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Exobiology in the Solar System & The Search for Life on Mars - ESA

Exobiology in the Solar System & The Search for Life on Mars - ESA

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provided that a depth below <str<strong>on</strong>g>the</str<strong>on</strong>g> str<strong>on</strong>g oxidis<str<strong>on</strong>g>in</str<strong>on</strong>g>g c<strong>on</strong>diti<strong>on</strong>s can be reached. This<br />

approach offers <str<strong>on</strong>g>the</str<strong>on</strong>g> possibility of determ<str<strong>on</strong>g>in</str<strong>on</strong>g><str<strong>on</strong>g>in</str<strong>on</strong>g>g a depth gradient of redox-sensitive<br />

geochemical parameters. This is particularly true <str<strong>on</strong>g>for</str<strong>on</strong>g> sulphur. In additi<strong>on</strong>, <str<strong>on</strong>g>the</str<strong>on</strong>g> presence<br />

of sulphur phases <str<strong>on</strong>g>in</str<strong>on</strong>g> different oxidati<strong>on</strong> states and <str<strong>on</strong>g>the</str<strong>on</strong>g>ir subsequent isotopic analysis<br />

will yield <str<strong>on</strong>g>in</str<strong>on</strong>g><str<strong>on</strong>g>for</str<strong>on</strong>g>mati<strong>on</strong> <strong>on</strong> <str<strong>on</strong>g>the</str<strong>on</strong>g> mode of redox reacti<strong>on</strong>s, specifically a possible<br />

participati<strong>on</strong> of biologically-c<strong>on</strong>trolled processes. <str<strong>on</strong>g>The</str<strong>on</strong>g> analytical approach could<br />

<str<strong>on</strong>g>in</str<strong>on</strong>g>clude previously applied techniques such as stepped combusti<strong>on</strong> and isotopic<br />

analyses of result<str<strong>on</strong>g>in</str<strong>on</strong>g>g SO 2 fracti<strong>on</strong>s and sulphur isotope measurements us<str<strong>on</strong>g>in</str<strong>on</strong>g>g an i<strong>on</strong><br />

microprobe. <str<strong>on</strong>g>The</str<strong>on</strong>g> full analytical spectrum, however, is still possible <strong>on</strong>ly <str<strong>on</strong>g>in</str<strong>on</strong>g> Earthbased<br />

laboratories, requir<str<strong>on</strong>g>in</str<strong>on</strong>g>g a sample-return missi<strong>on</strong>. Spacecraft analytical facilities<br />

might, however, obta<str<strong>on</strong>g>in</str<strong>on</strong>g> sufficient data through combusti<strong>on</strong> followed by isotope ratio<br />

mass spectrometry of sulphur-bear<str<strong>on</strong>g>in</str<strong>on</strong>g>g compounds (i.e. m<str<strong>on</strong>g>in</str<strong>on</strong>g>eral phases). It should be<br />

possible to per<str<strong>on</strong>g>for</str<strong>on</strong>g>m this type of analysis <strong>on</strong> surface and subsurface material. Sample<br />

material would have to be crushed (better: pulverised) be<str<strong>on</strong>g>for</str<strong>on</strong>g>e deliver<str<strong>on</strong>g>in</str<strong>on</strong>g>g it to <str<strong>on</strong>g>the</str<strong>on</strong>g><br />

furnace. S<str<strong>on</strong>g>in</str<strong>on</strong>g>ce <str<strong>on</strong>g>the</str<strong>on</strong>g> sample material will likely c<strong>on</strong>ta<str<strong>on</strong>g>in</str<strong>on</strong>g> o<str<strong>on</strong>g>the</str<strong>on</strong>g>r oxidisable comp<strong>on</strong>ents, a<br />

chromatographic separati<strong>on</strong> of <str<strong>on</strong>g>the</str<strong>on</strong>g> gas mixture (such as <str<strong>on</strong>g>in</str<strong>on</strong>g> elemental analysers with a<br />

c<strong>on</strong>flow-setup) is a prerequisite <str<strong>on</strong>g>in</str<strong>on</strong>g> order to obta<str<strong>on</strong>g>in</str<strong>on</strong>g> reas<strong>on</strong>ably pure SO 2 <str<strong>on</strong>g>for</str<strong>on</strong>g> mass<br />

spectrometric analyses. A temperature-based separati<strong>on</strong>, analogous to <str<strong>on</strong>g>the</str<strong>on</strong>g> stepped<br />

combusti<strong>on</strong> approach, might be used to study different m<str<strong>on</strong>g>in</str<strong>on</strong>g>eral phases of different<br />

sulphur oxidati<strong>on</strong> states.<br />

In c<strong>on</strong>clusi<strong>on</strong>, a MODULUS-like <str<strong>on</strong>g>in</str<strong>on</strong>g>strumentati<strong>on</strong>, based <strong>on</strong> chemical trans<str<strong>on</strong>g>for</str<strong>on</strong>g>mati<strong>on</strong>s,<br />

<str<strong>on</strong>g>in</str<strong>on</strong>g>clud<str<strong>on</strong>g>in</str<strong>on</strong>g>g stepped combusti<strong>on</strong> and pyrolysis, coupled to gas chromatography<br />

-mass spectrometry techniques can fulfil most of <str<strong>on</strong>g>the</str<strong>on</strong>g> scientific objectives described <str<strong>on</strong>g>in</str<strong>on</strong>g><br />

II.5.3.<br />

<str<strong>on</strong>g>The</str<strong>on</strong>g> analysis of <str<strong>on</strong>g>in</str<strong>on</strong>g>organic and organic compounds can be efficiently carried out by gas<br />

chromatography coupled to pyrolysis and mass spectrometry (PYR-GC-MS).<br />

II.5.9.1 Gas Chromatography (GC)<br />

Gas chromatography is a powerful technique <str<strong>on</strong>g>for</str<strong>on</strong>g> analys<str<strong>on</strong>g>in</str<strong>on</strong>g>g complex mixtures of gases<br />

or volatilisable c<strong>on</strong>stituents, and it will be a crucial comp<strong>on</strong>ent of <str<strong>on</strong>g>the</str<strong>on</strong>g> proposed<br />

exobiology <str<strong>on</strong>g>in</str<strong>on</strong>g>strumentati<strong>on</strong> package. Schematically, a gas chromatograph <str<strong>on</strong>g>in</str<strong>on</strong>g>cludes:<br />

(i) a carrier gas reservoir and pressure c<strong>on</strong>troller; (ii) an <str<strong>on</strong>g>in</str<strong>on</strong>g>jecti<strong>on</strong> subsystem, where a<br />

sample of <str<strong>on</strong>g>the</str<strong>on</strong>g> mixture to be analysed is <str<strong>on</strong>g>in</str<strong>on</strong>g>troduced and carried by <str<strong>on</strong>g>the</str<strong>on</strong>g> carrier gas <str<strong>on</strong>g>in</str<strong>on</strong>g>to<br />

(iii) <strong>on</strong>e or several (<str<strong>on</strong>g>in</str<strong>on</strong>g> series or <str<strong>on</strong>g>in</str<strong>on</strong>g> parallel) GC columns – <str<strong>on</strong>g>the</str<strong>on</strong>g> heart of <str<strong>on</strong>g>the</str<strong>on</strong>g> GC system,<br />

where <str<strong>on</strong>g>the</str<strong>on</strong>g> separati<strong>on</strong> occurs – and (iv) a detector, c<strong>on</strong>nected at <str<strong>on</strong>g>the</str<strong>on</strong>g> exit of <str<strong>on</strong>g>the</str<strong>on</strong>g> column,<br />

able to <str<strong>on</strong>g>in</str<strong>on</strong>g>dicate systematically eluti<strong>on</strong> of compounds (o<str<strong>on</strong>g>the</str<strong>on</strong>g>r than <str<strong>on</strong>g>the</str<strong>on</strong>g> carrier gas) from<br />

<str<strong>on</strong>g>the</str<strong>on</strong>g> column(s).<br />

<str<strong>on</strong>g>The</str<strong>on</strong>g> carrier gas is usually He, N 2, Ar or H 2. It flows c<strong>on</strong>t<str<strong>on</strong>g>in</str<strong>on</strong>g>uously through <str<strong>on</strong>g>the</str<strong>on</strong>g><br />

column, carry<str<strong>on</strong>g>in</str<strong>on</strong>g>g <str<strong>on</strong>g>the</str<strong>on</strong>g> different c<strong>on</strong>stituents at different rates, depend<str<strong>on</strong>g>in</str<strong>on</strong>g>g <strong>on</strong> <str<strong>on</strong>g>the</str<strong>on</strong>g>ir<br />

chemical structures and molecular weights. <str<strong>on</strong>g>The</str<strong>on</strong>g> column can be a tube of a few metres<br />

length and <strong>on</strong>e to a few mm <str<strong>on</strong>g>in</str<strong>on</strong>g>ternal diameter, packed with an absorbent (GSC: Gas<br />

Solid Chromatography) or with an absorbent impregnated with a stati<strong>on</strong>ary phase, a<br />

liquid of very low vapour pressure (GLC: Gas Liquid Chromatography). It can also<br />

be a l<strong>on</strong>ger (10-100 m) and open tube (wall-coated open tubular), with smaller<br />

<str<strong>on</strong>g>in</str<strong>on</strong>g>ternal diameter (0.5-0.1 mm), coated with a film of a solid absorbent (GSC) or of<br />

liquid phase (GLC). <str<strong>on</strong>g>The</str<strong>on</strong>g> chemical nature of <str<strong>on</strong>g>the</str<strong>on</strong>g> absorbent or <str<strong>on</strong>g>the</str<strong>on</strong>g> liquid phase is<br />

directly related to <str<strong>on</strong>g>the</str<strong>on</strong>g> chemical nature of <str<strong>on</strong>g>the</str<strong>on</strong>g> compounds to be analysed. <str<strong>on</strong>g>The</str<strong>on</strong>g> best<br />

universal detector is probably a mass spectrometer, able to provide <str<strong>on</strong>g>the</str<strong>on</strong>g> mass signature<br />

of each eluted compound and hence allow<str<strong>on</strong>g>in</str<strong>on</strong>g>g a secure identificati<strong>on</strong> of each GC peak.<br />

<str<strong>on</strong>g>The</str<strong>on</strong>g> GC-MS coupl<str<strong>on</strong>g>in</str<strong>on</strong>g>g requires that most of <str<strong>on</strong>g>the</str<strong>on</strong>g> carrier gas be removed from <str<strong>on</strong>g>the</str<strong>on</strong>g><br />

sample be<str<strong>on</strong>g>for</str<strong>on</strong>g>e it enters <str<strong>on</strong>g>the</str<strong>on</strong>g> mass spectrometer.<br />

In <str<strong>on</strong>g>the</str<strong>on</strong>g> case where multi-GC columns are used <str<strong>on</strong>g>in</str<strong>on</strong>g> parallel, specific GC detectors<br />

must be used (<str<strong>on</strong>g>in</str<strong>on</strong>g> additi<strong>on</strong> to MS coupl<str<strong>on</strong>g>in</str<strong>on</strong>g>g, as planned <strong>on</strong> Rosetta’s COSAC<br />

<str<strong>on</strong>g>in</str<strong>on</strong>g>strument). Nano-<str<strong>on</strong>g>the</str<strong>on</strong>g>rmal c<strong>on</strong>ductivity detectors (nano-TCDs) are commercially<br />

available <str<strong>on</strong>g>in</str<strong>on</strong>g> Europe, but <str<strong>on</strong>g>the</str<strong>on</strong>g>y need to be space qualified. Detectors able to<br />

team II: <str<strong>on</strong>g>the</str<strong>on</strong>g> search <str<strong>on</strong>g>for</str<strong>on</strong>g> chemical <str<strong>on</strong>g>in</str<strong>on</strong>g>dicators of life/II.5<br />

II.5.9 Molecular Analysis<br />

147

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