Exobiology in the Solar System & The Search for Life on Mars - ESA
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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SP-1231<br />
150<br />
determ<str<strong>on</strong>g>in</str<strong>on</strong>g>ed <str<strong>on</strong>g>in</str<strong>on</strong>g> <str<strong>on</strong>g>in</str<strong>on</strong>g>dividual phases <str<strong>on</strong>g>in</str<strong>on</strong>g> situ by add<str<strong>on</strong>g>in</str<strong>on</strong>g>g an LA-ICP i<strong>on</strong> source to <str<strong>on</strong>g>the</str<strong>on</strong>g> MS.<br />
This method is very fast and, if a separate MS can be dedicated to that task, it will<br />
give by far <str<strong>on</strong>g>the</str<strong>on</strong>g> most data <str<strong>on</strong>g>for</str<strong>on</strong>g> analys<str<strong>on</strong>g>in</str<strong>on</strong>g>g <str<strong>on</strong>g>the</str<strong>on</strong>g> phase equilibria and <str<strong>on</strong>g>for</str<strong>on</strong>g>mati<strong>on</strong> c<strong>on</strong>diti<strong>on</strong>s<br />
of:<br />
• primary phase assemblages;<br />
• sec<strong>on</strong>dary phases;<br />
• atmosphere-related phases (coat<str<strong>on</strong>g>in</str<strong>on</strong>g>gs, efflorescences, etc);<br />
• organic matter.<br />
This <str<strong>on</strong>g>in</str<strong>on</strong>g>strument should also be capable of per<str<strong>on</strong>g>for</str<strong>on</strong>g>m<str<strong>on</strong>g>in</str<strong>on</strong>g>g isotopic abundance measurements<br />
and thus could be very important <str<strong>on</strong>g>in</str<strong>on</strong>g> <str<strong>on</strong>g>the</str<strong>on</strong>g> search <str<strong>on</strong>g>for</str<strong>on</strong>g> life or life remnants.<br />
II.5.9.6 O<str<strong>on</strong>g>the</str<strong>on</strong>g>r Techniques<br />
O<str<strong>on</strong>g>the</str<strong>on</strong>g>r techniques can be envisaged <str<strong>on</strong>g>for</str<strong>on</strong>g> analys<str<strong>on</strong>g>in</str<strong>on</strong>g>g compounds of very low volatility or<br />
n<strong>on</strong>-volatile compounds (<str<strong>on</strong>g>in</str<strong>on</strong>g>organics, PAHs, am<str<strong>on</strong>g>in</str<strong>on</strong>g>o acids, pur<str<strong>on</strong>g>in</str<strong>on</strong>g>es, macromolecular<br />
organics). <str<strong>on</strong>g>The</str<strong>on</strong>g>y <str<strong>on</strong>g>in</str<strong>on</strong>g>clude derivatisati<strong>on</strong> system-GC-MS, High-Per<str<strong>on</strong>g>for</str<strong>on</strong>g>mance Liquid<br />
Chromatography (HPLC) and Supercritical Fluid Chromatography (SFC).<br />
Derivatisati<strong>on</strong> processes are often used <str<strong>on</strong>g>in</str<strong>on</strong>g> <str<strong>on</strong>g>the</str<strong>on</strong>g> laboratory to analyse n<strong>on</strong>-volatile<br />
organics by GC or GC-MS. This is <str<strong>on</strong>g>the</str<strong>on</strong>g> case with am<str<strong>on</strong>g>in</str<strong>on</strong>g>o acids. A two-step chemical<br />
derivatisati<strong>on</strong> (esterificati<strong>on</strong> of <str<strong>on</strong>g>the</str<strong>on</strong>g> acidic group followed by trifluoroacetylati<strong>on</strong> of<br />
<str<strong>on</strong>g>the</str<strong>on</strong>g> am<str<strong>on</strong>g>in</str<strong>on</strong>g>o group) trans<str<strong>on</strong>g>for</str<strong>on</strong>g>ms <str<strong>on</strong>g>the</str<strong>on</strong>g> n<strong>on</strong>-volatile am<str<strong>on</strong>g>in</str<strong>on</strong>g>o acids to volatile N-TFA esters,<br />
which can be quantitatively analysed by GC or GC-MS. However, this has never been<br />
used <str<strong>on</strong>g>in</str<strong>on</strong>g> space and an automatic derivatisati<strong>on</strong> system compatible with space<br />
c<strong>on</strong>stra<str<strong>on</strong>g>in</str<strong>on</strong>g>ts has yet to be developed.<br />
HPLC is also 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 high<br />
molecular weight, low-volatility compounds. It uses liquid solvent (<str<strong>on</strong>g>in</str<strong>on</strong>g>stead of <str<strong>on</strong>g>the</str<strong>on</strong>g><br />
GC’s carrier gas), a requirement that might be very difficult to qualify <str<strong>on</strong>g>for</str<strong>on</strong>g> space<br />
activity. However, if developed <str<strong>on</strong>g>for</str<strong>on</strong>g> space applicati<strong>on</strong>, it would be an <str<strong>on</strong>g>in</str<strong>on</strong>g>strument of<br />
tremendous importance <str<strong>on</strong>g>for</str<strong>on</strong>g> exobiological studies. Thus, <str<strong>on</strong>g>the</str<strong>on</strong>g>re is a clear need <str<strong>on</strong>g>for</str<strong>on</strong>g><br />
research and development of space HPLC and HPLC-MS systems.<br />
A related method to HPLC is SFC. In this case, a very unreactive gas is compressed<br />
to a temperature at which it becomes supercritical. Under such circumstances,<br />
some species such as CO 2, can become an extremely powerful solvent, with<br />
properties that can be varied extensively by <str<strong>on</strong>g>the</str<strong>on</strong>g> additi<strong>on</strong> of small amounts of<br />
modify<str<strong>on</strong>g>in</str<strong>on</strong>g>g agents. Compounds <str<strong>on</strong>g>in</str<strong>on</strong>g> soluti<strong>on</strong> <str<strong>on</strong>g>in</str<strong>on</strong>g> supercritical fluids can be separated<br />
chromatographically. An <str<strong>on</strong>g>in</str<strong>on</strong>g>terest<str<strong>on</strong>g>in</str<strong>on</strong>g>g possibility <str<strong>on</strong>g>for</str<strong>on</strong>g> <strong>Mars</strong> might be utilis<str<strong>on</strong>g>in</str<strong>on</strong>g>g <str<strong>on</strong>g>the</str<strong>on</strong>g><br />
atmosphere itself as a supercritical reagent <str<strong>on</strong>g>for</str<strong>on</strong>g> carry<str<strong>on</strong>g>in</str<strong>on</strong>g>g out organic analysis. Land<str<strong>on</strong>g>in</str<strong>on</strong>g>g<br />
spacecraft would <str<strong>on</strong>g>the</str<strong>on</strong>g>n not have to transport hazardous c<strong>on</strong>sumables <str<strong>on</strong>g>for</str<strong>on</strong>g> chromatographic<br />
separati<strong>on</strong>s, <strong>on</strong>ly <str<strong>on</strong>g>the</str<strong>on</strong>g> hardware and an appropriate pump. SFC has also not<br />
been used <str<strong>on</strong>g>in</str<strong>on</strong>g> space, but it might be somewhat easier to develop than HPLC.<br />
European laboratories are study<str<strong>on</strong>g>in</str<strong>on</strong>g>g <str<strong>on</strong>g>the</str<strong>on</strong>g> feasibility of <str<strong>on</strong>g>the</str<strong>on</strong>g>se different c<strong>on</strong>cepts.<br />
II.5.9.7 <str<strong>on</strong>g>The</str<strong>on</strong>g> Analysis of H 2O 2<br />
<str<strong>on</strong>g>The</str<strong>on</strong>g> quantitative analysis of H 2O 2 will be difficult by GC, MS or GC-MS techniques<br />
and, ow<str<strong>on</strong>g>in</str<strong>on</strong>g>g to its scientific importance, it will require a specific <str<strong>on</strong>g>in</str<strong>on</strong>g>strumentati<strong>on</strong>.<br />
Hydrogen peroxide is usually analysed <str<strong>on</strong>g>in</str<strong>on</strong>g> envir<strong>on</strong>mental sciences by complex<br />
techniques based <strong>on</strong> chemilum<str<strong>on</strong>g>in</str<strong>on</strong>g>escence or UV fluorescence. <str<strong>on</strong>g>The</str<strong>on</strong>g>se techniques<br />
<str<strong>on</strong>g>in</str<strong>on</strong>g>volve, after air sampl<str<strong>on</strong>g>in</str<strong>on</strong>g>g, chemical derivatisati<strong>on</strong>, us<str<strong>on</strong>g>in</str<strong>on</strong>g>g liquid transfers, chemical<br />
reactors, <str<strong>on</strong>g>in</str<strong>on</strong>g>jecti<strong>on</strong> valves and enzyme storage. Fur<str<strong>on</strong>g>the</str<strong>on</strong>g>rmore, <str<strong>on</strong>g>the</str<strong>on</strong>g>y require very<br />
accurate calibrati<strong>on</strong>. Thus, although <str<strong>on</strong>g>the</str<strong>on</strong>g>ir sensitivity is very high (a few ppt – parts per<br />
trilli<strong>on</strong>, 10 12 !), <str<strong>on</strong>g>the</str<strong>on</strong>g>y do not seem adequate <str<strong>on</strong>g>for</str<strong>on</strong>g> space applicati<strong>on</strong>.<br />
Ano<str<strong>on</strong>g>the</str<strong>on</strong>g>r type of <str<strong>on</strong>g>in</str<strong>on</strong>g>strumentati<strong>on</strong> can also be used to analyse H 2O 2 quantitatively,<br />
although it is less sensitive (parts per milli<strong>on</strong> range). It <str<strong>on</strong>g>in</str<strong>on</strong>g>volves electrochemical<br />
measurements with:<br />
i. rotat<str<strong>on</strong>g>in</str<strong>on</strong>g>g electrode (amperometric titrati<strong>on</strong>),<br />
ii. specific H 2O 2 electrode (oxidati<strong>on</strong> or reducti<strong>on</strong> <strong>on</strong> a plat<str<strong>on</strong>g>in</str<strong>on</strong>g>um disc electrode),