The Goddard Center for Astrobiology – Theme IV In-situ extraction, separation, and analysis of organics Theme IV activities and synergies Paul Mahaffy Topics 1.Organics on Mars – a MSL snapshot 2.Chemical Derivatization 3.Comet Mission Opportunities 4.Svalbard Field Campaign 5.Theme IV synergies

1.Organics on Mars – a MSL snapshot

Exploration approach  “follow the water” path to understand potential for life on Mars Meridiani Planum  evidence of aqueous alteration in sulfates (MER team argues are evidence of sedimentary layers) Mars Express OMEGA  spectroscopic evidence in (Mawrth Vallis, Nili-Syrtis, and elsewhere) of phyllosilicates. These clays may have formed under wet alkaline conditions and may provide a preservation environment for biosignatures (map below from Poulet, Bibring et al., 2006 LPSC. MSL designed to “assess a potential habitat”  AO solicited scientific investigations Objectives include a search for organics, definitive mineralogy, and light isotope measurements 1.Organics on Mars – where to look

Remote Sensing Investigations MastCam(Imaging, Atmospheric Opacity) ChemCam (Chemical Composition, Imaging) MARDI (Landing Site Descent Imaging) Contact Investigations APXS (Chemical Composition) MAHLI (Microscopic Imaging) Analytic Laboratory Investigations CheMin (Mineralogy, Chemical Composition) SAM (Chemical/Isotopic Comp., Organics) Environmental Investigations DAN (Subsurface Hydrogen) REMS (Meteorology / UV Radiation) RAD (High-Energy Radiation) SAM is a suite of 3 instruments a quadrupole mass spectrometer (QMS) a gas chromatograph (GC) a tunable laser spectrometer (TLS) SAM Core Science 1) Explore sources and destruction paths for carbon compounds 2) Search for organic compounds of biotic and prebiotic relevance including methane 3) Reveal chemical state of other light elements that are important for life as we know it on Earth 4) Study habitability of Mars by measuring oxidants such as hydrogen peroxide 5) Investigate atmosphere and climate evolution through isotope measurements of noble gases and light elements 1.Organics on Mars – MSL investigations

SMS and Housing Tunable Laser Spectrometer Electronics Solid Sample Inlets Gas Chromatograph Chemical Separation and Processing Laboratory Quadrupole Mass Spectrometer Wide Range Pump Atmospheric Inlets Solid sample inlets penetrate through MSL top deck Atmospheric inlets and vents located on side of SAM box and penetrate +Y face of MSL WEB 1.Organics on Mars – the Sample Analysis at Mars (SAM) suite

Site Context MastCamand ChemCam provide a geological and chemical survey for more detailed sampling by Analytical Laboratory instruments and DAN identifies potentially very interesting sites with enhanced subsurface H Sample Screening APXS and MAHLI chemically and with microscopic imaging screen surface materials, sampled cores or processed samples – after such screening samples can either be discarded or delivered to Analytical Laboratory Winds and Radiation REMS wind, temperature, and UV measurements are most relevant to SAM atmospheric sampling RAD provided information on surface radiation is relevant to models of transformation of organics Definitive Mineralogy CheMin’s elemental analysis and unambiguous identification of mineral types is highly complementary to the SAM volatile and organics analysis 1.Organics on Mars – synergy of MSL payload elements

Possible Sources of Organic Compounds on Mars Exogenous Sources: infall of meteorites and interplanetary dust particles (IDPs); major cometary impacts [IDP influx kg/yr] C-condrites are primarily kerogen-like macromolecular compounds but contain discrete pre- biotic compounds  in absence of efficient destruction paths percentages of regolith could be organic Indigenous Sources: pre-biotic/abiotic chemicals, martian life (extinct or extant)  life leaves distinct chemical and isotopic patterns in organic residues Terrestrial contamination: MSL will arrive at Mars with kilograms of organic compounds – some of fraction of which will make their way to SAM ingested samples Transformation and preservation of organic compounds on Mars UV reaches Mars surface and destroys exposed organics (stable refractory organics survive best) Oxidation by hydrogen peroxide or other oxidants  may transform reduced organics into metastable carboxylic acids Galactic cosmic radiation is expected to transform organics in the near surface (~several cm) and natural radioactivity over longer time periods 1.Organics on Mars – SAM first core science goal - explore sources and destruction paths for carbon compounds

Molecules or classes of molecule most directly relevant to life Methane: Mars Express PFS 10 ppbv average (variable over planet 0-30 ppbv), ground based observations also in progress  ~90 % of terrestrial methane is likely of biological origin although abiotic production mechanisms such as serpentization reactions also contribute Methane in the Mars atmosphere has a photochemical half life of years Formaldehyde: Tentatively reported by Phobos; typically produced terrestrially by biogenic sources or photochemical decomposition of organic matter Amino Acids: Building blocks of proteins and enzymes in life on Earth and often found in ancient sedimentary depostis;  distinguished from meteoritic abiotically produced amino acids by type; for example, AIB (alpha-aminoisobutyric acid) is used as tracer for meteorite impacts Amines: Ammonia derivatives essential to terrestrial life and analyzed as tracers of biological processes; also produced by thermal decarboxylation of several amino acids Nucleobases: purines and pyrimidines that play a key role in terrestrial biochemistry; although these are also produced abiotically their source can be identified by type distribution Carboxylic acids: predicted to be stable chemical end products of organic molecule oxidation  source may be identified by examination of molecular distribution 1.Organics on Mars – SAM second core science goal - search for organic compounds of biotic and prebiotic relevance including methane

The oxidant H 2 O 2 recently discovered by Mars Express PFS Electrochemistry associated with Martian aeolian processes (dust devils, storms, and normal saltation) is predicted to be a significant source of H 2 O 2 H 2 O 2 may precipitate to the surface and destroy near surface organics CH 4 may also be destroyed by heterogeneous processes and thus the CH 4 source may be stronger than if just photochemical processes were at work measurement of other photochemically active species is necessary to quantify the production and loss mechanisms 1.Organics on Mars – SAM’s 4th core science goal - study habitability of Mars by measuring oxidants such as hydrogen peroxide

2. Chemical Derivatization

ParameterVikingSAMScience Benefit Pyrolysis No. of sample cups374More samples analyzed – each cup can be used multiple times Temperature50, 200, 350, or 500ºCContinuous heating up to 1100ºCIdentification of mineral decomposition products Gas Chromatography ColumnsPoly MPE-TenaxMolsieve 5A carbo-bond, MXT 1,5, MXT PLOT U, RTX 5 Amine, Chirasil-Val Analysis of a wider range of organics, noble gases, VOCs, derivatized compounds, enantiomers and amines DerivatizationNoYes, MTBSTFATransforms key organic biomarkers Mass Spectrometer Mass range (Da) ID of wider range of species; derivatized compounds High throughput pumpsnoyesIncrease in sensitivity Static/dynamic modesDynamic onlyStatic or dynamicHigh precision noble gas isotopes Direct EGA monitoringnoyesDetect complex, less volatile species Tunable Laser Spectrometer (TLS) CH 4 and H 2 O 2 No TSL & MS isobaric interference Dedicated laser channels for CH 4 and H 2 O 2 Enables detection of these important by very trace species Isotope of C, O, HNo TLS & MS isobaric interference Isotopes of CO 2, H 2 O, and CH 4 Great improvement in precision of isotope measurements for C, O, H 2. Chemical Derivatization – Viking vs. MSL

2. Chemical Derivatization - simplified SAM derivatization process

The percent recovery of the derivatized amino acids at various transfer line temperatures relative to the standard recovery at a temperature of 280ºC. The uncertainty in the measurements shown is ± 10%. Abbreviations: ala, alanine; val, valine; ser, serine; and glu, glutamic acid. 2. Chemical Derivatization – temperature effects

Organic compounds MTBSTFA Volatile Derivative Derivatization required to transform reactive or fragile molecules that would not have been detected by Viking instruments into species that are sufficiently volatile to be detected by GCMS 2. Chemical Derivatization – the selected MSL derivatization agent

Chromatogram obtained at the University of Paris showing the GCMS response under the same operating conditions after injection of a solution of non- derivatized amino acids (red line) and the same solution of amino acids after derivatization with MTBSTFA (black line). Only derivatized amino acids could be detected by GCMS. 2. Chemical Derivatization – amino acids

Chromatogram from the Goddard Space Flight Center (GSFC) laboratory showing GC separation and several examples of mass spectra in a standard mixture containing 14 different amino acids and 7 nucleobases after derivatization using the MTBSTFA silylation agent selected for SAM using one of the SAM flight columns. 2. Chemical Derivatization – nucleobases & amino acid standards

GCMS analysis of organic compounds extracted from an Atacama Desert soil sample after chemical derivatization in a mixture of MTBSTFA and DMF using the SAM prototype derivatization cell and GC column at GSFC (top) and after direct pyrolysis of the Atacama soil without derivatization, data provided by R. Navarro-González (bottom). The peaks labeled X in the top chromatogram could not be identified by their mass fragmentation patterns. 2. Chemical Derivatization – Atacama extractions

GCMS analysis of an Atacama soil sample after single step extraction and derivatization with MTBSTFA and DMF at LISA. 2. Chemical Derivatization – more Atacama extractions

Arrhenius plot showing the evaporation loss rate vs. temperature of the MTBSTFA-DMF derivatization solvent mixture when exposed to Martian ambient pressure (7 torr air) inside a prototype derivatization cell. The percent mass loss of the derivatization solvent mixture 1 h after puncture at various elevated temperatures inside the MSL payload warm electronics box (WEB) is indicated by the dashed lines. To avoid significant solvent evaporation the maximum cup temperature during puncture shall be less than 9ºC. 2. Chemical Derivatization – how to make this work on MSL

3. Comet mission opportunities

NGIMS Specifications: Neutral Gas Sampling: (1) open source/molecular beaming (2) closed source/thermalized gas PositiveIon Sampling: thermal and suprathermal Ion Source: electron beam ionization Electron Energy: 75 eV Mass Range: 1 to 150 amu Detector System: dual detector pulse counting electron multipliers Scan Modes: (1) programmed mass mode (2) survey (scan amu in 1/10 or 1 amu steps (3) adaptive mode Deployment Mechanism: metal ceramic breakoff cap pyrotechnically activated Direct Heritage: CONTOUR, Cassini INMS 3. Comet mission opportunities – currently Discovery flyby proposal New Frontier program also provides opportunity for in situ measurements

4. Complementary activity Svalbard Field Campaign

ASTEP Mars Analogue Svalbard Expedition NRA 04-OSS-01 Astrobiology Science and Technology for Exploring Planets Andrew Steele Geophysical Lab CIW 4. Svalbard Field Campaign

4. Planned Field Campaign - Svalbard Objectives examine preservation of biotic processses in Mars analog materials test a range of analytical techniques in the field study issues of sample integrity and cross contamination compare field and laboratory instrumentation instruments/techniques  CHEMIN  GCMS  rover imaging system  life detection instruments  etc.

Mars analog carbonate deposits in vertical lava conduits Intimately associated with olivine which is also strewn across the base of Sverrefjell Abiological Stromatolites Sverrefjell 100 m 1 cm 20 µ Sverrefjell conduit Magnesite + dolomite cemented breccia ALH84001 type globules

10 km Bockfjord Volcanic Complex The worlds northernmost hot springs penetrating ~400 m permafrost Troll Springs travertine deposit Subglacial hot spring 10 m

Theme IV work and synergies Determine how to measure the history and the chemical state of organics in situ  wet extraction (Glavin, Botta, Tronick, Dworkin, Buch, Coll)  thermal extraction (Demick, Mahaffy, Franz)  LDMS extraction (Brinckerhoff)  hybrid ionization techniques (Brinckerhoff, Mahaffy) In situ and sample return studies and comet coma modeling  actively pursuing in situ opportunities  positioning members of GCA to participate in analysis of organics in sample return mission (Glavin, Dworkin) Comet coma modeling  3D MHD large computational scale model (Benna) Utilize the best available analogs to develop and calibrate instruments  weathered basalts and clays, meteoritic, Atacama and other terrestrial Mars analogues (Botta, Glavin, Mahaffy, Demick, Franz, Ming, Morris, Scott, Brinckerhoff)