Analysis of Carbaryl and carbofuran in tobacco samples by HRGC,HPLC, and CZE

Determination of carbamate residues in tobacco samples was carried out by three different methods, two having been described in the literature and one developed for the purpose of this work. The extracts were analyzed by HRGC-FID (using derivatization), by HPLC-RP with photodiode array detection and by Capillary Zone Electrophoresis (CZE) with UV detection. The extraction method developed used in conjunction with capillary zone electrophoresis showed to be the most suitable for carbamate residue analysis in real tobacco samples. The developed method presented better recovery results in relation to the others. CZE allowed the determination of carbamate residue in real tobacco sample while HPLC and HRGC could not do this, due to co-elution problems.     

Supercritical fluid extraction of flumetralin in tobacco

Summary This work evaluates the level of Flumetralin residues in real tobacco samples. Conventional extraction methods were compared with SFE methods in both static and dynamic modes using CO₂ and CO₂ with modifier. Additionally, in the dynamic SFE mode, different collection approaches, such as collection at room temperature without solvent, collection at room temperature in the presence of solvent (hexane) and collection in an ice bath, without solvent, were studied. SFE showed itself to be a promising extraction technique for pesticide residues in tobacco samples.     

Fast determination of chlorogenic acid in tobacco residues using microwave-assisted extraction and capillary zone electrophoresis technique

In this work, for the first time, capillary zone electrophoresis (CZE) technique combined with microwave-assisted extraction (MAE) was developed for the fast quantification of chlorogenic acid (CA) in tobacco residues. CA in tobacco residue samples were extracted by MAE technique, and then analyzed by CZE. As a new sample preparation method for tobacco residues, the MAE procedure is optimized, validated and compared with conventional methods including ultrasonic extraction (USE) and reflux extraction (RE). It is found that MAE gives the best result due to the highest extraction efficiency within shortest extraction time (only 4.0 min). Here, CA is determined by CZE based on the calibration curve of its authentic standard. The method linearity, detection limit, precision and recovery are studied. The results show that the combined MAE and CZE method has a linearity (R² 0.991, 0.003-0.5 mg ml⁻¹), a limit of detection (0.003 mg ml⁻¹), a limit of quantification (0.01 mg ml⁻¹), good precision (R.S.D. = 4.28%) and a finer recovery (89.0%). The proposed method was successfully applied to the analysis of CA in tobacco residue samples. The experiment results have demonstrated that the CZE combined with MAE is a convenient, fast, economical and reliable method for the determination of CA in tobacco residues.     

Off-line SFE-CGC-ECD analysis of 2,4-D and Dicamba residues in real sugar cane,rice and corn samples

Determination of 2,4-D (2,4-dichlorophenoxyacetic acid) and Dicamba (2-methoxy-3,6-dichlorobenzoic acid) residues in sugar cane, rice, and corn was carried out both by solid liquid extraction (SLE), as already described in the literature, and by a supercritical fluid extraction (SFE) method developed in our laboratory. The extracts were esterified and cleaned-up by passing through a Florisil column. Extracts were analyzed by high resolution gas chromatography, with electron capture detection. The tested methods presented good recoveries (above 90%); the SFE CO₂/acetone method showed better extraction efficiencies (extracted 30 % more herbicide in real samples), shorter extraction time and lower organic solvent consumption than the SLE method.     

Effect of temperature,collection mode,and modifier on the supercritical CO2 extraction of dicofol residues from fish samples

Toxicity evaluation of Dicofol to Astyanax bimaculatus schubarti, a characteristic fish species living in tropical rivers and lakes was carried out through LC₅₀ – 96 Hours. These experiments were performed under laboratory controlled conditions with atmospheric air flow and dilution water at 25°C in the static mode, supercritical fluid extraction (SFE) with pure CO₂ and CO₂ modified with hexane and methanol were used at 50, 70, 80, and 100°C and 300 atm. Several collection modes were studied to extract Dicofol from fish samples. The extraction efficiencies were directly comparedd with those obtained after 8 h of Soxhlet extraction using the same clean-up with Florisil and analysis by HRGC/ECD and HRGC/MS as a confirmatory analytical technique. The SFE recoveries at temperatures lower than 80°C were typically lower than soxhlet recoveries; however a temperature increase enhanced the efficiency of SFE. The results showed that under certain conditions, supercritical fluid gave higher extractio power (extracted 11 % more pesticide), shorter extraction time, and lower solvent consumption than Soxhlet, thus affording an excellent alternative to the conventional method for extracting Dicofol from fish sample.     

Determination of PAHs in dust from Shanghai by optimized SFE and GC/MS

EPA 16 priority polycyclic aromatic hydrocarbons (PAHs) were extracted from dust by supercritical fluid extraction (SFE). Parameters (pressure, temperature and time) affecting the collection efficiencies of PAHs were assessed according to the extraction efficiency, and 30 MPa, 80 degrees C and 30 min dynamic extraction time were confirmed to be the best and simplest conditions of SFE to extract 16 priority PAHs from dust. The characterization of the extracts was carried out by gas chromatography with mass detector in selective ion mode (GC/MS/SIM). Ultrasonic extraction (USE) was used as a comparison with SFE. The results showed that the SFE method has a better efficiency than USE for the extraction of PAHs in dust. With the optimized conditions of SFE, the distribution of PAHs in dust samples in urban areas of Shanghai from Mar 10, 2005 to May 28, 2005 was investigated. The results demonstrated that traffic emission, especially from gasoline engines, was the main source of PAHs in dust of Shanghai.     

Potential artifact formation of dioxins in ball clay during supercritical fluid extraction

Earlier surveys indicate that meat, fish and dairy products are the principal source of polychlorinated dibenzo-p-dioxin (PCDD) exposure in the diet. A recent finding by others of PCDDs in chickens that consumed a feed containing PCDD led to the finding of ball clay, an anti-caking agent, as the source. Supercritical fluid extraction (SFE) was studied as a means to isolate PCDDs from commercial ball clays using GC-electron capture detection (muECD) as a means to screen for these contaminants. The finding of ng/g amounts and recoveries >100% in several samples of ball clay containing octachlorodibenzo-p-dioxin (OCDD) suggested that PCDD may form artifactually as a result of analysis. Studies on pentachlorophenol (PCP) fortified ball clay were carried out by SFE and soxhlet extraction and the results compared. The values obtained by SFE were considered more problematic. The results obtained from ball clay suggest that precautions need to be exercised when using SFE to analyze for dioxins in solid samples containing chlorophenols.     

Inert matrix and Na4EDTA improve the supercritical fluid extraction efficiency of fluoroquinolones for HPLC determination in pig tissues

A supercritical fluid extraction method combined with high-performance liquid chromatography-fluorescence detection was developed for the determination of enrofloxacin, danofloxacin, and ciprofloxacin in pig muscle, lung, and kidney samples. The optimal SFE conditions were 80 °C, 300 kg/cm², 30% methanol for 40 min as a dynamic extraction time, in addition to 0.2 g Na₄EDTA and 7.0 g sea sand in the extraction vessel. The use of Na₄EDTA and sea sand on SFE extraction resulted in improvement of the recoveries of ciprofloxacin, a polar and hydrophilic compound, as well as enrofloxacin and danofloxacin. Overall, the recoveries ranged from 86.7 to 113.1% using the Na₄EDTA/sea sand-assisted SFE extraction method. The Na₄EDTA/sea sand-assisted SFE-HPLC-FLD validated method was successfully carried out in pig tissues, and proved to be specific, sensitive, reliable, and accurate. The method was also applied satisfactorily for accurate quantitative residue analysis in incurred pig tissues.     

Comparison of Supercritical Fluid Extraction with Solvent Sonication for Chemical Warfare Agent Determination in Alkyd Painted Plates

Supercritical fluid extraction (SFE) of alkyl alkylphosphonofluoridates and dialkyl alkylphosphonates from painted plates was investigated. It was found that SFE recoveries compared favorably with conventional solvent sonication results. Stability studies of the samples were carried out over a period of two months. This investigation showed that the concentration of phosphonofluoridates decreased over a long period.     

Supercritical fluid extraction of carbamate pesticides from soils and cereals

Summary A method for the supercritical fluid extraction of carbamate pesticides (propoxur, aminocarb, carbaryl and methiocarb) from soil and cereal samples using CO₂ is proposed. Extractions were at 378 bar and 54 °C. Analytes were determined in the extracts by HPLC with fluorescence detection after post-column derivatization. Recoveries from spiked soil ranged between 39.6 and 91.7%, depending on analyte and soil components. Lowest recoveries were from sandy soils. Aminocarb could not be recovered from any soil using CO₂. Recovery of aminocarb from diatomaceous earth was improved by adding methanol to the extraction cell prior to SFE, but the effect was not observed in soil samples. Recoveries for propoxur and aminocarb from spiked wheat were about 75%, and only between 30–50% for aminocarb from corn and oats, and carbaryl from wheat. Fat was coextracted using CO₂ and retained in the trap together with the analytes, however, appropriate rinsing solvent allowed on-line clean-up of the extract.     

Comparison of various extraction techniques for isolation and determination of isoflavonoids in plants

In the present paper, the following extraction techniques have been used for extracting isoflavonoids from the species Matricaria recutita, Rosmarinus officinalis, Foeniculum vulgare, and Agrimonia eupatoria L.: supercritical fluid extraction (SFE), pressurized fluid extraction, matrix solid phase dispersion, ultrasonic extraction in an ultrasonic bath (USE) and by means of an ultrasonic homogeniser (HOM), extraction by means of Soxhlet apparatus (SOX), and solid phase extraction. Experimental optimization of all techniques has been carried out using a soybean flour. Subsequent analyses of the extracts were carried out by liquid chromatography with UV detection. The maximum yields of daidzein and genistein were obtained by extraction with the SOX, USE, and HOM techniques. The maximum yields of apigenin and biochanin A from herb samples were obtained by SFE.     

Screening of pesticide-contaminated soil by supercritical fluid extraction (SFE) and high-performance thin-layer chromatography with automated multiple development (HPTLC/AMD)

A method for screening of pesticide-contaminated soil was developed. The extraction is carried out by supercritical carbon dioxide (CO₂) with methanol as a modifier. The different components of the extracts are separated by high-performance thin-layer chromatography with automated multiple development (HPTLC/AMD) and evaluated densitometrically. The technique can be carried out without any previous clean-up step. Compared with other extraction techniques, SFE has the advantages of reducing the amount of co-extracted soil contents, which can seriously deteriorate the results. A 35-step development of the TLC-plate with gradient elution offers an application over a wide range of polarity. Migration data for 107 pesticides, recoveries and detection limits for 20 pesticides were determined.     

Analytical supercritical fluid extraction of Chinese herbal medicines

Summary An analytical supercritical fluid extraction (SFE) technique, followed by GC/MS, was developed to separate and determine the volatile components in Chinese herbal medicine. Three kinds of herbs, frankincense, myrrh, andEvodia rutaecarpa were extracted and analyzed. The extraction was carried out using supercritical fluid CO₂ at 20 MPa and 50°C. The main factors affecting the efficiency and selectivity of the extraction are discussed. The results revealed the potential of supercritical fluid extraction as an analytical procedure for the study of medicinal plants.     

Sub-critical fluid extraction of morphinic alkaloids in urine and other liquid matrices after adsorption on solid supports

Summary Supercritical fluid extraction (SFE) of liquid matrices is difficult and requires special instrumentation. An alternative is to load the liquid on a solid support prior to extraction. This procedure yields higher selectivity and can be used as a clean-up step when very complex liquid matrices, such as urine, are to be analyzed. This paper demonstrates the use of various solid supports in order to extract morphinic alkaloids with subcritical fluids (CO₂ + polar modifier). Optimization of the procedure with regard to loading conditions, SFE parameters such as pressure, extraction time, flow rate and eluent composition, was carried out with morphinic alkaloids in aqueous solution. As a real-life application, SFE of opiates in urine were tested with two silica bonded phase supports (C18 (polygosil 60-4063, from Macherey-Nagel) and Bond Elut Certify from Analytichem International). Recovery, variation coefficients and linearity are described for each procedure. Bond Elut Certify silica was chosen as the best solid support and SFE is compared with conventional solid phase extraction.     

Analysis of poly(vinyl chloride) additives by supercritical fluid extraction and gas chromatography

The use of supercritical fluid extraction (SFE) is growing, with an expanding range of applications in many different fields as a consequence of its advantages compared with traditional extraction methods. In order to develop an analytical method to determine dibutyl phthalate (DBP) and dioctyl phthalate (DOP) traces (<20 ppm) in flexible poly(vinyl chloride) (PVC) formulations, a maximum efficiency in the extractive process and an adequate separative system are needed to avoid interferences between these two plasticizers and other additives that could be present at high concentrations in flexible PVC formulations. In order to determine the optimum SFE conditions, the extraction time, temperature and pressure were controlled. The separation and quantitation of individual components in the PVC extracts were carried out off-line by using a semicapillary column in gas chromatography (GC). Samples with different DOP content (41.18%, 33.33% and 23.08%) and DBP content (41.18%), as well as samples with both plasticizers (20.59% DOP and 20.59% DBP) were prepared. Some other samples were also prepared to study detection limits for these two PVC additives. Recoveries and reproducibilities were studied in every sample. Finally, this method was compared with Soxhlet liquid extraction. Determination by gravimetric analysis of the total extracted material was found to be particularly suitable for PVC. This study demonstrates the potential of SFE to shorten extraction times with similar or even better extraction efficiencies compared with traditional liquid methods.     

Comparison of supercritical fluid and Soxhlet extractions for the isolation of nitro compounds from soils

Supercritical fluid extraction (SFE) with CO(2), a clean and rapid alternative to conventional Soxhlet extraction, was investigated for the extraction of nitro compounds from soil samples. Quantitative extraction by SFE was accomplished at a pressure of 25 MPa and an extraction temperature of 60 degrees C, for 30 min in dynamic mode and using acetonitrile as modifier, and the results were comparable with those obtained by acetonitrile Soxhlet extraction (3 h) for all soil samples. Extracts from these two procedures were analyzed by gas chromatography coupled with mass spectrometry. Quantitative reproducibility for SFE extracts was acceptable (RSD 2-10%), and the quantity of solvent was reduced from 160 mL for Soxhlet extraction to 5 mL in the case of SFE.     

Selective extraction of astaxanthin from crustaceans by use of supercritical carbon dioxide

An on-line supercritical fluid extraction (SFE) system coupled to a continuous flow manifold including a UV detector was used as a screening system to extract astaxanthin from crayfish, which was found to be the major carotenoid present in the samples. This compound constitutes the principal additive used to dye salmon flesh. The flow manifold was used to confirm the presence of astaxanthin in the crustacean samples. Also, an HPLC/UV-vis method was used to ascertain that this compound was the major carotenoid extracted under the optimum SFE conditions employed. The influence of SFE operating variables such as pressure, temperature, equilibration time, extraction time, trap temperature, and volume of CO₂ modifier was examined in order to maximize the efficiency of analyte extraction. The use of supercritical CO₂ enables the expeditious, selective, quantitative extraction of astaxanthin from crustaceans.     

土壤中烃类污染物的超临界流体萃取

采用超临界流体萃取技术提取环境样品中的烃类污染物，以色谱－质谱联用仪测定了萃取物的化学成分，考察了影响萃取效率的主要因素。比传统的索氏萃取能更有效地从复杂环境样品中萃取分析物。     

Supercritical fluid extraction of the fluoroquinolones norfloxacin and ofloxacin from orally treated-chicken breast muscles

Supercritical fluid extraction (SFE) of the fluoroquinolones norfloxacin and ofloxacin from chicken breast muscles was examined. A liquid chromatography with fluorescence detection was used for the determination of the fluoroquinolones. Extraction conditions of the SFE were optimized by determining the extraction parameters to achieve a sufficiently high recovery of each fluoroquinolone in fortified-muscle samples. Recovery values for the extraction of the fluoroquinolones using the SFE ranged from 70 to 87%. Chickens were treated orally with each fluoroquinolone and their muscles were extracted at set time intervals for time-course determination of the fluoroquinolones in chickens. The SFE combined with liquid chromatographic analysis showed that the concentrations of the fluoroquinolones decreased gradually with time in the chicken muscles after oral treatment, giving a concentration less than 5 ng/ml in 120 h. No further sample cleanup procedures were required after the SFE. These results suggest that SFE method is an extraction method for the determination of norfloxacin and ofloxacin in chicken muscle.     

Optimization of parameters for the supercritical fluid extraction in the determination of N-nitrosamines in rubbers

The study of the possibilities of supercritical fluid extraction (SFE) with N-nitrosamines in rubbers has been carried out. Home-made materials fortified with several N-nitrosamines were prepared in order to optimize the SFE parameters. A Plackett-Burman design was employed to evaluate the influence of those parameters to be controlled in SFE, such as pressure, temperature, static and dynamic time, restrictor temperature and volume of modifier while CO2 was used as the extraction fluid. An extra central composite design for the main factors (according to the previously obtained results) was also developed in order to refine the best supercritical conditions for the extraction of N-nitrosamines from rubbers. Gas chromatography with a nitrogen and phosphorus sensitive detector was used to achieve sensitivity and limits of detection for the concentrations expected in plastic materials. The proposed analytical method has shown to be useful in the determination of N-nitrosamines even for complex matrices.