Splitless injection in capillary supercritical fluid chromatography

A splitless injection technique, allowing 0.5 μl injections on 50 μm i.d. columns, has been developed.     

Concurrent solvent recondensation large sample volume splitless injection

Concurrent Solvent Recondensation Large Sample Volume (CRS‐LV) splitless injection overcomes the limitation of the maximum sample volume to 1–2 μL valid for classical splitless injection. It is based on control of the evaporation rate in the vaporizing chamber, utilization of a strong pressure increase in the injector resulting from solvent evaporation, and greatly accelerated transfer of the sample vapors from the injector into the inlet of an uncoated precolumn by recondensation of the solvent. The sample vapors are transferred into the column as rapidly as they are formed in the injector (concurrent transfer). 20–50 μL of liquid sample is injected with liquid band formation. The sample liquid is received by a small packing of deactivated glass wool positioned slightly above the column entrance at the bottom of the vaporizing chamber. Solvent evaporation strongly increases the pressure in the injector (auto pressure surge), provided the septum purge outlet is closed and the accessible volumes around the vaporizing chamber are small, driving the first vapors into the precolumn. Transfer continues to be fast because of recondensation of the solvent, obtained by keeping the oven temperature below the pressure‐corrected solvent boiling point. The uncoated precolumn must have sufficient capacity to retain most of the sample as a liquid. The experimental data show virtually complete absence of discrimination of volatile or high boiling components as well as high reproducibility.     

Splitless injection of large volumes of aqueous samples – A basic feasibility study

Experiments with splitless injection of large volumes of aqueous samples by the overflow technique have shown that an organic co-solvent is necessary to help the packing material (Tenax) retain the liquid. With 25–30% propanol or 15–20% 2-butoxyethanol, some 800 μl can be injected into a 5 mm i.d. liner. The application of the method is restricted to components eluting above ca 200 °C.     

Splitless injection of up to hundreds of microliters of liquid samples in capillary GC: Part II,experimental results

Sample evaporation in splitless injection of large volumes is rapid: depending on the experiment, results indicate that 200 μl of hexane, for instance, evaporates in 2–10 s, producing vapor at a rate of many hundreds of milliliters per minute. A 60 × 4 mm packed bed of 20–35 mesh Tenax TA enabled injection of 200 μl volumes of all solvents tested, and even 1 ml injections were possible provided they were performed over a period of 30 s. Retention of volatile sample components depends on the sample solvent, the injection volume, and the injection speed, but only little on the injector temperature. Losses of n-tridecane varied from hardly 15 % (when dissolved in pentane) to ca 60 % (ethyl acetate); losses of n-heptadecane were usually below 20 %. The column temperature during injection should be at least ca 20–30°C above the standard solvent boiling point.     

Splitless injection of large volumes: Improved carrier gas regulation system

The classical vaporizing injector has been modified for splitless injection of large volumes: during solvent evaporation in the packed vaporizing chamber, the carrier gas supply is interrupted and the septum purge outlet fully opened. This prevents vapors penetrating the gas regulation system and keeps the pressure increase in the injector to a minimum.     

Splitless injection of large volumes of aqueous samples: Further experience. Experiments on analyzing triazines by direct injection of drinking water

Conditions were optimized for the introduction of large volumes of drinking water by splitless injection with vapor overflow, experimenting with the determination of triazines. No co-solvent was added, and the maximum injection volume was 400 μl. A vapor outlet beyond a coated precolumn was used to discharge water vapors released belatedly from the packing. Using alkali flame ionization detection (AFID), detection limits were around 0.5 μg/l.     

Separation of 28 to 114°C hydrocarbons with glass capillary columns

Techniques have been developed for the rapid separation (about 20 minutes) of the 39 compounds in crude petroleums, or petroleum distillates, which boil between 28 and 114°C. A 300 meter glass column (0.25 mm i.d.) which is etched, coated with a mixture of normal hexadecane and Kel-F10157 is utilized to perform this separation at room temperature. The separations obtained with this non–polar liquid mixture and the «inert» glass surface are much more rapid than those previously obtained with stainless steel capillary columns.     

A new configuration for coupling purge-and-trap/cryogenic focusing/capillary column gas chromatography with splitless injection mode

A new configuration for coupling a purge-and-trap unit to a capillary column gas chromatograph via a cryogenic focusing interface has been developed. In this configuration, the precolumn of the cryogenic focusing interface was inserted through the septum of a split/splitless injection port where it served as both sample transfer and carrier gas supply lines. The injection port of the gas chromatograph was modified by plugging the carrier gas and the septum purge lines. This configuration allowed for the desorption of analytes at high flow rates while maintaining low, analytical-column flow rates which are necessary for optimum capillary column operation. The capillary column flow rate is still controlled by the column backpressure regulator. Chromatograms of purgeable aromatics exhibited improved resolution, especially for early eluting components compared to those obtained by direct liquid injection using the normal splitless injection mode. Quantitative sample transfer to the analytical column afforded excellent linearity and reproducibility of compounds studied.     

Comparison of On-Column and Splitless Injections for the Capillary Gc Quantitation of Organics Extracted from Landfill Leachatesl

Abstract

An extensive study of the organic components of the leachate from the University of Connecticut landfill has been carried out. A modification of EPA Method 625 for base/neutral extractable organics was used to obtain both the gas chromatographic profiles and the mass spectrometric identification of the organics in groundwater samples from six test wells and several private wells in the vicinity of the landfill. A characteristic fingerprint representing a number of components was consistently found in the analysis of the landfill leachate but not in the drinking water of the private residences located on an adjoining road. Gas chromatographic parameters for optimum qualitative and quantitative analysis of field samples were determined using an acetone solution of the model leachate sample. It was confirmed that the on-column injection mode resulted in greater flame ionization detector (FID) response and more reproducible peak areas than the splitless mode. The major variable in obtaining reproducible data was the field sampling at the landfill, not the solvent reduction step or the injection mode used to introduce the sample into the gas chromatograph.     

Large volume splitless injection with concurrent solvent recondensation: keeping the sample in place in the hot vaporizing chamber

An injector liner packed with a plug of glass wool is compared with a laminar and a mini laminar liner for large volume (20-50 microL) splitless injection with concurrent solvent recondensation (CSR-LV splitless injection). Videos from experiments with perylene solutions injected into imitation injectors show that glass wool perfectly arrested the sample liquid and kept it in place until the solvent had evaporated. The sample must be transferred from the needle to the glass wool as a band, avoiding 'thermospraying' by partial solvent evaporation inside the needle. The liquid contacted the liner wall when the band was directed towards it, but from there it was largely diverted to the glass wool. In the laminar liners, part of the liquid remained and evaporated at the entrance of the obstacle, while the other proceeded to the center cavity. Vapors formed in the center cavity drove liquid from the entrance of the obstacle upwards, but the importance of such problems could not be verified in the real injector. Some liquid split into small droplets broke through the obstacle and entered the column. Breakthrough through the laminar liners was confirmed by a chromatographic experiment. An improved design of a laminar liner for large volume injection is discussed as a promising alternative if glass wool causes problems originating from insufficient inertness.     

Automated glass capillary gas chromatographic analysis of PCB and organochlorine pesticide residues in agricultural products

Complicated PCB mixtures can be separated in individual compounds using glass capillary gas chromatography, (GC)². Depending on extraction and clean-up procedure it is also possible to separate and determine organochlorine pesticides at the same time. This (GC)² technique can be used to determine the contents of individual chlorinated biphenyls in milk products and animal feedstuffs and in the analysis of complicated extracts of soil and vegetable material. Practical aspects concerning connection of the capillary, automatic splitless injection, repeatability of the retention time, quality of the column with respect to separation and adsorption and degradation of DDT are discussed. The detection of individual chlorinated biphenyls is possible at the ppb level in fats and vegetable materials, using an extraction and clean-up procedure, based on saponification of the sample. Preliminary results for milk, obtained from several areas, are shown.     

Interlaboratory studies of the determination of selected chlorobiphenyl congeners with capillary gas chromatography using splitless- and on-column injection techniques

The Community Bureau of Reference has organized a collaborative interlaboratory project to improve the analytical protocol for some specific chlorobiphenyls (CBs) within the European Community (EC). A series of test procedures were prescribed to optimize the gas chromatographic conditions for splitless and on-column injection, which substantially improved the quality of data. Important parameters included the initial column and injector temperatures and the choice of the polarity of the stationary phase. In a study with cleaned eel-fat extracts, coefficients of variation for reproducibility CV(R) ranging from 11 to 24% at the 0.04–0.3 mg/kg level per CB congener were obtained. No significant difference could be found between splitless- and on-column injection.     

Splitless injection of up to hundreds of microliters of liquid samples in capillary GC: Part 1, concept

If a sample evaporates by flash vaporization in an empty injector insert, the solute material is well mixed with the expanding solvent vapors and the maximum injection volume is determined by the requirement that no vapors must leave the vaporizing chamber. If evaporation occurs from a surface (e.g., of Tenax packing), however, the solvent evaporates first. The site of evaporation is cooled to the solvent's boiling point, and the cool island formed in the hot injector retains solutes of at least intermediate boiling point (visually observed for perylene). Solvent vapors, free from such solutes, may now expand backwards from the injector insert and leave through the septum purge exit. When solvent evaporation is complete, the site of evaporation warms up, causing the high boiling solutes to evaporate and to be carried into the column by the carrier gas. The technique somewhat resembles PTV injection, but is performed using a classical vaporizing injector.