Investigation of parameters affecting the on-line combination of supercritical fluid extraction with capillary gas chromatography

Two different injectors, a split/splitless injector and a programmed temperature vaporizer (PTV) injector were investigated as the interface in on-line supercritical fluid extraction (SFE)-capillary gas chromatography (cGC). The parameters affecting the chromatographic peak shapes as well as the quantitative performance of the interfaces in on-line SFE-cGC were identified and studied. Particular attention was paid to the case where modified extraction fluids were used. Experiments were performed on two different samples. The first sample consisted of PAHs spiked on sand at different concentration levels. The other sample was a polymeric material.     

Use of open-tubular trapping columns for on-line extraction–capillary gas chromatography of aqueous samples

The applicability of open-tubular trapping columns for on-line extraction–capillary GC analysis is evaluated. The extraction step involves sorption of the analytes from water into the stationary phase of an open-tubular column, removal of the water by purging the trap with nitrogen, and desorption of the analytes with an organic solvent. The effect of swelling of the stationary phase with organic solvents on the retention power of the trap is studied. When using pentane or hexane as swelling agent breakthrough volumes of at least 10 ml can easily be obtained for non-polar compounds. For a number of medium polarity compounds breakthrough volumes of 5 ml can be achieved when chloroform is used as the swelling agent. The required drying time is less than 1 minute. Quantitative desorption requires only 75 μl of organic solvent. Solvent elimination prior to transfer to the GC column is carried out using a PTV injector and a multidimensional GC system. The system is applied for the analyses of river water, urine, and serum samples.     

Coupling device for desorption of drugs from solid-phase extraction-pipette tips and on-line gas chromatographic analysis.

Solid-phase extraction-pipette tips were used for micro solid-phase extraction of lidocaine and diazepam. Off-line desorption was done after in-vial collection for reference purposes, whereas with on-line desorption the eluate was directly introduced in the gas chromatograph. With both methods the total eluate (100 microl) was introduced into the GC system, which was equipped with a programmed-temperature vaporiser (PTV) for large volume injection. For on-line desorption a laboratory-made coupling device was developed to connect the pipette tips with the injector of the PTV. The coupling device was applied successfully since no leakage occurred at the connection of the coupling device and the pipette tip. No significant differences in recovery of lidocaine and diazepam and in presence of impurities were observed between chromatograms obtained with either off-line or on-line desorption. Preliminary experiments with standard solutions showed recoveries of about 75% for a concentration level of 1 microg/ml. The system seems particularly suitable for high-throughput analysis.     

A simple approach to on-line oxidative pyrolysis-capillary gas chromatography—Mass spectrometry

Summary A simple and robust approach to on-line oxidative pyrolysis-capillary gas chromatographymass spectrometry (OxPYR-CGC-MS) analysis is presented. Only minor adaptations on a conventional filament pyrolysis unit are required. Air is introduced into the pyrolyzer through a bypass-valve during pyrolysis and the degradation products are focused in a cryo-cooled programmed temperature vaporization (PTV) injector. Before GC analysis, the system is switched back to helium and after equilibration PTV injection is carried out. The potential of the system is illustrated with normal and oxidative pyrolyses of polystyrene (PS) and polyethylene (PE).     

Some practical experiences in the use of a solventless injection system for packed column supercritical fluid chromatography

The operating characteristics of a solventless injector for packed column supercritical fluid chromatography are described. Successful operation depends on the difference between the volatilities of the analytes and the solvent or matrix being sufficient for their separation by gas purging in a thermostatted precolumn, and also on the existence of an effective re-focusing mechanism at the head of the analytical column for the sample dissolved in liquid or supercritical fluid carbon dioxide. The latter is easily achieved in density programmed operation by stationary phase trapping at low fluid densities or phase ratio trapping by changing the temperature at low to moderate fluid densities. The solventless injector can easily accommodate sample volumes from 1–100 μl and is easily adapted for in-line derivatization using reagents which can, after reaction, be eliminated by gas purging. For general purposes the solventless injector can be used to overcome most of the problems encountered when rotary valve loop injectors are used with small bore packed columns, and will probably replace this type of injector as the injector of choice for supercritical fluid chromatography with mobile phases of low polarity.     

On-line coupling of subcritical water extraction with high-performance liquid chromatography via solid-phase trapping

Although ambient water is very polar and cannot dissolve many organic species, water at elevated temperatures behaves like a polar organic solvent. Thus, subcritical water has been proven to be an effective extraction fluid for several classes of organic compounds. While solvent trapping was used to collect the extracted analytes in most of previous subcritical water extractions, sorbent trapping has also been developed for subcritical water extraction. In this study, an on-line system for subcritical water extraction and high-performance liquid chromatography (HPLC) was built and tested. A sorbent trap was used as the interface between subcritical water extraction and HPLC. Several shut-off valves have been utilized to switch the system from one mode to another (e.g., from the extraction mode to HPLC mode). The coupling technique of subcritical water extraction and HPLC eliminates the liquid-liquid extraction used in solvent trapping subcritical water extraction and provides higher sensitivity. Compared to the off-line system reported in an earlier work, the operation of this on-line system is even easier. Some peak broadening occurred after the coupling the water extraction with HPLC for the analytes studied. The performance of this on-line system was evaluated by the extraction and determination of caffeine, nitrotoluenes, polychlorinated biphenyls, chlorophenols and anilines.     

Use of a temperature programmed injector with a packed liner for direct water analysis and on-line reversed phase LC–GC

A system is described that allows the introduction of large volumes of water samples in capillary GC. Water elimination is carried out in the solvent split mode in a PTV injector with a packed liner. Two ways of separating water and analytes, i.e. evaporative and non-evaporative (solid-phase extraction), are compared. Sampling in the solid-phase extraction mode is favorable both in terms of recovery as well as with regard to sampling time. Quantitative recovery is obtained for priority pollutants ranging in volatility from dimethyl-phenol to phenanthrene. Losses occur for more volatile compounds, but even for these compounds the repeatability of the recoveries remains acceptable. With the system described here, water samples up to at least 1 ml of water can be directly analyzed. The detection limits are in the sub-ppb range.     

Optimization of dynamic headspace sampling for the analysis of trace volatile components of grape juice: Use of a PTV injector for intermediate trapping

The use of a programmed temperature vaporizing (PTV) injector has been evaluated for the on-line concentration and injection of trace organic compounds either sampled from the head-space above grape juices or purged from solution. The Simplex method was used to improve the sensitivity of the method by optimization of the experimental conditions.     

Analysis of 35 priority semivolatile compounds in water by stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry. I. Method optimisation

A multiresidue method for the determination of 35 organic micropollutants (pesticides and polycyclic aromatic hydrocarbons) in water has been optimised using stir bar sorptive extraction (SBSE) and thermal desorption coupled to capillary gas chromatography-mass spectrometry (GC-MS). In the present work, the different parameters affecting the extraction of the analytes from the water samples to the PDMS-coated stir bars and optimisation of conditions affecting thermal desorption are investigated. The optimised conditions consist of a 100-ml water sample with 20% NaCl addition extracted with 20 mm length x 0.5 mm film thickness stir bars at 900 rpm during 14 h at ambient temperature. Desorption is carried out at 280 degrees C during 6 min under a helium flow of 75 ml/min in the splitless mode while maintaining a cryofocusing temperature of 20 degrees C in the programmed-temperature vaporisation (PTV) injector of the GC-MS system. Finally, the PTV injector is ramped to a temperature of 280 degrees C and the analytes are separated in the GC and detected by MS using full scan mode (m/z 60-400). Under the described conditions, the good repeatability, high analyte recoveries and robustness, make SBSE a powerful tool for routine quality control analysis of the selected semivolatile compounds in water samples.     

Rhodium and palladium β-diketonate determination with on-line supercritical fluid extraction-high performance liquid chromatography via solid phase extraction

 An on-line system of supercritical fluid extraction (SFE) and high performance liquid chromatography (HPLC) via solid phase extraction (SPE) is described for the determination of palladium and rhodium 2,2,6,6-tetramethyl-3,5-heptanedione-(thd) as well as rhodium-acetylacetonate-(acac) and benzylacetonate-(bzac) chelates. The chelates were extracted with supercritical CO₂ from sand and humic acid, concentrated on SPE cartridges and analysed with HPLC. Two cartridge materials were tested and compared to off-line trapping. The percentage of the breakthrough and cartridge retained material were measured in liquid dichloromethane. The SFE conditions could be optimized to separate metal chelates during the extraction. The supercritical fluid (SF) behaviour of different ligands on rhodium were investigated. Received: 19 July 1996/Revised: 11 December 1996/Accepted: 14 December 1996     

Construction of on-line supercritical fluid extraction with reverse phase liquid chromatography–tandem mass spectrometry for the determination of capsaicin

A column-switching system, composed of supercritical fluid extraction (SFE) and reverse phase liquid chromatography/mass spectrometry (RPLC/MS) was constructed for on-line extraction and reverse-phase separation of capsaicinoids in capsicum fruits.     

Monitoring industrial wastewater by online GC-MS with direct aqueous injection

An online GC–MS-system for automated monitoring of crude wastewater at a complex chemical production site is presented. The modular system is, in principal, based on commercial equipment, but utilizes a special, two-stage injector, which consists of a splitless vaporization chamber on top of a PTV injector filled with Tenax. This set-up enables direct injection of wastewater. Almost 140 volatile and semi-volatile compounds are calibrated down to 1 mg L⁻¹, which is sufficient for analysis of the influent of the wastewater-treatment plant. Two instruments analyze alternately, every 20 min, and the instrument cycle time is 40 min. The quantitative results are transferred to a database which is connected to a process-control system. Depending on the nature and concentration of a compound, an alarm can be generated and the wastewater stream can be diverted into an “off spec tank” if necessary. The GC–MS-system operates quasi-continuously with a system availability >98%. Data quality is automatically controlled in each run and by daily analysis of a quality-control sample. The development of a novel stacked PTV–PTV injector design to expand the range of analytes to selected basic compounds is described.     

Programmable Temperature Vaporizer (PTV) Applied to the Triglyceride Analysis of Milk Fat

The PTV (Programmable Temperature Vaporizer) is a split/splitless injector which allows the sample to be introduced at a relatively low temperature, thus affording accurate and reproducible sampling. After injection the PTV is rapidly heated to transfer the vaporized components into the capillary column. This type of injector has proved to be an efficient tool for the evaluation of fatty acids, essential oils, and pesticides in food analysis. In this work the suitability of PTV for the analysis of milk fat purity by the Official EU method was evaluated. This method is based on the gas chromatographic determination of triglycerides only according to their total number of carbon atoms followed by the application of formulae deriving from multiple linear regressions. The analysis is currently carried out with a packed column or a short capillary column and an on-column injection system. Several samples of pure milk fat and mixtures of milk fat with foreign fat were analyzed with the same capillary column and by using both PTV and on-column injection systems. The results show that the gas chromatographic profile obtained by PTV is comparable with that obtained by the on-column injector, while repeatability and reproducibility data meet the requirements indicated in the Official Method. Therefore, this study demonstrates that it is possible to use the PTV instead of the on-column injector to determine the purity of milk fat with this method.     

Comparison of methods for quantitative analysis of additives in low-density polyethylene using supercritical fluid and enhanced solvent extraction.

On-line supercritical fluid extraction-supercritical fluid chromatography (SFE-SFC) with cryogenic trapping was used to extract and separate five additives from a low-density polyethylene (LDPE) sample. A glass tube filled with glass wool afforded excellent collection efficiency for the extracted analytes. Additive spiked sand was employed to optimize the various parameters of the on-line SFE-SFC system. Calibration curves from the spiked sand studies for on-line SFE-SFC were obtained with good linearities for quantitation. Results obtained on additives in LDPE from on-line SFE-SFC were comparable to those from off-line SFE-HPLC and off-line enhanced solvent extraction (ESE)-HPLC for all additives except Irganox 1076. However, the precision obtained with on-line SFE-SFC was lower than that from off-line SFE-HPLC and off-line ESE-HPLC due to the small sample size employed in the on-line system. Considerable clean-up of the ESE extract was required prior to chromatographic analysis. On-line SFE-SFC minimized the sample handling and eliminated the use of organic solvent. Despite the lower than expected precision, the on-line SFE-SFC method for quantitation of polymer additives appears to be reliable and robust for application in routine quality control analysis.     

Vaporising systems for large volume injection or on-line transfer into gas chromatography: Classification, critical remarks and suggestions

Techniques for large volume introduction of liquid samples into capillary gas chromatography (GC) follow a small number of principals. Vaporising systems, vapour discharge modes and methods for solvent-solute separation are classified and evaluated.

Presently, programmed temperature vaporising (PTV) solvent split injection is the preferred method if on-column techniques cannot be applied. Critical re-evaluation suggests, however, that solvent evaporation and solvent-solute separation should be performed in separate compartments and optimized individually. Permanently hot chambers offer the highest capacity for solvent evaporation. The preferred techniques for solvent-solute separation are stationary phase focusing in a coated capillary or solvent trapping in an uncoated capillary precolumn. The vaporising chamber-precolumn solvent split-gas discharge system is proposed for large volume injection and on-line transfer of water-containing solvent mixtures, and in-line vaporiser-precolumn solvent split-overflow system for most on-line transfer applications.     

On-line size exclusion chromatography-pyrolysis-gas chromatography-mass spectrometry for copolymer characterization and additive analysis

On-line coupled size exclusion chromatography-pyrolysis gas chromatography mass spectrometry (SEC-Py-GC-MS) is studied as a novel tool for the characterization of complex polymer samples. An automated system for on-line SEC-Py-GC-MS allowing transfer of multiple fractions was developed based on stop-flow operation of the SEC dimension, syringe-based transfer of the SEC fraction to the GC instrument and solvent elimination with subsequent pyrolysis in a programmed temperature vaporization (PTV) injector. After optimization the system was applied to the characterization of a complex terpolymer composed of very similar monomers. The use of the system for combined pyrolysis and additive analyses in polycarbonate was also demonstrated. Results obtained with the new method indicate the interesting potentials of the method for detailed characterization of polymeric materials.     

Trace analysis of complex organic mixtures using capillary gas-liquid chromatography and the dynamic solvent effect

A sampling system for high resolution gas-liquid chromatography, based on the dynamic solvent effect, is described. Volatiles are accumulated off-line in a concentrator/injector and delivered to the column using an on-line inlet. Volatiles may be accumulated from gaseous or liquid matrices; they may be transferred to these by gas sparging or solvent extraction of any type of sample. The sampling technique is quantitatively precise; e.g. coefficients of variation of peak percentage areas better than 5% for a range of solutes at a concentration of 2:10⁷. Examples of the application of the sampling system are presented.     

Trace analysis by intermediate trapping with a modified programmable temperature vaporizer

Summary A system for quantitative transfer of thermally desorbed substances onto capillary columns is described. During desorption substances are intermediately trapped in a programmable temperature vaporizer (PTV) cooled to –150°C. After condensation the injector is heated to a preset temeprature in a few seconds. Various applications are mentioned.Extract from planned Thesis of E. Jülich with authorization of the Faculty     

Gas chromatographic water analysis by direct injection of large sample volumes in an adsorbent-packed PTV injector

Chromatographia - A GC method is described for the determination of pollutants in aqueous samples by direct enrichment out of large sample volumes in a PTV injector. The vaporized water is...     

并行捕集柱SFE-HPLC在线联用系统的构建及应用

在前期研究的基础上, 发展了采用自动十通阀/并行捕集柱接口构建了SFE和HPLC在线联用的新装置, 并利用该系统对灵芝子实体的超临界萃取过程进行实时监测.