title: Gas chromatography coupled to tunable pulsed glow discharge time-of-flight mass spectrometry for environmental analysis.
abstract: A tuneable microsecond pulsed direct current glow discharge (GD)-time-of-flight mass spectrometer MS(TOF) developed in our laboratory was coupled to a gas chromatograph (GC) to obtain sequential collection of the mass spectra, at different temporal regimes occurring in the GD pulses, during elution of the analytes. The capabilities of this set-up were explored using a mixture of volatile organic compounds of environmental concern: BrClCH, Cl(3)CH, Cl(4)C, BrCl(2)CH, Br(2)ClCH, Br(3)CH. The experimental parameters of the GC-pulsed GD-MS(TOF) prototype were optimized in order to separate appropriately and analyze the six selected organic compounds, and two GC carrier gases, helium and nitrogen, were evaluated. Mass spectra for all analytes were obtained in the prepeak, plateau and afterpeak temporal regimes of the pulsed GD. Results showed that helium offered the best elemental sensitivity, while nitrogen provided higher signal intensities for fragments and molecular peaks. The analytical performance characteristics were also worked out for each analyte. Absolute detection limits obtained were in the order of ng. In a second step, headspace solid phase microextraction (HS SPME), as sample preparation and preconcentration technique, was evaluated for the quantification of the compounds under study, in order to achieve the required analytical sensitivity for trihalomethanes European Union (EU) environmental legislation. The analytical figures of merit obtained using the proposed methodology showed rather good detection limits (between 2 and 13 microg L(-1) depending on the analyte). In fact, the developed methodology met the EU legislation requirements (the maximum level permitted in tap water for the "total trihalomethanes" is set at 100 microg L(-1)). Real analysis of drinking water and river water were successfully carried out. To our knowledge this is the first application of GC-pulsed GD-MS(TOF) for the analysis of real samples. Its ability to provide elemental, fragments and molecular information of the organic compounds is demonstrated.
authors.affiliation: Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo, c/Julián Clavería, 8, 33006 Oviedo, Spain.
authors.forename: Auristela
authors.initials: A
authors.lastname: Solà-Vázquez
authors.forename: Azucena
authors.initials: A
authors.lastname: Lara-Gonzalo
authors.forename: José M
authors.initials: JM
authors.lastname: Costa-Fernández
authors.forename: Rosario
authors.initials: R
authors.lastname: Pereiro
authors.forename: Alfredo
authors.initials: A
authors.lastname: Sanz-Medel
mesh_terms: D008401:Gas Chromatography-Mass Spectrometry / Q000295:instrumentation / Q000379:methods*; D005740:Gases / Q000737:chemistry; D052617:Solid Phase Microextraction; D055549:Volatile Organic Compounds / Q000032:analysis* / Q000737:chemistry / Q000302:isolation & purification; D014874:Water Pollutants, Chemical / Q000032:analysis* / Q000737:chemistry / Q000302:isolation & purification
chemical_list: D005740:Gases; D055549:Volatile Organic Compounds; D014874:Water Pollutants, Chemical