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Laboratory Mass Spectrometry Facility TNA 7 and JRA 15

Laboratory Mass Spectrometry Facility TNA 7 and JRA 15. Activity PI: R. Thissen ( LPG, Grenoble, France) List of laboratories: LPG (Grenoble, France) LCBOB (Paris, France) IOCB (Prague, Czech Republic) AMPL (Trento, Italy). Description of the proposed infrastructure activity.

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Laboratory Mass Spectrometry Facility TNA 7 and JRA 15

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  1. Laboratory Mass Spectrometry FacilityTNA 7 and JRA 15 Activity PI: R. Thissen (LPG, Grenoble, France) List of laboratories: LPG (Grenoble, France) LCBOB (Paris, France) IOCB (Prague, Czech Republic) AMPL (Trento, Italy)

  2. Description of the proposed infrastructure activity • Bring to planetary sciences community expertise of physical chemists in mass spectrometry • Offer to planetary sciences community access to a Facility with top-grade mass spectrometers distributed in different laboratories in Europe

  3. Mass spectrometers with sophisticated characteristics • Very high resolution mass spectrometry (Fourier Transform MS with resol. 105) • Gas or liquid chromatography coupled with mass spectrometry (GC-MS, LC-MS) • Pyrolysis coupled with GC-MS (solid samples) • MS/MS analysis and D/H exchange (chemical structure of molecules) • Different sources for introduction of gas and liquid (soluble extract) samples

  4. -CH2NH2 -NH3 -HCN Example: MS/MS study chemical structure analysis of tholins Collision induced dissociation of mass-selected ions MS/MS of CxHyNz+ fragment ions obtained from tholins (laboratory analogues of Titan aerosols) Somogyi et al. JACS (2005)

  5. Specific contribution to EuroPlaNet I3 • Mass Spectrometry Facility = network of European top-grade MS instruments for Planetary Sciences • Bring together MS physical chemist expertise for • interpretation of space data on complex molecular species • chemical sample analysis Question: common integrated activity with Mass Spectrometers for solid sample analysis? (see B. Marty’s talk)

  6. TNA and JRA with budget • TNA (520 keuros) • Travel costs for external users • Mass Spectrometers operation costs (20% of time operation for external users) • Postdoc positions • JRA (600 keuros) • Improvements of the mass spectrometer sources (ex: development of a VUV continuum source)

  7. m/z 68 C5H8+ C3H4N2+ complex CxHyNz+ions ! Cassini mass spectrometer (INMS) First results (April 2005) • Important molecular synthesis, • even at 1200 km altitude • Mass spectrum up to 100 • Mass resolution limited to 1 • Modelisation is essential to identify CxHyNz+ ions

  8. Example: what are the CxHyNz+ ions observed by INMS on Cassini in Titan ionosphere? • CxHyNz+ can have the same nominal mass as C(x+1)H(y+2)N(z-1)+ as CH2 has the same mass as N Ex: m/z 173 C11H13N2+ or C13H17+ --> needs very high mass resolution • CxHyNz+ ions correspond to many possible isomers --> needs for structural/functional analysis • Reactions forming CxHyNz+ ions are not well known --> what is the growth chemical scheme and where does it stop?

  9. Reactions MS/MS High Resolution Mass spectrom New experimental set-up:

  10. High mass resolution?Example of cigarette smoke analysis Resolution: 6000 Resolution: 12000

  11. 42 30 54 CH3CN C2H3CN CH2NH NH3 18 56 C2H5CN The « underestimated channels »active synthesis of neutral molecules Assuming that the missing peaks correspond to protonated, N-containing molecules, ion densities allow To propose a density for neutral molecules, totally Unexptected at such high altitudes and revealing a process of neutral syntheses in the ionosphere Vuitton et al. 2006

  12. 30 18 14 strongly underestimated Result of the uncertainty propagationCarrasco et al, Planet. Space Sci. 2006, in press Ionospheric model of M. Banaszkiewicz et al. Icarus (2000)Uncertainties on rate constants and branching ratios HCNH+ Cassini INMS mass spectrum Simulated mass spectrum 1200 km Same simulated spectrum with 248 reactions instead of 584 ! many reactions are missing

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