Supercritical fluid extraction of Beauvericin from maize

Beauvericin (BEA), a supercritical fluid extraction with supercritical carbon dioxide from maize was investigated. Extraction efficiencies under several different extraction conditions were examined. Pressure, temperature, extraction time, organic modifier and water matrix content (10%) were investigated. The best extraction conditions were at a temperature of 60 °C, 3200 psi, for 30 min static extraction time and methanol as modifier solvent. Extraction recovery of 36% without modifier by adding water to the matrix in the extraction vessel (reproducibility relative standard deviations (R.S.D.)=3-5%) were recorded. Extraction recovery of 76.9% with methanol as co-solvent (reproducibility R.S.D.=3-5%) was obtained. Data shows that SFE gives a lower BEA recovery compared to conventional extraction protocol with organic solvents while SFE with modifier and conventional extraction yields are comparable. BEA extract contents were determined by high pressure liquid chromatography (HPLC) with a diode array detector (DAD) at 205 nm and BEA peak confirmed by LC-MS. Acetonitrile-water as mobile phase and column C-18 were both tested. Instrumental and analytical parameters were optimized in the range linear interval from 1 to 500 mg kg⁻¹ and reached a detection limit of 2 ng.     

Comparisons of soxhlet extraction, pressurized liquid extraction, supercritical fluid extraction and subcritical water extraction for environmental solids: recovery, selectivity and effects on sample matrix

Extractions of a polycyclic aromatic hydrocarbon (PAH)-contaminated soil from a former manufactured gas plant site were performed with a Soxhlet apparatus (18 h), by pressurized liquid extraction (PLE) (50 min at 100 degrees C), supercritical fluid extraction (SFE) (1 h at 150 degrees C with pure CO2), and subcritical water (1 h at 250 degrees C, or 30 min at 300 degrees C). Although minor differences in recoveries for some PAHs resulted from the different methods, quantitative agreement between all of the methods was generally good. However, the extract quality differed greatly. The organic solvent extracts (Soxhlet and PLE) were much darker, while the extracts from subcritical water (collected in toluene) were orange, and the extracts from SFE (collected in CH2Cl2) were light yellow. The organic solvent extracts also yielded more artifact peaks in the gas chromatography (GC)-mass spectrometry and GC-flame ionization detection chromatograms, especially compared to supercritical CO2. Based on elemental analysis (carbon and nitrogen) of the soil residues after each extraction, subcritical water, PLE, and Soxhlet extraction had poor selectivity for PAHs versus bulk soil organic matter (approximately 1/4 to 1/3 of the bulk soil organic matter was extracted along with the PAHs), while SFE with pure CO2 removed only 8% of the bulk organic matrix. Selectivities for different compound classes also vary with extraction method. Extraction of urban air particulate matter with organic solvents yields very high concentrations of n- and branched alkanes (approximately C18 to C30) from diesel exhaust as well as lower levels of PAHs, and no selectivity between the bulk alkanes and PAHs is obtained during organic solvent extraction. Some moderate selectivity with supercritical CO2 can be achieved by first extracting the bulk alkanes at mild conditions, followed by stronger conditions to extract the remaining PAHs, i.e., the least polar organics are the easiest organics to extract with pure CO2. In direct contrast, subcritical water prefers the more polar analytes, i.e., PAHs were efficiently extracted from urban air particulates at 250 degrees C, with little or no extraction of the alkanes. Finally, recent work has demonstrated that many pollutant molecules become "sequestered" as they age for decades in the environment (i.e., more tightly bound to soil particles and less available to organisms or transport). Therefore, it may be more important for an extraction method to only recover pollutant molecules that are environmentally-relevant, rather than the conventional attempts to extract all pollutant molecules regardless of how tightly bound they are to the soil or sediment matrix. Initial work comparing SFE extraction behavior using mild to strong conditions with bioremediation behavior of PAHs shows great promise to develop extraction methodology to measure environmentally-relevant concentrations of pollutants in addition to their total concentrations.     

Supercritical fluid extraction of Kava lactones from Kava root and their separation via supercritical fluid chromatography

Summary Seven Kava lactones were extracted from Kava root using both pure and 15% ethanol modified CO₂. Most of the Kava lactones were extracted employing 100% CO₂ with an efficiency greater than 90% relative to conventional solvent extraction using organic solvents. Extraction efficiency did not increase significantly when using 15% ethanol-modified CO₂ as an extraction fluid. Separation of extracted Kava lactones was obtained using various packed columns and methanol-modified CO₂. An optimized separation was achieved using either an amino or protein C₄ column at 125 atm and 80°C. Semi-preparative separation of Kava lactones was also obtained using two columns connected in series.     

Effect of plant matrix and fluid ethanol concentration on supercritical fluid extraction efficiency of schisandrin derivatives

An investigation of the effect of plant matrix on the supercritical fluid extraction efficiency of five schisandrin derivatives is reported, exhibiting a great difference with respect to extraction efficiency depending on the matrix. Pure supercritical CO2 at 60 degrees C and 34.0 MPa cannot fully recover schisandrin derivatives from the leaves as much as from the other matrices. Only 36.9% of these compounds are extracted from leaves of Schisandra chinensis by supercritical CO2 in comparison with organic solvent extraction. However, more than 80% of schisandrin derivatives are obtained from both stem and fruit parts. Ethanol addition also shows a different effect depending on plant matrix; that is, CO2 modified with 10% ethanol could enhance the yield of schisandrin derivatives from leaves by four times when compared with that of pure CO2, but it has little effect on both stems and fruits.     

Supercritical carbon dioxide extraction of ubiquinones and menaquinones from activated sludge

Supercritical CO2 (scCO2) extraction, with methanol as modifier, was applied to the determination of ubiquinones and menaquinones in activated sludge. Four ubiquinones and 12 menaquinones species were identified based on retention time and UV spectrum in 0.1g dried activated sludge. The optimum extraction conditions were at a pressure of 25 MPa, a temperature of 55 degrees C, and 10% (v/v) methanol for 15 min. At this condition, the concentrations of extracted ubiquinones and menaquinones were found to be 0.181 and 0.326 micromol/g-dry-cell, respectively. The results were comparable with those obtained by organic solvent extraction based on diversity and dissimilarity indices. Furthermore, the method was evaluated in term of repeatability, which resulted in an RSD of < or =10%. The experimental results have demonstrated the technique to be simple, fast, and with less consumption of organic solvents. This work shows the potential application of supercritical CO2 extraction to microbial community analysis using quinone profile.     

SFE of PAHs from soils with a high carbon content and analyte collection via combined liquid/solid trapping

Polynuclear aromatic hydrocarbons (PAHs) are recovered from a soil with a high carbon content (ca. 50%) with supercritical fluid extraction (SFE) as well as with conventional Soxhlet extraction. The influence of temperature and modifier volume on SFE efficiency and the effect of a combined liquid/solid trap for analyte collection are investigated in this study. Such traps, which make analyte collection and clean-up possible in one step, are compared with conventional analyte collection in pure organic solvents. A comparison between reproducibility and efficiency of SFE and Soxhlet extraction is presented.     

Supercritical fluid extraction of nylon 6,6 oligomers and their characterization via liquid chromatography coupled with mass spectrometry.

This research extends previous studies regarding the application of supercritical fluid extraction (SFE) for the analysis of oligomers from nylon 6,6 fibers. The effects of CO2 pressure, extraction temperature, CO2-modifier percentage, static extraction time and dynamic extraction time on the SFE efficiency of nylon 6,6 oligomers were examined. Results from the SFE methods for oligomer extractions were compared to results from conventional solvent extraction. The extracted oligomers were identified by high-performance liquid chromatography (HPLC) with coupled on-line atmospheric pressure chemical ionization mass spectrometry and HPLC fractionation coupled with off-line liquid secondary ion mass spectrometry.     

Use of supercritical fluid extraction in the analysis of polychlorinated dibenzodioxins and dibenzofurans

Summary Supercritical fluid extraction is a powerful technique with great promise in organic analytical chemistry. To date little has been published on the use of SFE in the analysis of polychlorinated dibenzodioxins and dibenzofurans (PCDD/F). The data point, however, to the feasibility of a selective and exhaustive extraction of these compounds. Solid phase trapping of the extracted PCDD/F allows for on-line class separation and clean-up and seems to be the most flexible choice of collection mode. Both CO₂ and N₂O can be used as supercritical fluids. Extraction recoveries can be improved with a small percentage of an organic solvent added to the supercritical fluid as modifier. Methanol and benzene have proven to be efficient. Relatively strong supercritical fluid conditions are needed for the extraction of PCDD/F from fly ash (350–400 atm at 330–370 K). Spiked internal standards are easily extracted even at mild conditions whereas native PCDD/F are not; thus caution should be taken when an isotopic dilution technique is used for a future evaluation of SFE in the analysis of PCDD/F.     

Influence of the characteristics of soil and fly ash on the supercritical carbon dioxide extraction of dioxins.

Several investigations on the extraction of dioxins from soil and fly ash with supercritical fluid have been reported; however, few of them describe the influence of components on the extraction. We extracted dioxins from eight samples with different values of organic carbon content and surface area with supercritical CO(2) at a temperature of 463 K, a pressure of 40 MPa, and using 10% toluene as an entrainer. We researched the influence of the characteristics of soil and fly ash on supercritical CO(2) extraction of dioxins. The results revealed that the extraction efficiencies of PCDD/DFs and PCBs were high for all soil samples, while that of fly ash samples decreased with the increase in organic carbon content and surface area. The extraction efficiencies of dioxins from four standard samples, activated carbon, humic acid, alumina, and florisil, were also examined. The results revealed that the extraction efficiencies were strongly influenced by activated carbon like components present in the samples.     

Supercritical fluid clean-up of environmental samples for the analysis of polycyclic aromatic hydrocarbons using time-of-flight secondary ion mass spectrometry.

A novel sample-pretreatment method for time-of-flight secondary ion mass spectrometry (TOF-SIMS) was developed using supercritical fluid extraction (SFE). In SFE, the extraction efficiency of a certain organic matter is controlled by the pressure and temperature of supercritical CO2. Two-step SFE (1st step at 10 Mpa, 40 degrees C; 2nd step at 30 MPa, 120 degrees C) was applied to diesel exhaust particles containing many kinds of n-alkanes and aromatic species. n-Alkanes and polycyclic aromatic hydrocarbons (PAHs) were extracted in the 1st and 2nd steps, respectively. This selectivity was utilized for the sample preparation of TOF-SIMS analysis. Diesel exhaust particles after the 1st step of extraction were analyzed with TOF-SIMS, aiming at PAHs as analytical targets. The obtained spectrum was simplified, and mass peaks of individual PAHs were easily assigned, because unwanted compounds, like n-alkanes, were selectively removed by SFE. Furthermore, a simple calculation elucidated the outline of the spectrum.     

Analysis of organic pollutants in sewage by supercritical fluid extraction

Summary Analytical methods have been developed for the determination of organic pollutants of intermediate polarity in sewage. Water samples are first passed through a solid phase adsorption cartridge. The analytes are then extracted from the absorbent with supercritical CO₂ into a small volume of trapping solvent. Finally, the extracts are analyzed directly by capillary gas chromatography and gas chromatography-mass spectrometer. The various parameters (pressure, temperature, type and concentration of modifiers, trapping solvent, flow rate and volume of supercritical fluid and equilibrium time) influencing the efficiency of extraction were studied. Extraction efficiencies for the test compounds are >70%, and relative standard deviations are <4.6% (n=3). The methods established were applied to the analysis of sewage at the Lanzhou Wastewater Treatment Plant, China. 66 organic pollutants were detected, of which 15 compounds appeared in the list of priority pollutants suggested by the US EPA.     

Optimization of supercritical fluid extraction by carbon dioxide with organic modifiers of polycyclic aromatic hydrocarbons from urban particulate matter

The main advantages of using supercritical fluids for the extractions of organic pollutants from environmental matrix is that they are inexpensive, contaminant free, and less costly to dispose safely than organic solvents. In this work, a series of extraction experiments were carried out using CO2 as supercritical fluid on a certified sample of "Urban dust" (NIST S.R.M. 1649a) to optimize the analytical parameters with the aim of investigating the extraction limit of organic pollutant by using an almost "organic solvent-free" technique. The certified sample contains small concentrations of several organic pollutants, as PAH and PCB. The initial tests of extraction were carried out with only CO2 in supercritical phase, by maintaining the temperature at 50 degrees C and 80 degrees C and by making the pressure vary between 230 bar and 600 bar. The effect of three organic modifiers (methanol, n-hexane and toluene), added at 5% in volume, has been considered. The yield of recovery has been estimated for anthracene, fluoranthene, chrysene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene by GC-MS according to the increasing molecular weight.     

On-line coupling of supercritical CO2 extraction with reversed-phase liquid chromatography for the quantitative analysis of analytes in aqueous matrices

The first report of on-line coupled supercritical fluid extraction (SFE) with reversed-phase liquid chromatography for the quantitative analysis of analytes in aqueous matrices is described. Two commercial systems (e.g. SFE and HPLC) were connected via a single six-port injection valve. By using water to eliminate residual decompressed CO2 gas in the solid-phase extraction trap, quantitative extraction and transfer were achieved for the target analytes (progesterone, phenanthrene, and pyrene) spiked in water, as well as in real samples (urine and environmental water). During each extraction, no restrictor plugging was realized. Extraction temperature and pressure were optimized. Different amounts of salt were added to the aqueous matrix to enhance ionic strength and thus extraction efficiency. Methanol and 2-propanol were used as CO2 modifiers. Compared with dynamically mixing modifier with the CO2 extraction fluid, pre-spiking the same amount of modifier in the extraction vessel enhanced the recovery approximately 30% for progesterone, phenanthrene, and pyrene due to a "co-extraction effect".     

Towards more rational techniques for the isolation of valuable essential oils from plants

Attention is drawn to the use of new and clean alternative methods for the isolation of essential oils from plants. A critical overview is presented of conventional methods (based on either organic solvent extraction or distillation) and new alternatives (including microwave-assisted extraction (MAE) as well as supercritical CO₂ (SC-CO₂) extraction and subcritical water extraction). The advantages and disadvantages of each technique are reported and special emphasis is given to the use of continuous subcritical water extraction which emerges as clearly advantageous over conventional techniques (by avoiding the use of organic solvents and considerably shortening the extraction time, as well as increasing the efficiency) and recent techniques, such as MAE (by increasing the efficiency) and SC-CO₂ extraction (by avoiding the co-extraction of cuticular waxes and lipids and the need for a sample drying stage prior to extraction).     

神华煤直接液化残渣超临界溶剂萃取研究

利用甲苯、苯和乙醇三种溶剂在反应釜中对神华煤直接液化残渣进行了超临界溶剂萃取,考察了压力、温度、萃取时间、溶剂/残渣比等对萃取产物收率和重质液体萃取组成的影响。结果表明,以甲苯为溶剂进行萃取时,萃取时间对重质液体产率及HS和A收率的影响不大,而温度、压力以及溶剂/残渣质量比都会影响萃取产物的产率及组成。溶剂超临界萃取过程中,有其他组分向HS组分转化,提高了HS的收率。三种溶剂中,苯显示了和甲苯相似的萃取性能,而乙醇的萃取性能相比苯和甲苯则较差,但乙醇萃取得到的重质液体中轻质组分含量高于苯和甲苯。萃取过程中,残渣中的灰分和硫分主要富集至萃取残渣中。     

Preparation and properties of surfactant-bacillolysin ion-pair in organic solvents

The transesterification-active enzyme bacillolysin was extracted into organic solvents such as isooctane by enzyme-AOT (bis (2-ethylhexyl) sulfosuccinate) ion-pairing preserving its natural second structure and catalytic activity. Extraction efficiency was affected by the interaction mode of the two phases, ionic strength, and pH of aqueous phase, surfactant and enzyme concentration. Magnetic stirring with phase mixing was favorable for the enzyme extraction. Optimal ionic strength and pH were 8 mM CaCl₂ and 5.0, respectively. Critical number of AOT molecule for an enzyme molecule to be extracted into isooctane was 89. Optimal initial enzyme concentration in the aqueous phase was 7 mg mL⁻¹ while the initial AOT concentration in isooctane was 3 mM. Within CMC (critical micellar concentration) of AOT in isooctane, the increase of initial AOT concentration enhanced the extraction efficiency.     

Solvent extraction of ionic solutes in aqueous solutions

Extraction of ionic solutes in aqueous solutions into various organic solvents is reviewed by showing several examples. The extraction of strong acids into polar organic solvents and nonpolar solvents containing hydrogen-bonding extractants is described as the first example and the extraction of simple metal salts into strongly dielectric or solvating polarsolvents and nonpolar solvents containing solvating extractants is then reported. Finally, the solvent extraction of anionic metal complexes with bulky cations into nonpolar solvents as ion-paris is described and the statistical method for such extraction equilibria is considered.     

A Unified Sample Preparation System for Extraction of Various Analyte/Matrix Combinations

A supercritical fluid extraction/enhanced solvent extraction system (SFE/ESE) was used to remove polar and non-polar analytes from various matrices. Extraction of environmental pollutants from soil, additives from low density polyethylene, sulfa drugs from animal tissue, and drug from tablet was performed using both SFE and ESE. Results showed that a single instrumental system can be used to perform both ESE with organic solvents and SFE with carbon dioxide-based fluids. Each method has its own unique advantages and applications. The ability to carry out both solvent extraction and supercritical fluid extraction with one system has obvious economical advantages.     

A two-step supercritical fluid extraction of polycyclic aromatic hydrocarbons from roadside soil samples

A two-step procedure for the supercritical fluid extraction (SFE) of polycyclic aromatic hydrocarbons from soil samples was developed. The procedure consists of a static supercritical fluid treatment in a closed extraction cell at a high temperature (T=250 or 340degreesC for 20 min) and an SFE with a solvent trapping. During the static phase, the sample is exposed to a supercritical organic solvent (methanol, toluene, dichloromethane, ACN, acetone, and hexane). The solvent penetrates particles of the matrix to substitute strongly bonded molecules and dissolves the analytes in the supercritical phase. At ambient temperature, supercritical fluids became liquid and lost their solvation abilities. Most of the analytes condense on the surface of the particles or on the extraction cell walls without forming strong bonds or penetrating deep into the matrix. Thus, the pretreatment liberates the analytes and they behave similar to those in freshly spiked samples. The common SFE with toluene-modified CO2 as an extraction fluid follows the static phase. With the use of the most suitable extraction phases (toluene, ACN), the extraction efficiency of the combined procedure is much higher (approximately100%). The results of the combined procedure are compared to the SFE procedure of the same untreated sample (difference less than 5%) and to the Soxhlet extraction. The extracts were analyzed using a GC with the flame ionization detection.