Unravelling the composition of very complex samples by comprehensive gas chromatography coupled to time-of-flight mass spectrometry. Cigarette smoke

The potential and current limitations of comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC x GC-TOF-MS) for the analysis of very complex samples were studied with the separation of cigarette smoke as an example. Because of the large number of peaks in such a GC x GC chromatogram it was not possible to perform manual data processing. Instead, the GC-TOF-MS software was used to perform peak finding, deconvolution and library search in an automated fashion; this resulted in a peak table containing some 30000 peaks. Mass spectral match factors were used to evaluate the library search results. The additional use of retention indices and information from second-dimension retention times can substantially improve the identification. The combined separation power of the GC x GC-TOF-MS system and the deconvolution algorithm provide a system with a most impressive separation power.     

A trapping column for the coupling of reversed-phase liquid chromatography and capillary gas chromatography

A new technique for coupling reversed-phase liquid chromatography (RPLC) with gas chromatography is described. A fraction eluting from an RPLC column is trapped on a short column packed with polymeric adsorbent. After the mobile phase has been displaced with water, the analytes are desorbed with ethyl acetate. Following a delay time to enable the water to be flushed to waste, the ethyl acetate containing the analytes is introduced into the gas chromatograph under conditions suitable for partially concurrent solvent evaporation, i.e. below the solvent boiling point and at a rate just exceeding the evaporation rate. Post-column addition of water to the RPLC eluent helps to prevent breakthrough of compounds which are only modestly retained on the trapping column. The relationship between the capacity factors of the analytes on the trapping column and the required dilution factor is discussed. Polycyclic aromatic hydrocarbons are used as test compounds to study the system.     

Miniaturized automated matrix solid-phase dispersion extraction of pesticides in fruit followed by gas chromatographic-mass spectrometric analysis

In this study a simple and fast miniaturized automated matrix solid-phase dispersion method for the sample preparation and quantitative extraction of pesticides was developed and evaluated. Only 25 mg of sample and 100 microl of organic solvent were used per analysis for this new miniaturized set-up. The extracts were subsequently analysed by GC-MS without any further purification. The method was optimized for oranges and tested for the determination of a variety of organophosphorus pesticides and a pyrethroid at concentration levels below the maximum residue levels set by the European Union and authorities in The Netherlands. The limits of detection were 4-90 microg/kg. The recoveries for pesticides in orange were 83-118% and the relative standard deviations for the total procedure were 10-13% (n=4) at the limit of quantification. The feasibility of the developed method for apple, pear and grapes was also studied. Equally good results were obtained, but for apple the washing step should be omitted.     

Automated determination of pyrethroid insecticides in surface water by column liquid chromatography with diode array UV detection, using on-line micelle-mediated sample preparation

A liquid chromatographic method using gradient elution and diode array UV detection for the trace level determination of seven synthetic pyrethroids is described. The procedure involves automated on-line preconcentration on precolumns containing octadecylbonded silica using a Prospekt. Although the analytes display a mixed hydrophobic/hydrophilic behaviour, both breakthrough on the precolumn and adsorption to inner walls and surfaces can be prevented by adding Brij-35, a neutral surfactant, to the aqueous sample. The procedure has been tested for the analysis of surface water; detection limits typically are at the sub-g/l level and repeatability is excellent. The automated system is robust and there are no maintenance problems.Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday     

Determination of organophosphorus pesticides in aqueous samples by on-line membrane disk extraction and capillary gas chromatography

Summary A fast and simple procedure for the analysis of aqueous samples by on-line membrane disk extraction and capillary gas chromatography (GC) is presented. As an example, organophosphorus pesticides are preconcentrated from aqueous samples on three 0.5 mm thick, 4.2 mm diameter extraction disks. The layers are dried by a stream of nitrogen (10–15 min; ambient temperature). Desorption of the analytes is carried out with ethyl acetate which is directly introduced into a retention gap under partially concurrent solvent evaporation conditions, using an early solvent vapour exit. The final analysis is carried out by GC with thermionic detection. The technique is applied to the determination of a series of organophosphorus pesticides in tap water and water from two European rivers. With a sample volume of only 2.5 ml, detection limits of 10–30 ppt are achieved in tap water and of 50–100 ppt in river water.     

Comparison of comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry and gas chromatography-mass spectrometry for the qualitative characterisation of roasted barley by solid-phase microextraction

Volatile compounds of roasted barley used in the production of barley coffee, the most common coffee substitute, were analysed by using solid-phase microextraction (SPME) followed by GC-MS and comprehensive GC x GC-TOF-MS, respectively. The optimised SPME extraction conditions in terms of selection of the fibre coating, extraction time and extraction temperature allowed to obtain the highest GC response, thus enhancing the identification capabilities of the developed method. As for the SPME-GC x GC-TOF-MS analysis, 64 compounds with similarity, reverse and probability values above 800, 900 and 6000, respectively, were identified, by using a polar x apolar column set combination; in contrast, GC-MS was able to identify a lower number of compounds, i.e. 40 volatiles.     

Trace-level determination of polar flavour compounds in butter by solid-phase extraction and gas chromatography-mass spectrometry.

Volatile compounds are responsible for the aromas of butter. A simple technique for the determination of these components is described which is based on solid-phase extraction (SPE) after melting of the butter and separation of the aqueous phase from the fat. Volatile flavours present in the water fraction are collected by off-line SPE on cartidges packed with a copolymer sorbent. After desorption with 500 microliters of methyl acetate, 1-microliter aliquots are quantified and/or identified by gas chromatography-mass spectrometry. The procedure was tested with respect to recovery, linearity and limit of detection in real-life samples using five polar model analytes. It allows the characterisation of polar flavour compounds in butter prior to and after heat treatment at 170 degrees C. From the five model compounds, vanillin, traces of diacetyl and maltol were found to be present in the butter samples. After heat treatment 500-1000-fold increased concentration of maltol, and substantial amounts of furaneol were detected.