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ECN heeft een simpele en goedkope methode ontwikkeld om te voorkomen dat capillaire kolommen in massa spectrometers en gas chromatografen verstoppen door ophoping van stof. Bij sommige processen zijn in de te analyseren gasstroom stofdeeltjes aanwezig. De methode van ECN helpt op een slimme manier te voorkomen dat de stofdeeltjes in de analyzer terecht komen.

A large-volume on-column GC-cryotrapping-IR system was developed for injections of up to 100 μl of organic extracts. Considerable reduction of the solvent-and-water background and enhanced analyte detectability was achieved by using an open-split interface between the GC column and the IR detector and improving the leak-tightness of the system. The system was combined with solid-phase extraction to yield on-line SPE-GC-IR. With this set-up, sample volumes of only 20 ml sufficed to detect, and identify, microcontaminants in tap and surface water at the 0.1-1 μg/L level. Detection limits were on the order of 15 ng/L for tap water when using appropriate functional-group chromatograms. Or, in other words, SPE-GC-IR is a suitable technique for the screening of environmental water samples for functional groups, i.e. classes of compounds, of interest.

A number of headspace techniques have been compared, using a standard solution containing 12 compounds and a wine sample, viz.: (1) purge and cold trap injection; (2) dynamic headspace combined with liquidliquid extraction; (3) static headspace with and without preconcentration; (4) direct liquid injection. The sensitivity, reproducibility and speed of analysis were determined. Considering the results obtained and dependent on the purpose of the experiments and the number of samples to be examined the appropriate technique can be selected. ?? 1980 Friedr. Vieweg & Sohn Verlagsgesellschaft mbH.

A straightforward method based on GC-MS was developed to determine the booster biocide dichlofluanid and its metabolite DMSA in sediment and water. Special attention was paid to conservation of samples, conversion of dichlofluanid to DMSA during analysis and the effect dichlofluanid-containing paint particles might have on the analysis results. The analytical method is suitable for the quantitative determination of dichlofluanid and its metabolite DMSA in seawater down to a level of 10 ng L-1. Dichlofluanid could not be detected in marine sediment as it was immediately degraded to DMSA. However, dichlofluanid could be determined as DMSA. The analytical method is suitable for the determination of DMSA in marine sediment down to 5 μg kg-1 (wet weight). © 2005 Friedr. Vieweg & Sohn/GWV Fachverlage GmbH.

Chemicals/CAS: soman, 96-64-0; Organophosphorus Compounds; Soman, 96-64-0

The features of a resistive-heated capillary column for fast temperature-programmed gas chromatography (GC) have been evaluated. Experiments were carried out using a commercial available EZ Flash GC, an assembly which can be used to upgrade existing gas chromatographs. The capillary column is placed inside a metal tube which can be heated, and cooled, much more rapidly than any conventional GC oven. The EZ Flash assembly can generate temperature ramps up to 1200 °/min and can be cooled down from 300 to 50 °C in 30 s. Samples were injected via a conventional split/splitless injector and transferred to the GC column. The combination of a short column (5 m x 0.25 mm i.d.), a high gas flow rate (up to 10 mL/min), and fast temperature programmes typically decreased analysis times from 30 min to about 2.5 min. Both the split and splitless injection mode could be used. With n-alkanes as test analytes, the standard deviations of the retention times with respect to the peak width were less than 15% (n = 7). First results on RSDs of peak areas of less than 3% for all but one n-alkane indicate that the technique can also be used for quantification. The combined use of a short GC column and fast temperature gradients does cause some loss of separation efficiency, but the approach is ideally suited for fast screening as illustrated for polycyclic aromatic hydrocarbons, organophosphorus pesticides, and triazine herbicides as test compounds. Total analysis times - which included injection, separation, and equilibration to initial conditions - were typically less than 3 min.

The tyrosine-containing peptide Gly-Tyr-Gly (GYG) was oxidatively cross-linked by horseradish peroxidase in the presence of hydrogen peroxide. As products, covalently coupled di- to pentamers of the peptide were identified by LC-MS. Oxidative cross-linking of ferulic acid with horseradish peroxidase and hydrogen peroxide resulted in the formation of dehydrodimers. Kinetic studies of conversion rates of either the peptide or ferulic acid revealed conditions that allow formation of heteroadducts of GYG and ferulic acid. To a GYG-containing incubation mixture was added ferulic acid in small aliquots, therewith keeping the molar ratio of the substrates favorable for heterocross-linking. This resulted in a predominant product consisting of two ferulic acid molecules dehydrogenatively linked to a single peptide and, furthermore, two ferulic acids linked to peptide oligomers, ranging from dimers to pentamers. Also, mono- and dimers of the peptide were linked to one molecule of ferulic acid. A mechanism explaining the formation of all these products is proposed. Chemicals/CAS: Coumaric Acids; Cross-Linking Reagents; ferulic acid, 1135-24-6; Horseradish Peroxidase, EC 1.11.1.-; Hydrogen Peroxide, 7722-84-1; Tyrosine, 55520-40-6

A gas chromatographic method, with electron capture detection and mass spectrometric confirmation, is described for the determination of chlorothalonil and its metabolite 4-hydroxy-2,5,6-trichloroisophtalonitrile (HTI) in water samples. Water is saturated with sodium chloride and acidified to pH < 2 with dilute sulfuric acid. After extraction with dichloromethane, HTI was methylated with diazomethane. The extract obtained was cleaned with basic alumina. Chlorothalonil and the methylated HTI-derivative were determined by gas chromatography with electron capture detection (GC-ECD) and confirmed by gas chromatography-mass spectrometry (GC-MS). The limit of detection, depending on the nature of the water samples is for both compounds between 0.01-0.03 μg l-1 water. The average recovery in ground water is 87% for chlorothalonil and 82% for HTI.

Quantitative analysis using comprehensive two-dimensional (2D) gas chromatography (GC) is still rarely reported. This is largely due to a lack of suitable software. The objective of the present study is to generate quantitative results from a large GC x GC data set, consisting of 32 chromatograms. In this data set, six target components need to be quantified. We compare the results of conventional integration with those obtained using so-called "multiway analysis methods". With regard to accuracy and precision, integration performs slightly better than Parallel Factor (PARAFAC) analysis. In terms of speed and possibilities for automation, multiway methods in general are far superior to traditional integration. © 2003 Elsevier B.V. All rights reserved.

Studying links between triacetone triperoxide (TATP) samples from crime scenes and suspects can assist in criminal investigations. Isotope ratio mass spectrometry (IRMS) and gas chromatography (GC)-IRMS were used to measure the isotopic compositions of TATP and its precursors acetone and hydrogen peroxide. In total, 31 TATP samples were synthesized with different raw material combinations and reaction conditions. For carbon, a good differentiation and a linear relationship were observed for acetone–TATP combinations. The extent of negative (d13C) fractionation depended on the reaction yield. Limited enrichment was observed for the hydrogen isotope (d2H) values of the TATP samples probably due to a constant exchange of hydrogen atoms in aqueous solution. For oxygen (d18O), the small isotopic range and excess of water in hydrogen peroxide resulted in poor differentiation. GC-IRMS and IRMS data were comparable except for one TATP sample prepared with high acid concentration demonstrating the potential of compound-specific isotope analysis. Carbon IRMS has practical use in forensic TATP investigations. © 2016 American Academy of Forensic Sciences

Plant sterols are added as their FA esters to vegetable oil table spreads at levels of approximately 8% as a means to reduce blood cholesterol levels. A new chromatographic method was designed to quantify quickly the level of plant sterol FA esters in incoming (raw) materials and to monitor their processing and final product quality with respect to total sterol level. The method shows a significant improvement in elapsed time and thus labor cost over the classical methods for sterols published in normative references. This improvement was obtained together with high performance characteristics, as shown by the internal method validation for recovery and repeatability. Its validity and robustness were further tested and confirmed in an international collaborative test. The method allows monitoring of sterol content of raw materials, fat-blends, and consumer products at the target level, with a range of 10% or less around this target. The calculated within- and between-laboratory reproducibility were 0.680 and 1.194 w/w%, respectively, for sterol-containing spreads. The results afforded by this method can be used for setting tight product specifications or to monitor trade between companies. We propose to add this new and fast method for total 4-desmethyl sterol(s) to analytical method collections as an adjunct to methods already listed for more detailed sterol analysis.

The thermal energy analyser (TEA) is considered to be the gold standard for the determination of nitrosamines. However, since many laboratories cannot justify the use of such a very specific detection system, alternative detection methods are useful. While standard gas chromatography (GC) detectors lack the selectivity of the TEA detector, mass spectrometry (MS) seems to be the method of choice to combine GC separation with mass selective detection. Moreover, the detection limits of the GC-MS assay in general use are about 4 times lower than those of the GC-TEA assay. A comparison of GC-MS and GC-TEA data on N-nitrosodimethylamine determinations showed a strong correlation between the two assays (R2 = 0.86), demonstrating the exchangeability of these methods. © 2001 Lippincott Williams & Wilkins. Chemicals/CAS: Carcinogens; Indicators and Reagents; N-nitrosodiphenylamine, 86-30-6; Nitrosamines

A procedure is described for the (non-target) screening of hetero-atom-containing compounds in tap and waste water by correlating data obtained by gas chromatography (GC) using atomic emission (AED) and mass selective (MS) detection. Solid-phase extraction (SPE) was coupled on-line to both GC systems to enable the determination of microcontaminants at the 0.02-1 μg L-1 level in 7-50 mL of aqueous sample. The screening was limited to compounds present in at least one heteroatom-selective GC-AED trace above a predetermined concentration level. These compounds were identified by their partial formulae (AED) and the corresponding mass spectra, which were obtained from the CC-MS chromatogram via the retention index concept. The potential of the approach was demonstrated by the identification of target compounds as well as all unknowns present in tap and waste water above the predetermined threshold of 0.05 μg L-1 (tap water) or 0.5 μg L-1 (waste water).

A new concept for cleanup, based on volume overloading of the cleanup column, has been developed for on-line coupling of gel permeation chromatography (GPC), solid-phase extraction (SPE), or both, to gas chromatography (GC). The principle is outlined and the applicability demonstrated by the determination of pesticide residues in food matrixes using integrated and automated cleanup-GC-MS. Compared to conventional approaches for on-line cleanup-GC, the new technique involves introduction of much smaller volumes (e.g., 2-20 μL) into the GC without sacrificing method LODs. The much smaller injection volumes involved greatly simplify on-line coupling, improve robustness, and increase attractiveness for implementation in routine laboratories. © 2007 American Chemical Society.

Comprehensive two-dimensional gas chromatography (GC × GC) has proven to be an extremely powerful separation technique for the analysis of complex volatile mixtures. This separation power can be used to discriminate between highly similar samples. In this article we will describe the use of GC × GC for the discrimination of crude oils from different reservoirs within one oil field. These highly complex chromatograms contain about 6000 individual, quantified components. Unfortunately, small differences in most of these 6000 components characterize the difference between these reservoirs. For this reason, multivariate-analysis (MVA) techniques are required for finding chemical profiles describing the differences between the reservoirs. Unfortunately, such methods cannot discern between 'informative variables', or peaks describing differences between samples, and 'uninformative variables', or peaks not describing relevant differences. For this reason, variable selection techniques are required. A selection based on information between duplicate measurements was used. With this information, 292 peaks were used for building a discrimination model. Validation was performed using the ratio of the sum of distances between groups and the sum of distances within groups. This step resulted in the detection of an outlier, which could be traced to a production problem, which could be explained retrospectively. © 2005 Elsevier B.V. All rights reserved.

Polymer coated glass fibers were applied as disposable samplers to measure dissolved concentrations of persistent and bioaccumulative pollutants (PBPs) in sediment porewater. The method is called matrix solid-phase microextraction (matrix-SPME), because it utilizes the entire sediment matrix as a reservoir for an equilibrium extraction: A glass fiber with a 15 μm coating of poly-(dimethylsiloxane) (PDMS) was placed in a sediment sample until the PBPs reached their equilibrium distribution between the PDMS and the sediment matrix (1-30 days). PBP concentrations in the PDMS were determined by gas chromatography, and they were divided by PDMS water partition coefficients to derive at dissolved porewater concentrations. This approach was applied to measure porewater concentrations of spiked as well as field sediment, and several hydrophobic organic substances (log K(ow) 5.2-7.5) were measured with high precision in the pg to ng/L range. Simple equilibrium partitioning is the basis for the substantial concentration factors that are built into matrix-SPME and for the low demands in materials and operation time. Matrix-SPME was in this study directed at the determination of dissolved porewater concentrations in sediment, and it is further expected to be applicable to other environmental media, to field sampling, and to the sensing of fugacity. Polymer coated glass fibers were applied as disposable samplers to measure dissolved concentrations of persistent and bioaccumulative pollutants (PBPs) in sediment porewater. The method is called matrix solid-phase microextraction (matrix-SPME), because it utilizes the entire sediment matrix as a reservoir for an equilibrium extraction: a glass fiber with a 15 μm coating of poly-(dimethylsiloxane) (PDMS) was placed in a sediment sample until the PBPs reached their equilibrium distribution between the PDMS and the sediment matrix (1-30 days). PBP concentrations in the PDMS were determined by gas chromatography, and they were divided by PDMS water partition coefficients to derive at dissolved porewater concentrations. This approach was applied to measure porewater concentrations of spiked as well as field sediment, and several hydrophobic organic substances (log KOW 5.2-7.5) were measured with high precision in the pg to ng/L range. Simple equilibrium partitioning is the basis for the substantial concentration factors that are built into matrix-SPME and for the low demands in materials and operation time. Matrix-SPME was in this study directed at the determination of dissolved porewater concentrations in sediment, and it is further expected to be applicable to other environmental media, to field sampling

17α-Boldenone (17α-BOL) and/or 17β-boldenone (17β-BOL) appear occasionally in fecal matter of cattle. In addition to 17α-BOL, a whole array of boldenone related substances can be found in the same samples. In vitro experiments with microsomal liver preparations and isolated hepatocytes combined with the excretion profiles found in urine and feces samples of in vivo experiments made it possible to identify several metabolites of 17β-BOL in 17β-BOL positive feces samples. In one animal treated with 17β-BOL, no 17β-BOL or its metabolites were present before treatment and most of these compounds disappeared gradually in time after the treatment was stopped. It is not clear what the origin is of 17α-BOL and boldenone metabolites in samples screened routinely for the abuse of anabolic steroids and considered to be 'negative' because of the absence of 17β-BOL since other workers showed some evidence that 17α-BOL can be of endogenous origin. However, in our hands, most of these 17α-BOL positive samples, obtained during routinely performed screenings of cattle contained large amounts of Δ4-androstene-3,17-dione (AED), which normally is absent from routinely screened negative samples. Furthermore, AED was absent in all samples obtained from the animals treated with 17β-BOL. We have no direct evidence that 17α-BOL or 17β-BOL is of endogenous origin.