Orbitrap Mass Analyser: a Tool for Titan Complex Molecular Content

Exploration

Roland Thissen GrenobleStefano Cornelli GrenoblePascal Puget Grenoble

Christelle Briois OrléansLaurent Thirkell OrléansAmirouche Boukrara OrléansJean-Pierre Lebreton Orléans

Patricia Beauchamp PasadenaEvan Neidholdt PasadenaJack Beauchamp Pasadena

Hervé Cottin CreteilNoel Grand Creteil

Cyril Szopa VersaillesNathalie Carrasco VersaillesClaude Chapuis VersaillesAbdel Bouabdellah Versailles

Cécile Engrand Orsay

Alexander Makarov Bremen

ToulouseParis

High mass-resolution for Titan?

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Quad masse filter

60 uma luckily upgraded in 100 amu

Resolution limited to 1 amu

m/z 28

N2+, C2H4

+, HCNH+

Cassini (INMS) ionic densities in Titan ionosphere

C7NH+ 99.0109 resolution

C8H3+ 99.0235 7857

C4N3H9+ 99.0797 1761

C5N2H11+ 99.0923 7857

C6NH13+ 99.1049 7853

C7H15+ 99.1174 7920

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Big molecule synthesis …

Positive ions <350 Negative ions >1000

m/z

+ -

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Bio molecules synthesis…

Horst et al. Accepted in Astrobiology

6 / 46 Tholins mass spectrum at high resolution

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Zoom on mass 262

100

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0

x10

3

262.35262.30262.25262.20262.15262.10262.05262.00

100

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x103

070511_Lot1MeOH_b #663-697 RT: 19,32-20,28 AV: 35 NL: 1,02E5T: FTMS + p ESI Full ms [50,00-500,00]

262,0 262,1 262,2 262,3m/z

0

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90

100

Rela

tive A

bundance

262,1774

262,1526

262,2026

262,1412

262,1275262,1004262,0216 262,2161 262,3478

C9H16N7

C11H20N5

C7H12N9

C=12.0000H= 1.0078N=14.0031

C7H12N5O2

ISOTOPES

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fulvique pos SIM700-800FT #6-336 RT: 0.15-9.77 AV: 331 NL: 5.08E3T: FTMS + p ESI SIM ms [700.00-800.00]

773.2 773.4 773.6 773.8 774.0 774.2 774.4 774.6 774.8 775.0 775.2 775.4 775.6

m/z

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Re

lative

Ab

un

da

nce

773.30243C39 H49 O16

775.28195C38 H47 O17

773.33907C40 H53 O15

773.26603C38 H45 O17

775.24527C37 H43 O18

773.22966C37 H41 O18

775.35458C40 H55 O15

775.20911C36 H39 O19

775.13636C34 H31 O21

773.37535C41 H57 O14

774.30463

774.34089

775.10005C33 H27 O22

774.26786

774.22613

774.19037775.39105

C41 H59 O14

774.51638

774.37241

774.12421

774.59469773.41210

C42 H61 O13

775.06434C50 H15 O10

774.08702775.51910

C41 H75 O13774.69143773.89316

773 774 775

13C

Isotopical abundancies,example on complex mixture…

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fulvique pos SIM700-800FT #6-336 RT: 0.15-9.77 AV: 331 NL: 5.08E3T: FTMS + p ESI SIM ms [700.00-800.00]

773.2 773.4 773.6 773.8 774.0 774.2 774.4 774.6 774.8 775.0 775.2 775.4 775.6

m/z

0

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Re

lative

Ab

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da

nce

773.30243C39 H49 O16

775.28195C38 H47 O17

773.33907C40 H53 O15

773.26603C38 H45 O17

775.24527C37 H43 O18

773.22966C37 H41 O18

775.35458C40 H55 O15

775.20911C36 H39 O19

775.13636C34 H31 O21

773.37535C41 H57 O14

774.30463

774.34089

775.10005C33 H27 O22

774.26786

774.22613

774.19037775.39105

C41 H59 O14

774.51638

774.37241

774.12421

774.59469773.41210

C42 H61 O13

775.06434C50 H15 O10

774.08702775.51910

C41 H75 O13774.69143773.89316

18O

Orbitrap mass Analyser ?

11 / 46 Preliminary remark, what is orbitrap…

Mass Spectrometry :

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Perfect quadro logarithmic potential

zm

k

/

record movement of unperturbed ions during

>500mspressure <10-9 mbar!

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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 / 46 Orbitrap, potential

Ultra high resolution: 100 000 at mass 400, adjustable during mission, as it depends only on the integration timeVery small volume, lightweight : l=4 , = 4 cmGood detection Dynamic : 50 000 per spectrumPositive or negative Ions as only one potential to invertAll ions are analysed simultaneouslyNo detector, no saturation, …no RF, no moving partIdeal for solids or aerosols

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Study of optimizedMS instrument for the analysis of aerosols/solids/liquids present in the deep atmosphere/surface of

Titan

Orbitrap for Titan

Orbitrap prototype in

OrléansSample handling

ionization

Ion accumulation

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Performances of prototype…

Without laser

With laser

FREQUENCY /KHz

17 / 46 1 laser shot on Stainless steel

m/z

R=280 000

18 / 46 Tholins survive the laser desorption/ionization

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ConclusionsGoing back to Titan, we need to do much better than Cassini.We know that very large (bio)organic molecules are produced/present in Atmosphere Aerosols 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/BBriois, Cornelli and Thirkell