results were obtained. The method was then applied to real samples from eighteen volunteers collecting urines after single oral doses administration (1, 5 and 10μg) of clenbuterol-enriched yogurts.

Liquid-liquid equilibria for systems composed of refined soybean oil, free fatty acids, ethanol, and water at different temperatures

Soybean oil can be deacidified by liquid-liquid extraction with ethanol. In the present paper, the liquid-liquid equilibria of systems composed of refined soybean oil, commercial linoleic acid, ethanol and water were investigated at 298.2 K. The experimental data set obtained from the present study (at 298.2 K) and the results of Mohsen-Nia et al. [1] (at 303.2 K) and Rodrigues et al. [2] (at 323.2 K) were correlated by applying the non-random two liquid (NRTL) model. The results of the present study indicated that the mutual solubility of the compounds decreased with an increase in the water content of the solvent and a decrease in the temperature of the solution. Among variables, the water content of the solvent had the strongest effect on the solubility of the components. The maximum deviation and average variance between the experimental and calculated compositions were 1.60% and 0.89%, indicating that the model could accurately predict the behavior of the compounds at different temperatures and degrees of hydration. (C) 2010 Elsevier B.V. All rights reserved.

Quantification of chlordesmethyldiazepam by liquid chromatography-tandem mass spectrometry: application to a cloxazolam bioequivalence study

A rapid, sensitive and specific LC-MS/MS method was developed and validated for quantifying chlordesmethyldiazepam (CDDZ or delorazepam), the active metabolite of cloxazolam, in human plasma. In the analytical assay, bromazepam (internal standard) and CDDZ were extracted using a liquid-liquid extraction (diethyl-ether/hexane, 80/20, v/v) procedure. The LC-MS/MS method on a RP-C18 column had an overall run time of 5.0 min and was linear (1/x weighted) over the range 0.5-50 ng/mL (R > 0.999). The between-run precision was 8.0% (1.5 ng/mL), 7.6% (9 ng/mL), 7.4% (40 ng/mL), and 10.9% at the low limit of quantification-LLOQ (0.500 ng/mL). The between-run accuracies were 0.1, -1.5, -2.7 and 8.7% for the above mentioned concentrations, respectively. All current bioanalytical method validation requirements (FDA and ANVISA) were achieved and it was applied to the bioequivalence study (Cloxazolam-test, Eurofarma Lab. Ltda and Olcadil (R)-reference, Novartis Biociencias S/A). The relative bioavailability between both formulations was assessed by calculating individual test/reference ratios for Cmax, AUClast and AUCO-inf. The pharmacokinetic profiles indicated bioequivalence since all ratios were as proposed by FDA and ANVISA. Copyright (C) 2009 John Wiley & Sons, Ltd.

Ciprofibrate quantification in human plasma by high-performance liquid chromatography coupled with electrospray tandem mass spectrometry for pharmacokinetic studies

A rapid, sensitive and specific method for quantifying ciprofibrate in human plasma using bezafibrate as the internal standard (IS) is described. The sample was acidified prior extraction with formic acid (88%). The analyte and the IS were extracted from plasma by liquid-liquid extraction using an organic solvent (diethyl ether/dichloromethane 70/30 (v/v)). The extracts were analyzed by high performance liquid chromatography coupled with electrospray tandem mass spectrometry (HPLC-MS/MS). Chromatography was performed using Genesis C18 4 mu m analytical column (4.6 x 150 mm i.d.) and a mobile phase consisting of acetonitrile/water (70/30, v/v) and 1 mM acetic acid. The method had a chromatographic run time of 3.4 min and a linear calibration curve over the range 0.1-60 mu g/mL (r > 0.99). The limit of quantification was 0.1 mu g/mL. The intra- and interday accuracy and precision values of the assay were less than 13.5%. The stability tests indicated no significant degradation. The recovery of ciprofibrate was 81.2%, 73.3% and 76.2% for the 0.3, 5.0 and 48.0 ng/mL standard concentrations, respectively. For ciprofibrate, the optimized parameters of the declustering potential, collision energy and collision exit potential were -51 V, -16 eV and -5 V, respectively. The method was also validated without the use of the internal standard. This HPLC-MS/MS procedure was used to assess the bioequivalence of two ciprofibrate 100 mg tablet formulations in healthy volunteers of both sexes. The following pharmacokinetic parameters were obtained from the ciprofibrate plasma concentration vs. time curves: AUC(last), AUC(0-168 h), C(max) and T(max). The geometric mean with corresponding 90% confidence interval (CI) for test/reference percent ratios were 93.80% (90% CI = 88.16-99.79%) for C(max), 98.31% (90% CI = 94.91-101.83%) for AUC(last) and 97.67% (90% CI = 94.45-101.01%) for AUC(0-168 h). Since the 90% Cl for AUC(last), AUC(0-168 h) and C(max) ratios were within the 80-125% interval proposed by the US FDA, it was concluded that ciprofibrate (Lipless (R) 100 mg tablet) formulation manufactured by Biolab Sanus Farmaceutica Ltda. is bioequivalent to the Oroxadin (R) (100 mg tablet) formulation for both the rate and the extent of absorption. (C) 2011 Published by Elsevier B.V.