1. Orbitrap Mass Analyser: a Tool for Titan Complex Molecular Content Exploration Roland ThissenGrenoble Stefano CornelliGrenoble Pascal PugetGrenoble Christelle BrioisOrléans Laurent ThirkellOrléans Amirouche BoukraraOrléans Jean-Pierre LebretonOrléans Patricia BeauchampPasadena Evan NeidholdtPasadena Jack BeauchampPasadena Hervé CottinCreteil Noel GrandCreteil Cyril SzopaVersailles Nathalie Carrasco Versailles Claude ChapuisVersailles Abdel Bouabdellah Versailles Cécile Engrand Orsay Alexander Makarov Bremen Toulouse Paris

2. High mass-resolution for Titan?

3. 3 / 46  Quad masse filter  60 uma luckily upgraded in 100 amu  Resolution limited to 1 amu m/z 28 N 2 +, C 2 H 4 +, HCNH + Cassini (INMS) ionic densities in Titan ionosphere C 7 NH + 99.0109resolution C8H3+C8H3+ 99.02357857 C4N3H9+C4N3H9+ 99.07971761 C 5 N 2 H 11 + 99.09237857 C 6 NH 13 + 99.10497853 C 7 H 15 + 99.11747920

4. 4 / 46 Big molecule synthesis … Positive ions <350Negative ions >1000 m/z + -

5. 5 / 46 Bio molecules synthesis… Horst et al. Accepted in Astrobiology

6. 6 / 46 Tholins mass spectrum at high resolution

7. 7 / 46 Zoom on mass 262 C9H16N7 C11H20N5 C7H12N9 C=12.0000 H= 1.0078 N=14.0031 C7H12N5O2 ISOTOPES

8. 8 / 46 773774775 13 C Isotopical abundancies, example on complex mixture…

9. 9 / 46 18 O

10. Orbitrap mass Analyser ?

11. 11 / 46 Preliminary remark, what is orbitrap… Mass Spectrometry :

12. 12 / 46 Perfect quadro logarithmic potential record movement of unperturbed ions during >500ms pressure <10 -9 mbar!

13. 13 / 46 How to inject and stabilize ions in this perfect potential? “Electrodynamic squeezing” (r,φ) (r,z) a bunch of ions enters in the field, tangentially ions are squeezed towards central electrode by variation of its potential (deepening of well) The excitation of quadratic movement is inherent to “off axis” injection Need to pulse ions in the trap! Need for very stable HV potential During measurement!

14. 14 / 46 Orbitrap, potential Ultra high resolution: 100 000 at mass 400, adjustable during mission, as it depends only on the integration time Very small volume, lightweight : l=4,  = 4 cm Good detection Dynamic : 50 000 per spectrum Positive or negative Ions as only one potential to invert All ions are analysed simultaneously No detector, no saturation, … no RF, no moving part Ideal for solids or aerosols

15. 15 / 46 Study of optimized MS instrument for the analysis of aerosols/solids/liquids present in the deep atmosphere/surface of Titan Orbitrap for Titan Orbitrap prototype in Orléans Sample handling ionization Ion accumulation

16. 16 / 46 Performances of prototype… Without laser With laser FREQUENCY /KHz

17. 17 / 46 1 laser shot on Stainless steel m/z R=280 000

18. 18 / 46 Tholins survive the laser desorption/ionization

19. 19 / 46 Conclusions Going back to Titan, we need to do much better than Cassini. We know that very large (bio)organic molecules are produced/present in AtmosphereAerosols Surface Liquids / solids Request for very high resolution mass spectrometry to be characterized. Orbitrap is a very promising analyser/detector for this purpose. However big challenges remain: Sample handling ? Ionization method ? High-Vacuum generation/maintenance ? Beyond formulas, what about structural analysis ? … Further info ? Come & visit posters 7A/B Briois, Cornelli and Thirkell