Search

Some aroma compounds found in alcoholic beverages are characteristic of a certain beverage (i.e. 2,4-decadienoic acid ethyl ester is characteristic of pear spirit and 5-butyltetrahydro-4-methylfuran-2-on “whiskey lactone” is characteristic of aged spirits like whiskey). These substances were detectable in beverages but not in blood samples. The aim of this investigation was to find a sensitive sampling technique for aroma compounds in whole blood samples. This technique may be used in forensic toxicology for examination of drinking claims. The method comprises dynamic headspace sampling using a purge and trap concentrator, followed by quantitative gas chromatography–mass spectrometry (dynamic HS–GC–MS). The influence of sample preparation, trap adsorbents and sample temperature as well as desorption time and purge time on the quality of the analytical results were investigated. The following optimal parameters were determined: stirred and diluted whole blood sample without salt addition, use of Carbotrap C as trap material, sample temperature at 80 °C, desorption time 20 min and purge time 30 min. These optimal parameters were used for the determination of detection limits (LOD). The LOD of aroma compounds by means of dynamic headspace sampling were compared with the results of conventional sampling: the static headspace technique. Limits of detection for the aroma compounds with conventional static headspace GC are in the range 400–10,000 μg L−1. Dynamic headspace–GC was found to be a more sensitive sampling technique for most of the aroma compounds investigated (e.g. C4–C8 ethyl esters, benzoic acid ethyl ester, linalool oxide and 4-ethylguaiacol) with detection limits between 1 and 50 μg L−1, but there were also limits to the sampling of substances with lower volatility like decanoic acid ethyl ester, 2,4-decadienoic acid ethyl ester, eugenol and whiskey lactone with detection limits of about 1,000 μg L−1.

The present study is concerned with the application of nonaqueous capillary electrophoresis (NACE) with electrochemical detection (ED) to the separation and quantitative determination of hydrazine (Hy) and its methyl derivatives. The best performance of NACE-ED was found when using 4 mM sodium acetate/10 mM acetic acid/methanol: acetonitrile = 1:2 as the running buffer, with a bare platinum working electrode set at +1.0 V in an end-column amperometric detection cell. The choice and ratio of suitable solvents for the separation and injection media played an essential role for the performance characteristics of the method. The limits of detection for Hy, methylhydrazine, symmetrical dimethylhydrazine, and unsymmetrical dimethylhydrazine were 5, 2, 12, and 1 ng/mL, respectively. This is between one and two orders of magnitude lower than that achieved by previously reported CE-ED methods in aqueous buffer systems in conjunction with various types of chemically modified electrodes. The practical utility of the new NACE-ED methodology is demonstrated in terms of the determination of traces of Hys in spiked environmental samples containing a wide range of explosives and related compounds.

To enable high sample throughput, an automated solid-phase microextraction (SPME) method coupled with GC-MS for the trace analysis of technical nonylphenol, bisphenol A and 17alpha-ethinylestradiol was developed. The extraction performance of different SPME fibre coatings was examined, with polyacrylate proving most suitable. Although study of the extraction time showed that the analytes have not reached equilibrium after 3 h, as a compromise an extraction time of 1 h was applied in all the experiments with detection limits between 0.04 and 1 microg l(-1) for wastewater effluent. The mean reproducibility of the technique is 8% RSD. Carry-over effects are negligible. The linearity of calibration curves ranges over three orders of magnitude. The method was tested for determining the analytes in influents and effluents of constructed wetland plants and in model wastewater used in laboratory experiments.

Headspace solid-phase microextraction (HS-SPME) has been successfully applied to the determination of perfume components in scented candle wax, liquid laundry detergent, and fabric softener. Different fiber coatings (100 μm polydimethylsiloxane, 50/30 μm divinylbenzene/Carboxen/polydimethylsiloxane, 70 μm Carbowax/divinylbenzene, and 85 μm polyacrylate) were tested and the extraction conditions were optimized. For most compounds extraction efficiency, reproducibility, and long-term stability were highest for polydimethylsiloxane. The compatibility of SPME with fast gas chromatographic separation was investigated. The speed of conventional gas chromatography was increased by a factor of 2.5, without loss of separation efficiency, simply by reducing the column length and inner diameter and adjusting the separation conditions by use of method translation software. It was demonstrated that SPME is a suitable sample-introduction technique for fast GC if split injection is used.

This work describes methodical studies of thermally assisted hydrolysis and methylation (THM) of fatty acids (FA) and triglycerides comparing different derivatization reagents, such as tetramethylammonium hydroxide (TMAH), tetramethylammonium acetate (TMAAc), trimethylsulfonium hydroxide (TMSH), trimethylphenylamine hydroxide (TMPAH), and (m-trifluoromethylphenyl) trimethylammonium hydroxide (MethPrep 2). The performance of these reagents using different injection techniques, such as pyrolysis, hot split injection, and programmed temperature vaporization (PTV) has been investigated.

Thermally assisted hydrolysis and methylation (THM) provides an interesting alternative to other derivatizing sample preparation techniques because of its simplicity and rapidness. The paper presents THM–GC/MS data obtained from standard compounds (cholesteryl stearate, 2-hydroxypalmitic acid) and several types of wax (candelilla wax, beer wax, lanolin, beeswax) using tetramethylammonium hydroxide (TMAH) as reagent. Application of tetramethylammonium acetate (TMAAc) instead of TMAH enables selective analysis of free fatty acids in the presence of esters. Comparison of the results with those obtained from Py–GC/MS illustrates that THM provides a much higher extent of information. The thermochemolytic behaviour of several wax compounds is discussed. THM yields may differ from compound to compound due to specific thermal and chemical behaviour. While structurally simple wax esters, e.g. cholesteryl stearate, gave very efficient conversion within a wide temperature range between 350 and 600°C, compounds of less thermal stability (e.g. 2-hydroxyfatty acids) yielded substantial amounts of pyrolysis products (aldehydes) even at the lowest temperature applied (350°C). Some phytosterols present in candelilla wax showed less affinity to TMAH and were only partly converted into methyl ethers. Various applications of THM–GC/MS are described: analysis of lipid based leather polish, identification of wax content in spots in ancient Egyptian textiles, profiling of pharmaceutical lanolin batches, characterization of aging processes in lanolin. Fingerprints and characteristic marker compounds were employed for discrimination and identification purposes.

AGC method has been developed for the analysis of tricholoroacetic acid (TCA) in water samples. It entails large-volume injection (LVI) and programmed-temperature vaporization (PTV) of water samples, thermal decarboxylation of TCA to chloroform in the injector, and GC-ECD analysis of the decarboxylation product. Conditions such as final injector temperature, splitless time, and injection volume were optimized. The limit of detection is approximately 0.1 μg L−1 Several real samples were analyzed. The method presented is an easy means of determination of TCA and eliminates sample-preparation steps such as extraction and derivatization.

Laboratory experiments have been performed to examine the potential of adsorptive enrichment thermal desorption and gas chromatography for the analysis of low molecular-weight oxygenated compounds in gaseous samples. The experiments were conducted with test atmospheres containing, for example, acetaldehyde, propionaldehyde, acrolein, methacrolein, and acetone. The suitability of the graphitized carbon blacks Carbotrap X and Carbograph 5 for sampling these compounds was tested. In this context the influence of humidity on the recovery of the analytes and on the storage stability of the loaded adsorbent tubes over a period of seven days under different storage conditions was investigated. Losses of up to 60% propionaldehyde and acrolein were observed for Carbotrap X, even immediately after sampling. In contrast Carbograph 5 seems promising for the sampling of low molecular-weight oxygenated compounds, although with some limitations. The laboratory investigations were proved by use of an interlaboratory experiment.

Systematic investigations were performed to study the dependence of the extraction efficiency of persistent organic pollutants (POPs), including chlorobenzenes, HCH isomers, DDX, PCB congeners, and PAHs, on the accelerated solvent extraction (ASE) operating variables solvent and temperature. Mixed soil samples from two locations with considerable differences in soil properties and contamination in the Leipzig-Halle region (Germany) were used. The objective was to optimize ASE for the extraction of POPs from real soil samples and to improve on the results achieved with Soxhlet extraction (SOX). Solvents with differing polarities were tested. Quadruple and triple determinations were performed on the two soils, respectively, between 20 and 180 degrees C in 20 degrees C steps. All the results were compared with those obtained by SOX, as well as, in some cases during preliminary studies, by ultrasonic extraction (USE). In ASE, the optimum conditions proved to be two extraction steps at 80 and 140 degrees C (average RSD 10.7%) with three static cycles (extraction time 35 min) using toluene as solvent and at a pressure of 15 MPa. Owing to the superior analyte/matrix separation by ASE, in many cases for real soil samples analytical values better by up to 1 order of magnitude or even more were obtained compared to SOX results.

A new PLOT column (CP-LOWOX) designed specifically for the analysis of oxygenated compounds has been used for the gas chromatographic determination of semi-volatile carbonyl compounds. The separation behavior of the new column was investigated by comparing it with the widely used non-polar polydimethylsiloxane and polar poly(ethylene glycol) columns. The CP-LOWOX column has unique selectivity for aldehydes and ketones enabling a selective separation of these analytes from predominating hydrocarbon matrices. Application of the CP-LOWOX column for the analysis of polar compounds in ambient air is demonstrated. Sampling was performed by adsorptive enrichment coupled with thermal desorption. The suitability of Tenax TA and a multi-bed adsorbent trap Carbotrap C and Carbotrap) was tested for the sampling of semivolatile carbonyl compounds.

In reversed phase liquid chromatography, the retention indices of some neutral and acidic explosives and related compounds (nitramines, nitroaromatics, aminoaromatics, and nitrophenols) based on the alkan-2-one, alkyl aryl ketone, and 1-nitroalkane retention index standards have been determined by the application of a new mathematical adaptation method, viz. a multiparametric least-squares regression iterative method. This method was applied to two types of columns. The first group includes six octadecyl-C18 columns with different packing materials and obtained from different manufacturers, while the second group comprises one octyl-C8 column. The retention indices have been extensively studied using either methanol-water or methanol-phosphate buffer mobile phase systems. The calculated multiparametric retention indices values were compared with those obtained by Guardino's, Grobler's, and Kovats' methods. The influences of the concentration of the organic modifier in the mobile phase, aqueous mobile phase pH, and the column packing material on the retention indices of the explosives were also investigated. Good agreement was observed between the retention indices calculated by the use of the four mathematical methods for both neutral and acidic explosives.

In reversed phase liquid chromatography (RP-HPLC), the validity of a multiparametric non-linear least-squares regression iterative method for the determination of the column dead time tM and the regression parameter (slope b), based on the use of alkan-2-ones, alkyl aryl ketones, and 1-nitroalkanes has been evaluated. The determination of tM and b has been extensively studied for two mobile phase systems acetonitrile-water and methanol-water on seven octadecyl-C18 and one octyl C8 analytical columns. The calculated tM and b values were compared with those obtained by Guardino's and Grobler's methods. The influence exerted thereon by the nature of the homologous series, the mobile phase composition, and the packing materials were investigated.

THM–GC/MS was applied to the analysis of natural waxes (bleached beeswax, lanolin, yellow carnauba wax). By means of flash heating the wax samples in the presence of tetramethylammonium hydroxide (TMAH) as an alkaline derivatization reagent, the wax constituents, mainly high molecular weight esters, were hydrolyzed and converted into their methyl derivatives. Subsequent GC analysis of the methylation products resulted in chromatograms showing very specific signal patterns for each of the materials investigated. Mass spectrometric detection of the yielded methyl derivatives enabled the identification of more than ninety compounds present in the wax samples, i.e. fatty acids, hydroxy fatty acids, fatty alcohols, diols and sterols, respectively. Additionally to the analysis of real wax samples, several wax-relevant compounds (waxy esters, fatty acids, fatty alcohols) were studied with regard to their methylation behaviour. The investigations show that THM–GC/MS is able to overcome problems that arise from conventional Py–GC analysis of waxes, where thermal fragmentation can lead to rather non-specific pyrolysis products. Therefore, THM–GC/MS is an advantageous technique for the comprehensive analysis of natural waxes.

Three natural waxes (bleached beeswax, lanolin, yellow carnauba wax) were investigated by means of pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS). Pyrograms were obtained showing very characteristic signal patterns. Mass spectrometric detection enabled the structural identification of the pyrolytically formed fragments. For a more detailed investigation of the thermal degradation behaviour of waxy materials, relevant model compounds were selected. Hexadecylpalmitate, cholesterylstearate, heptadecanoic acid and 1-hexacosanol were examined under identical Py–GC–MS conditions. From the resulting product distribution general statements were able to be derived according to the thermal degradation pathways of typical wax constituents. The findings obtained from the model compounds were then applied to the interpretation of the real wax pyrograms. As a result, conclusions according to their origin from corresponding wax constituents were drawn for the majority of pyrolysis products. Thus, the extended potential of the method for the compositional analysis of natural waxes is demonstrated.

A pyrolysis–GC (Py–GC) method for the quantitative determination of poly(ethylacrylate-methylmethacrylate) (PEAMMA) layers on granules for pharmaceutical use is described. The PEAMMA copolymer layer ensures a sustained release of the active agent after oral intake of the granules by the patient. Because of the substantial influence of the copolymer content on the kinetics of the drug release, a reliable method for the PEAMMA quantification had to be developed. The method includes a pre-treatment step, separating the PEAMMA layer from the granule matrix by its selective dissolution in acetone. Employing the pyrolytically formed monomers ethylacrylate and methylmethacrylate as the target compounds and by means of external calibration, the PEAMMA content of the drug granules was determined with a relative standard deviation of less than 5%. Finally, the Py–GC data obtained from different batches of granule material were compared with the corresponding results of kinetic dissolution tests. For one of six samples investigated a too fast drug release was found to correlate with a too low PEAMMA content.

Accelerated solvent extraction (ASE) was used for the simultaneous extraction of semivolatile organic compounds (SOCs) including chlorobenzenes (1,2,3,4-tetra-, penta-, hexachlorobenzene), HCH isomers (α-, β-, γ-, δ-, e-HCH), DDX (p,p‘-DDT, -DDE, -DDD), PCB congeners (28, 52, 101, 138, 153, 180), and PAHs (phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]pyrene) from mosses (Pleurozium schreberi) growing in regional locations (central Germany) and pine needles (Pinus sylvestris L.) from southern Russia (near the Caspian Sea). The results were compared with those obtained by ultrasonic extraction (USE). Using mixed moss samples (thorough cleanup, only minor interference during GC/MSD analysis) from one location mainly served to optimize two parameters, extraction solvent and temperature. The most favorable extraction conditions proved to be n-hexane as the extraction solvent, two temperature stages of 40 and 120 °C, a pressure of 15 MPa, and three static cycles in each case. These conditions were th...

The potential of large-volume PTV injection was studied for the analysis of triazine herbicides in water samples. Direct water injection and in-vial extraction were described and compared. Detection limits were between 0.01–0.02 μg L−1 and relative standard deviations were

For the comprehensive characterization of ambient air concentrations of a broad spectrum of volatile organic compounds (VOCs) an analytical method is described, consisting of adsorptive enrichment, thermal desorption without cryofocusing, and capillary gas chromatographic separation. The method was applied during two-week measuring campaigns in winter and summer 1995, and in the winter of 1996. Long-term sampling was carried out at sampling points in residential areas in the suburbs and near the city center of Leipzig. About 70 VOCs – mainly hydrocarbons from propene to hexadecane – were identified both by GC-MS and chromatographic retention data and quantified after external calibration. Mean values of VOC concentrations obtained during the sampling periods are reported and discussed with regard to the topographical location of the sampling points in the Leipzig area, seasonal variations, and possible emission sources.

A method for the determination of di- and tetrachlorinated ethers (haloethers) in aqueous samples using solid-phase microextraction (SPME) combined with capillary GC has been developed. Using 100-μm polydimethylsiloxane fibers, the influence of several parameters on the SPME procedure like the exposure time of the fiber in the aqueous sample, the desorption temperature, and the salt content of the sample have been studied. Salt addition has a strong effect on the extraction efficiency of the haloethers investigated. Working with saturated salt solutions, the factor increase of the peak areas was in the range from 5 to 12. These improvements are accompanied by decreased precision and increased equilibration times. The SPME method combined with several detectors (FID, ECD, MS in SIM mode) was evaluated with respect to detection limits, linearities, and precisions. Working with salt addition and FID, detection limits of all compounds investigated were in the range of 0.3 to 1.2 μg/L. Using ECD, the LOD values (limits of detection) were only improved for the tetrachlorinated bis(propyl) ethers (

The capillary gas chromatographic retention behavior of α-pinene and tricyclene has been investigated on stationary phases of different polarities. On all but one of the columns employed, tricyclene eluted before α-pinene; only permethylated β-cyclodextrins dissolved in moderately polar polisiloxanes gave a reversed elution order. The intermolecular interactions which caused the unexpected retention behavior were investigated in detail, applying methods of computer simulation. To achieve this, we have developed a calculation algorithm on the basis of molecular mechanical optimizations and programmed it in a macro. This makes it possible to systematically investigate a given configuration space in which all the possible interactions can take place. It was shown that permethylated β-cyclodextrin as host molecule for both guest molecules offers an optimum cavity size. As a result the number of energetically favorable contacts between host and guest molecules as well as the strength of the interactions in this stationary phase were larger. As a consequence the elution order, normally only influenced by the vapor pressure of the compounds at a given temperature, was changed. Nonspecific interactions played an especially important role for these kinds of substances.

Electrochemical detection (ED) in the oxidative and reductive mode was applied to the analysis of nitroaromatics, nitramines, aminoaromatics and nitrophenols in groundwater samples from the surroundings of a former ammunition plant. Settings for working potential and eluent composition were optimized in terms of detection limit, linearity and selectivity. The results were compared with those obtained by UV detection and the advantages of combined UV-ED detection for the analysis of complex samples are shown.

α-Campholene and fencholene derivatives are compounds with interesting odour properties, e.g. sandalwood and woody notes. They have one (derived from the initial product, α-pinene) or several stereogenic centres. The stereoisomers of these compounds may have different odour properties; therefore, analysis methods are developed for the complete separation of the diastereomers and enantiomers. It is shown that the alcohols with one stereogenic centre as well as of the esters and ethers of α-campholene and fencholene derivatives with two stereogenic centres can be separated on permethylated α- und β-cyclodextrins dissolved in polysiloxanes. Factors influencing the separation are discussed.

Flumecinol and related compounds can, without derivatization, be separated into their enantiomers by gas chromatography on cyclodextrin phases; permethylated β-cyclodextrin dissolved in OV-1701 can be particularly recommended. Thermodynamic data describing the different intensities of interaction of the individual enantiomers with the stationary phases were determined. The values measured imply different separation mechanisms for the compounds investigated.

The separation of racemic side-chain fluorinated alkylbenzenes and bromofluorinated analogues by capillary gas chromatography using permethylated α, β and γ-cyclodextrins dissolved in polysiloxanes of different polarity as stationary phases is described. The influence of the achiral polysiloxane matrices on the separation of enantiomers is discussed in the light of the results obtained with the different phases. For a part of the tested compounds thermodynamic data are determined which describe the interaction of enantiomers with the stationary phase. The mechanism of separation is discussed on this basis and by comparison with data for structurally similar compounds.

Retention indices of 6 selected hydroxy compounds (aliphatic and bicyclic alcohols, phenols) were determined on 2 HP-5 fused-silica, capillary columns with different film thicknesses (0.11 μm and 0.33 μm) at 8 different oven temperatures between 80 and 150°C. For some substances the I-T plot was found to show a minimum which cannot be explained by the common retention-index temperature-dependence in gas-liquid chromatography. This result is discussed in terms of adsorption at the liquid-solid interface of the capillary column.

An indirect GC method is described for the determination of Ethephon in drinking water on the basis of the headspace analysis of the ethylene formed from Ethephon. In order to reach the necessary detection limit, the entire volume of the static headspace distribution is transferred into a cold injection system (CIS). There, the ethylene is adsorbed on Carbosieve SIII at 10°C and, subsequently, desorbed at 300 °C. The water vapour included in the headspace is completely eliminated through the splitting system. By means of this technique, a detection limit of 0.05 μg/l water was reached.

A quantitative method for the determination of organic acids in atmospheric particles is developed. The method couples a derivatisation step (thermally assisted hydrolysis and methylation) and a Curie point pyrolyser as a thermal desorption technique and gas chromatography–mass spectrometry (CPP-GC–MS). Among the reagents tested (tetramethylammonium hydroxide (TMAH), tetramethylammonium acetate (TMAAc) and phenyltrimethylammonium hydroxide (TMPAH)), the best performance was found using TMAAc as a derivatisation reagent for the reaction time of 4 s at 510 °C as heating temperature. Calibration was performed for a series of fatty acids (FA), dicarboxylic acids (DCA) and terpenoic acids (TA) under these conditions. Coefficients of determination (R2) were between 0.94 and 0.98. Limits of detection (LOD) were in the nanogram-range between 0.1 and 3.6 ng. The method is applied on atmospheric particle samples to obtain the quantification reproducibility and quantification limits. Reproducibility was determined in terms of relative standard deviations (RSD) for ambient aerosol samples collected by a high-volume-sampler (HVS, RSD = 6–45%, n = 10) and a Berner impactor (BI, RSD = 5–34%, n = 10). Based on 24 h sampling time the developed method enables quantification of all three classes of acids for both sampling techniques. Calibration data and presented volume concentrations are compared with literature data. A comparison with an off-line methylation-GC–MS using BF3 as a derivatisation reagent and capillary electrophoresis coupled mass spectrometry (CE-MS) showed a good agreement. Minimal sample preparation is the main advantage of the developed method. Depending on the sensitivity requirements the present method can be a fast and simple alternative to GC–MS techniques with conventional sample preparation steps for semi-volatile organic acids.

A high-resolution gas-chromatographic (HRGC) method with electron capture detection is described for the sensitive determination of PCBs and toxaphene in water in the lower ng/l range. The required low detection limits are guaranteed by isolation of the target compounds and concentration from the filtered water sample by solid phase extraction with specific C18 silica gel (200–250 μm) alone or combined with the injection of larger extract volumes into a programmed temperature vaporizer (PTV) operating in the solvent venting mode. The bonded silica gel was prepared by reaction of the surface silanol groups with octadecyltrichlorosilane. A C18 silica of reproducible coverage was received. Practical aspects of the use of the solid phase extraction in combination with the PTV injection technique are discussed. The recoveries for toxaphene and PCBs were 85 and 78%.

An analytical scheme was developed for the determination of Gd-diethylenetriaminepentaacetate (Gd-DTPA), Gd and the other rare earth elements (REE) in river water by inductively coupled plasma (quadrupole) mass spectrometry (ICP-Q-MS). The preconcentration step was essential, since the limits of detection of this multielemental analytical technique are higher than the trace concentrations of the interesting elements in river water. Solid phase extraction (SPE) with different commercially available complexing agents (Chelex 100, Toyopearl and ethylhexylphosphates) was employed for the preconcentration of REE. The investigations revealed that complex stability (varying in dependence of the pH value) has a strong influence on the degree of the enrichment of Gd-DTPA. Based on acidified water samples (pH

This paper presents a GC-MS confirmation method, based on large-volume programmed-temperature vaporisation (PTV) injection, for the determination of cannabinoids in plasma samples (or whole blood) with deuterium-labelled internal standards using only 25 microl of biological fluid. The analytes, Delta(9)-tetrahydrocannabinol (THC), 11-hydroxy-Delta(9)-tetrahydrocannabinol (11-OH-THC) and 11-nor-9-carboxy-Delta 9-tetrahydrocannabinol (THC-COOH), were enriched by means of solid-phase extraction cartridges containing octadecyl-bonded silica and were, subsequently, methylated. A 20 microl aliquot of an extract in hexane was injected into a PTV in solvent split mode. Method development and the results of the analyses of standard reference material and real samples are presented and discussed. This micro-method is precise and sensitive enough to assess relevant cannabinoid levels in human blood for forensic investigations as well as for clinical applications.

The API–MS signal response of several pesticides (atrazine, simazine, isoproturon, diuron, chlorfenvinphos, chlorpyrifos, alachlor, trifluralin) depending on the flow-rate of eluent entering the MS interface was investigated. The investigations were based on API–MS–MS analyses of standard pesticide mixtures in the flow injection mode (FIA) at systematically varied eluent flow-rates using both an ESI interface (Turboionspray) and a heated nebulizer type APCI source. In the result, the individual compounds included in this study showed significant differences in their signal response behaviour depending on the flow-rate of eluent applied. The most hydrophobic compounds among the investigated pesticides (chlorpyrifos and trifluralin) showed drastic losses of sensitivity with increasing eluent flow-rate in both ESI and APCI, while more hydrophilic compounds like atrazine, simazine and isoproturon showed the expected signal response (concentration-sensitive in ESI, mass-flow-sensitive in APCI) at least within a certain range of flow-rates (200–600 μl/min in ESI, 200–2000 μl/min in APCI). These findings lead to the conclusion that application of a programmed HPLC eluent flow-rate may be advantageous to achieve maximum sensitivity of API–MS detection for all pesticides of interest. This is exemplified by the implementation of a flow gradient into an online SPE–HPLC–APCI–MS/MS method for improved analysis of pesticides in drinking water.

The fundamental suitability of solid-phase microextraction (SPME) has been investigated for the enrichment of partially well water-soluble and differently substituted polar nitrophenols. Two commercially available fibers coated with 100 μm polydimethylsiloxane or 85 μm polyacrylate, respectively, were compared with regard to the efficiency of the enrichment of these compounds. For all the compounds investigated, polyacrylate fiber showed a better affinity when the exposure time was longer in comparison with polydimethylsiloxane fiber. The ‘salting-out’ and the enrichment at low pH-values increased the sensitivity of the process significantly.

Molecular structure and retention behaviour. XII. Refention behaviour of alkylnaphthalenes by gas-liquid and by gas-solid chromatography The retention indices of 1-alkyl- and 2-alkylnaphthalenes, of isomeric dimethylnaphthalenes, of some trimethylnaphthalenes and methylazulenes have been determined by gas—liquid chromatography (GLC) on glass capillaries of different polarity (methylsilicone OV-1, Ucon LB 550 X and Ucon 50 HB 280 X polar) and by gas—solid chromatography (GSC) on graphitized thermal carbon black, respectively. The retention within homologous series of straight chain 1-alkyl- and 2-alkylnaphthalenes, of isomeric butylnaphthalenes and dimethylnaphthalenes is discussed by means of homomorphic factors and index differences and compared with corresponding values of alkylbenzenes. The different retention behaviour of the isomeric dimethylnaphthalenes by GLC and by GSC can be described by an incremental approach.

For the study of relationships between retention behaviour and molecular structure in GLC and GSC the retention indices of alkenylbenzenes with 2–6 carbon atoms in a straight or branched side chain and of isotopological alkylbenzenes were determined on capillary columns coated with OV-1 and Ucon LB and on a micropacked column filled with graphitized thermal carbon black. From the values obtained index differences corresponding to the increments of the double bond in the side chain were derived. These differences depend significantly on the structure of the side chain and of the position of the double bond.

Molecular structure and retention behaviour. Retention behaviour of cycloaliphatic hydrocarbons in gas—solid chromatography and in gas—liquid chromatography The retention indices of cycloalkanes, cycloalkenes, and some cycloalkadienes of the ring size C6C13 have been determined on a column packed with graphitized thermal carbon black, and compared with the corresponding data on squalane. The relationships between molecular structure and retention indices as well as homomorphism factors are discussed. According to the different separation principles of gas—solid chromatography and gas—liquid chromatography, respectively, the homomorphism factors are negative on graphitized thermal carbon black, but positive on squalane.

Using n-heptane as eluent a direct linear correlation was found between the logk’ values of various polar test compounds and the silanol content determined by the methyllithium method. The peak asymmetries pass through a maximum at a medium silanol content. Peak asymmetries and logk’ values depend also on the chain length of the bonded alkyl group. A computer program was used to classify 25 home-made RP materials, 7 commercial products and the starting silica to achieve a hierarchical classification of them. The arrangement provides some detailed information about the presence and the effect of silanol groups.

By combined application of chemical pretreatments, and chromatographic and spectroscopic methods, it is possible to coordinate individual species of a complex lipid extract with high safety. In the sample studied, besides a high content of palmitic and cis -vaccenic acid, small amounts of unusual fatty acids containing hydroxy groups and cyclopropane rings were detected. The presence of polyunsaturated fatty acids was excluded by structure-retention relationships, which were obtained on phases of different polarity. On the basis of these studies, and without the use of reference substances, a routine analysis of these unusual fatty acids in biological materials is possible.

High silica molecular sieves (silicalite, ZSM-5) were tested as adsorbents for gas chromatographic trace analysis. Therefore the retention behaviour of low-boiling organic compounds (hydrocarbons, halogenated hydrocarbons, amines, alcohols and ethers) on these materials was investigated. The specific retention volumes at different temperatures have been determined and elution orders and peak shapes were studied. The retention data allow a simple calculation of the breakthrough volumes (dynamic adsorption capacity) and the chromatographic characterisation of the adsorbents. Both nitrogen and oxygen containing compounds could not—or at least unreproducibely—be eluated up to 300°. The elution order and the peak shape of compounds with the same number of carbon atoms but different geometric and electronic structure (e.g.n-butenes;n-hexane, cyclohexane, benzene) can be explained by the action of exclusion effects and different diffusion barriers.

Reaction products of the pyrolysis of n-dodecylpentane and n-hexylcyclohexane had been separated and identified on a glass capillary column coated with Polydimethylsiloxane OV-1.

Hydropyrenes, Alicyclic Model Compounds for GC–MS Investigations Hydrogenation of asymmetric and symmetric hexahydropyrene gives the five possible aromatic decahydropyrenes via different octahydropyrenes. From these compounds some dodecahydro- and tetradecahydro-pyrenes, the four isomers of perhydropyrene with chair conformations and five new stereoisomers with twist boat six-membered rings are obtained. The configurations of the hydrogenated pyrenes are assigned using chromatographic retention indices and mass spectrometric fragmentation in combination with force field calculations.

The thermodynamic functions of adsorption (Henry constants, retention incides, changes in internal energy and entropy at zero sample size) of geometric and structural isomers of polymethylcyclohexanes on graphitized thermal carbon black have been determined and their relationship to the structures of the molecules has been established. A molecular statistical calculation of these functions for the adsorption of cyclohexane, methylcyclohexane and some di-, tri- and tetramethylcyclohexanes has been carried out using the atom-atom approximation for the potential function of intermolecular interaction with graphitized thermal carbon black. Examples of the separation of some mixtures of these hydrocarbons are given.

Molecular structure and retention behaviour. VIII. Gas chromatographic retentionbehaviour of dicyclopentadiene derivatives The retention indices of exo—endo isomeric dicyclopentadienes, dihydrodicyclopentadienes and tetrahydrodicyclopentadienes have been determined by gas—liquid chromatography (GLC) on glass capillaries coated with squalane, Ucon LB 550X and Ucon 50HB 280 X polar, and by gas—solid chromatography on graphitized thermal carbon black. The influence of exo- and endo-configuration of the carbon skeleton and of the position of the double bond on retention is discussed by means of homomorphic factors and index differences. In the same manner the relationships between retention and configuration of the carbon skeleton and of the substituent are elucidated from the retention indices of 9-hydroxy-, 9-acetoxy-, 9-ketodihydrocyclopentadienes and substituted tetrahydrodicyclopentadienes, respectively, obtained by GLC on capillary columns with different polarity.