Daniel Fraisse

Identification of surfactants in water by fab mass spectrometry

Abstract An application of fast atom bombardment (FAB) for identification of some organic micro-pollutants was performed. A study of the most common surfactants, including non-ionic, cationic and anionic compounds was carried out and the results obtained used to build a table for rapid characterization of surfactants in real samples. Negative FAB and tandem mass spectrometry (CID-MIKE) were also occasionally employed, when two or more compounds gave the same series of peaks. Sensitivity limits for standards varied from low to upper nanogram range for cationic to anionic surfactants. Raw and drinking water extracts of Barcelona (N.E. Spain) were analysed and the most common surfactants and some brominated derivatives were identified.

Determination of chlorobenzidines in industrial effluent by solid-phase extraction and liquid chromatography with electrochemical and mass spectrometric detection

The analysis of chloroanilines in industrial effluents is severely complicated by the total organic content (TOC) (10–100 mg/l) and high particle content, which reflects the presence of many compounds other than the analytes of interest. Therefore, both the extraction procedure and the application of a selective and sensitive detection technique are important. Five different polymeric solid-phase extraction cartridges were tested to extract chloroanilines and benzidines from Milli-Q and industrial effluent waters. The analyses were performed by liquid chromatography with electrochemical detection and with atmospheric pressure chemical ionization mass spectrometry in positive ionization mode. These techniques were used to detect several mono- and dichloroanilines in industrial effluents, which had a TOC between 1 and 70 mg/l.

Efficient solid-phase extraction procedures for trace enrichment of priority phenols from industrial effluents with high total organic carbon content.

Polymeric solid-phase extraction (SPE) cartridges and Speedisks were used to extract 17 phenols from HPLC-grade water, tap water, river water and industrial effluents. With SPE cartridges, recoveries between 60 and 120% were obtained for waters with a total organic carbon (TOC) content below 20 mg C/l. However, when extracting industrial effluent waters with higher TOC values (75 mg C/l), only the polar phenols were recovered from the water fraction. Nonpolar compounds (di-, tri- and tetrachlorophenols) remained attached to the particulate matter and were recovered from the 0.45-microm filter membrane disks by Soxhlet extraction. Speedisks offered a high efficiency and permitted one to extract phenols without a prior filtration step. Acceptable recoveries were obtained when processing heavily charged industrial effluents with a TOC of 505 mg C/l. Liquid chromatography with electrochemical detection was used for the routine determination of 17 priority phenols.

Approach to the analysis of diuretics and masking agents by high-performance liquid chromatography—mass spectrometry in doping control

The application of thermospray and plasmaspray high-performance liquid chromatography-mass spectrometry to the analysis of diuretics and probenecid has been investigated. The latter method gave better ionization efficiency than the former, and its response was optimized by altering the solvent composition: best results were obtained with water-methanol-acetonitrile-trifluoroacetic acid. Using different proportions of these solvents, three isocratic systems were developed to separate the compounds under study. The principal characteristic of plasmaspray positive-ion mass spectra was a protonated molecular ion and very little fragmentation was evident. In the negative ionization mode, the plasmaspray method gave mass spectra showing more fragmentation, which resulted in additional structural information. The ability of trifluoroacetic acid to form negative cluster ions precluded its use as a mobile phase component. The minimum detectable amounts determined by the analysis in the positive-ion mode was compound-dependent, but generally ca. 10-150 ng. In many cases the compounds could be detected in urine extracts.

Extraction and GC/MS Analysis of the Essential Oil of Achillea millefolium L. complex (Compositae)

ABSTRACT The essential oil, which was obtained by hydrodistillation from aerial parts of Achillea millefolium L. complex (Compositae), was analyzed using both GC/MS and Kovats indices. The major components extracted from the stems, leaves and inflorescences were found to be β-thujone (8.3–21.7%), camphor (8.6–11.7%), 1, 8-cineole (7.7–15.2%), β-pinene (3.8–7.8%) and sabinene (5.7–8.9%). More than sixty components have been identified; forty of which, mainly oxygenated compounds, are reported for the first time. Variations in the essential oil composition and yield during hydrodistillation are also reported.

Comparison of gas chromatographic-mass spectrometric methods for screening of chlorotriazine pesticides in soil

The performance of a coupled technique resulting from the combination of gas chromatography with a selective mass spectrometric technique (tandem mass spectrometry) (GC-MS-MS) with collisionally activated dissociation (CAD) and multi-reaction monitoring (MRM) was compared with that of GC-low resolution MS (GC-LRMS) at a resolving power of 1000 and GC-high-resolution MS (GC-HRMS) at resolving powers of 5000 and 10,000 for the determination of atrazine, simazine, cyanazine, deethylatrazine and deisopropylatrazine in polluted soil samples. GC-MS-MS daughter ion spectra for the parent ions [M]+. and [M - CH3]+ were generated using collisionally activated dissociation and studied. Also, by optimizing the collision energy for maximum sensitivity a method for screening chlorotriazines by MRM was developed. Analyses of soil sample extracts showed that GC-MS-MS overcomes interferences from other chlorotriazines and interfering compounds that could not be removed by GC-HRMS or GC-LRMS at resolving powers of 10,000 and 1000, respectively. The limits of detection for GC-MS-MS and GC-HRMS at a signal-to-noise ratio of 10 ranged between 1 and 24 pg, with a mean relative standard deviation of 25-30%. Soil samples known to contain chlorotriazines and their degradation products were analysed by GC-MS-MS and the results obtained were compared with those given by GC-HRMS at resolving powers of 5000 and 10,000, with quantification differences of 25-30%.

Chemical Composition of Essential Oil of Callistemon citrinus (Curtis) Skeel from Reunion

Abstract The composition of the water-distilled essential oil of Callistemon citrinus (Curtis) Skeels was determined by GC, GC/MS and GC/FTIR. The oil was found to be rich in 1,8-cineole (68.0%), α-pinene (12.8%) and α-terpineol (10.6%).

GC-MS-SPECMA bank analysis of JUniperus communis needles and berries

Abstract Using a combination of gas chromatography-mass spectrometry (electron impact) as well as the headspace technique, more than 70 compounds were found in the juniper needle oil obtained from plants growing in southeastern France (Provence). A comparison between the headspace of fresh and bottled black berries shows a significant loss of the monoterpenoid fraction with time. In the green berries (unripe) this loss is more marked. A sesquiterpenoid fraction of the Juniperus communis needle oil was also investigated by means of the GC (FID) and GC-MS (EI, PCI). Among more than 100 isolated constituents, 64 were sesquiterpenoids. The presence of several oxygen-containing derivatives based on the calamene and calacorene isomers was established but their structures were not fully determined. The various compounds were identified on the basis of our SPECMA data bank (mass spectra and Kovats indices) and our own files.

Chemical composition of the essential oil of Senecio ambavilla (Bory) Pers. from Reunion Island

ABSTRACT Sixty-two compounds have been characterized by GC/MS and relative retention times in the essential oil of Senecio ambavilla (Bory) Pers. produced from plant material growing in Reunion (Indian Ocean). The oil was found to be rich in allo-aromadendrene (40%) and α-pinene (14%). While accounting numerically for approximatively third of the total number of compounds present in the oil, the monoterpene compounds contributed less than 23% of the oil content. On the other hand 70% of the oil was sesquiterpenoid in nature. In addition, long chain aldehydes, eremophilane, phytol (a diterpene alcohol) and indene derivatives were also identified as minor constituents.

The chemical composition of some cold-pressed citrus oils produced in Algeria

ABSTRACT The cold-pressed oils of five orange cultivars, a Tangor hybrid and the Clementine Tangerine, which were obtained from fruit grown in Algeria, were examined by GC/MS. The orange oils were found to contain the following number of constituents: Washington-Navel (43), Portuguese (61), Valencia (43), Hamlin (24) and Sanguine (23). The Tangor hybrid oil was found to contain 34 components, while 25 components were found in the Clementine oil. The use of preparative GC as a method to remove the monoterpene hydrocarbons prior to GC/MS analysis was demonstrated.