Restricted accessResearch articleFirst published online 2020-03
Testing Flight-like Pyrolysis Gas Chromatography–Mass Spectrometry as Performed by the Mars Organic Molecule Analyzer Onboard the ExoMars 2020 Rover on Oxia Planum Analog Samples
The Mars Organic Molecule Analyzer (MOMA) onboard the ExoMars 2020 rover (to be landed in March 2021) utilizes pyrolysis gas chromatography–mass spectrometry (GC-MS) with the aim to detect organic molecules in martian (sub-) surface materials. Pyrolysis, however, may thermally destroy and transform organic matter depending on the temperature and nature of the molecules, thus altering the original molecular signatures. In this study, we tested MOMA flight-like pyrolysis GC-MS without the addition of perchlorates on well-characterized natural mineralogical analog samples for Oxia Planum, the designated ExoMars 2020 landing site. Experiments were performed on an iron-rich shale (that is rich in Fe-Mg-smectites) and an opaline chert, with known organic matter compositions, to test pyrolytic effects related to heating in the MOMA oven. Two hydrocarbon standards (n-octadecane and phytane) were also analyzed. The experiments show that during stepwise pyrolysis (300°C, 500°C, and 700°C), (1) low-molecular-weight hydrocarbon biomarkers (such as acyclic isoprenoids and aryl isoprenoids) can be analyzed intact, (2) discrimination between free and complex molecules (macromolecules) is principally possible, (3) secondary pyrolysis products and carryover may affect the 500°C and 700°C runs, and (4) the type of the organic matter (functionalized vs. defunctionalized) governs the pyrolysis outcome rather than the difference in mineralogy. Although pyrosynthesis reactions and carryover clearly have to be considered in data interpretation, our results demonstrate that pyrolysis GC-MS onboard MOMA operated under favorable conditions (e.g., no perchlorates) will be capable of providing important structural information on organic matter found on Mars, particularly when used in conjunction with other techniques on MOMA, including derivatization and thermochemolysis GC-MS and laser desorption/ionization–MS.
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References
1.
AppelJ., BockhornH., and FrenklachM. (2000) Kinetic modeling of soot formation with detailed chemistry and physics: laminar premixed flames of C2 hydrocarbons. Combust Flame, 121:122–136.
2.
BrittP.F., Buchanan, IIIA.C., and Owens, JrC.V. (2004) Mechanistic investigation into the formation of polycyclic aromatic hydrocarbons from the pyrolysis of terpenes. Prepr Pap Am Chem Soc Div Fuel Chem, 49:868–871.
3.
BrocksJ.J., LoveG.D., SnapeC.E., LoganG.A., SummonsR.E., and BuickR. (2003) Release of bound aromatic hydrocarbons from late Archean and Mesoproterozoic kerogens via hydropyrolysis. Geochim Cosmochim Acta, 67:1521–1530.
4.
BrooksJ.D., GouldK., and SmithJ.W. (1969) Isoprenoid hydrocarbons in coal and petroleum. Nature, 222:257–259.
5.
BurnhamA.K., ClarksonJ.E., SingletonM.F., WongC.M., and CrawfordR.W. (1982) Biological markers from Green River kerogen decomposition. Geochim Cosmochim Acta, 46:1243–1251.
6.
CarterJ., QuantinC., ThollotP., LoizeauD., OdyA., and LozachL. (2016) Oxia Planum: a clay-laden landing site proposed for the ExoMars Rover Mission: Aqueous Mineralogy and Alteration Scenarios. In 47th Lunar and Planetary Science Conference Abstracts, The Woodlands,TX.
7.
ClarkB.C. and KounavesS.P. (2016) Evidence for the distribution of perchlorates on Mars. Int J Astrobiol, 15:311–318.
8.
DidykB.M., SimoneitB.R.T., BrassellS.C., and EglintonG. (1978) Organic geochemical indicators of palaeoenvironmental conditions of sedimentation. Nature, 272:216–222.
9.
DudaJ.-P., Van KranendonkM.J., ThielV., IonescuD., StraussH., SchäferN., and ReitnerJ. (2016) A rare glimpse of paleoarchean life: geobiology of an exceptionally preserved microbial mat facies from the 3.4 Ga Strelley Pool Formation, Western Australia. PLoS ONE, 11:e0147629.
10.
DudaJ.-P., ThielV., BauersachsT., MißbachH., ReinhardtM., SchäferN., Van KranendonkM.J., and ReitnerJ. (2018) Ideas and perspectives: hydrothermally driven redistribution and sequestration of early Archaean biomass—the “hydrothermal pump hypothesis.” Biogeosciences, 15:1535–1548.
11.
DurandB. (1980) Sedimentary organic matter and kerogen. Definition and quantitative importance of kerogen. In Kerogen: Insoluble Organic Matter from Sedimentary Rocks, edited by DurandB., Editions Technip., Paris, pp 13–34.
12.
EglintonT.I., Sinninghe DamstéJ.S., PoolW., de LeeuwJ.W., EijkG., and BoonJ.J. (1992) Organic sulphur in macromolecular sedimentary organic matter. II. Analysis of distributions of sulphur-containing pyrolysis products using multivariate techniques. Geochim Cosmochim Acta, 56:1545–1560.
13.
EigenbrodeJ.L., SummonsR.E., SteeleA., FreissinetC., MillanM., Navarro-GonzálezR., SutterB., McAdamA.C., FranzH.B., GlavinD.P., ArcherJr., P.D., MahaffyP.R., ConradP.G., HurowitzJ.A., GrotzingerJ.P., GuptaS., MingD.W., SumnerD.Y., SzopaC., MalespinC., BuchA., and CollP. (2018) Organic matter preserved in 3-billion-year-old mudstones at Gale Crater, Mars. Science, 360:1096–1101.
14.
FaureP., JeanneauL., and LannuzelF. (2006a) Analysis of organic matter by flash pyrolysis-gas chromatography–mass spectrometry in the presence of Na-smectite: when clay minerals lead to identical molecular signature. Org Geochem, 37:1900–1912.
15.
FaureP., SchleppL., Mansuy-HuaultL., ElieM., JardéE., and PelletierM. (2006b) Aromatization of organic matter induced by the presence of clays during flash pyrolysis-gas chromatography–mass spectrometry (PyGC-MS) a major analytical artifact. J Anal Appl Pyrolysis, 75:1–10.
16.
FlynnG.J. (1996) The delivery of organic matter from asteroids and comets to the early surface of Mars. In Worlds in Interaction: Small Bodies and Planets of the Solar System, edited by RickmanH. and ValtonenM.J., Springer, Dordrecht, pp 469–474.
17.
FreissinetC., GlavinD.P., MahaffyP., MillerK.E., EigenbrodeJ.L., SummonsR.E., BrunnerA.E., BuchA., SzopaC., ArcherJr., P.D., FranzH.B., AtreyaS.K., BrinckerhoffW.B., CabaneM., CollP., ConradP.G., Des MaraisJ., DworkinJ.P., FairénA.G., FrançoisP., GrotzingerJ.P., KashyapS., ten KateI.L., LeshinL.A., MalespinC., MartinM.G., Martin-TorresF.J., McAdamA.C., MingD.W., Navarro-GonzálezR., PavlovA.A., PratsB.D., SquyresS.W., SteeleA., SternJ.C., SumnerD.Y., SutterB., ZorzanoM.-P., and the MSL ScienceTeam. (2015) Organic molecules in the Sheepbed Mudstone, Gale Crater, Mars. J Geophys Res Planets, 120:495–514.
18.
GlavinD.P., FreissinetC., MillerK.E., EigenbrodeJ.E., BrunnerA.E., BuchA., SutterB., ArcherJr., P.D., AtreyaS.K., BrinckerhoffW.B., CabaneM., CollP., ConradP.G., CosiaD., DworkinJ.P., FranzH.B., GrotzingerJ.P., LeshinL.A., MartinM.G., McKayC., MingD.W., Navarro-GonzálezR., PavlovA., SteeleA., SummonsR.E., SzopaC., TeinturierS., and MahaffyP.R. (2013) Evidence for perchlorates and the origin of chlorinated hydrocarbons detected by SAM at the Rocknest Aeolian deposit in Gale Crater. J Geophys Res E Planets, 118:1955–1973.
19.
GoesmannF., BrinckerhoffW.B., RaulinF., GoetzW., DanellR.M., GettyS.A., SiljeströmS., MißbachH., SteiningerH., ArevaloJr., R.D., BuchA., FreissinetC., GrubisicA., MeierhenrichU.J., PinnickV.T., StalportF., SzopaC., VagoJ.L., LindnerR., SchulteM., BrucatoJ.R., GlavinD.P., GrandN., LiX., van AmeromF.H.W., and the MOMA ScienceTeam. (2017) The Mars Organic Molecule Analyzer (MOMA) Instrument: characterization of organic material in martian sediments. Astrobiology, 17:655–685.
20.
GoetzW., BrinckerhoffW.B., ArevaloJr., R.D., FreissinetC., GettyS.A., GlavinD.P., SiljeströmS., BuchA., StalportF., GrubisicA., LiX., PinnickV.T., DanellR.M., van AmeromF.H.W., GoesmannF., SteiningerH., GrandN., RaulinF., SzopaC., MeierhenrichU.J., BrucatoJ.R., and the MOMA ScienceTeam. (2016) MOMA: the challenge to search for organics and biosignatures on Mars. Int J Astrobiol, 15:239–250.
21.
GriceK., CaoC., LoveG.D., BöttcherM.E., TwitchettR.J., GrosjeanE., SummonsR.E., TurgeonS.C., DunningW., and JinY. (2005) Photic zone euxinia during the Permian-Triassic superanoxic event. Science, 307:706–709.
22.
HallmannC., KellyA.E., GuptaS.N., and SummonsR.E. (2011) Reconstructing deep-time biology with molecular fossils. In Quantifying the Evolution of Early Life, edited by LaflammeM., SchiffbauerJ. D., and DornbosS. Q., Springer, Dordrecht, pp 355–401.
23.
HartgersW.A., Sinninghe DamstéJ.S., and de LeeuwJ.W. (1994a) Geochemical significance of alkylbenzene distributions in flash pyrolysates of kerogens, coals, and asphaltenes. Geochim Cosmochim Acta, 58:1759–1775.
24.
HartgersW.A., Sinninghe DamstéJ.S., RequejoA.G., AllanJ., HayesJ.M., LingY., XieT.-M., PrimackJ., and de LeeuwJ.W. (1994b) A molecular and carbon isotopic study towards the origin and diagenetic fate of diaromatic carotenoids. Org Geochem, 22:703–725.
25.
HasslerD.M., ZeitlinC., Wimmer-SchweingruberR.F., EhresmannB., RafkinS., EigenbrodeJ.L., BrinzaD.E., WeigleG., BöttcherS., BöhmE., BurmeisterS., GuoJ., KöhlerJ., MartinC., ReitzG., CucinottaF.A., KimM.-H., GrinspoonD., BullockM.A., PosnerA., Gómez-ElviraJ., VasvadaA., GrotzingerJ.P., and MSL ScienceTeam. (2014) Mars' surface radiation environment measured with the Mars Science Laboratory's Curiosity Rover. Science, 343:1244797.
26.
HechtM.H., KounavesS.P., QuinnR.C., WestS.J., YoungS.M.M., MingD.W., CatlingD.C., ClarkB.C., BoyntonW.V., HoffmanJ., DeFloresL.P., GospodinovaK., KapitJ., and SmithP.H. (2009) Detection of perchlorate and the soluble chemistry of martian soil at the Phoenix Lander Site. Science, 325:64–67.
27.
Hickman-LewisK., CavalazziB., FoucherF., and WestallF. (2018) Most ancient evidence for life in the Barberton greenstone belt: microbial mats and biofabrics of the ∼3.47 Ga Middle Marker horizon. Precambrian Res, 312:45–67.
28.
HorsfieldB. (1989) Practical criteria for classifying kerogens: some observations from pyrolysis-gas chromatography. Geochim Cosmochim Acta, 53:891–901.
29.
HorsfieldB. and DouglasA.G. (1980) The influence of minerals on the pyrolysis of kerogens. Geochim Cosmochim Acta, 44:1119–1131.
30.
HuizingaB.J., TannenbaumE., and KaplanI.R. (1987) The role of minerals in the thermal alteration of organic matter—III. Generation of bitumen in laboratory experiments. Org Geochem, 11:591–604.
31.
HuizingaB.J., AizenshtatZ.A., and PetersK.E. (1988) Programmed pyrolysis-gas chromatography of artificially matured Green River Kerogen. Energy Fuels, 2:74–81.
32.
HurowitzJ.A., GrotzingerJ.P., FischerW.W., McLennanS.M., MillikenR.E., SteinN., VasavadaA.R., BlakeD.F., DehouckE., EigenbrodeJ.L., FairénA.G., FrydenvangJ., GellertR., GrantJ.A., GuptaS., HerkenhoffK.E., MingD.W., RampeE.B., SchmidtM.E., SiebachK.L., Stack-MorganK., SumnerD.Y., and WiensR.C. (2017) Redox stratification of an ancient lake in Gale crater, Mars. Science, 356:eaah6849.
33.
KatritzkyA.R., LobanovV.S., and KarelsonM. (1998) Normal boiling points for organic compounds: correlation and prediction by a quantitative structure−property relationship. J Chem Inf Comput Sci, 38:28–41.
34.
KoopmansM.P., KösterJ., van Kaam-PetersH.M.E., KenigF., SchoutenS., HartgersW.A., de LeeuwJ.W., and Sinninghe DamstéJ.S. (1996a) Diagenetic and catagenetic products of isorenieratene: molecular indicators for photic zone anoxia. Geochim Cosmochim Acta, 60:4467–4496.
35.
KoopmansM.P., de LeeuwJ.W., LewanM.D., and Sinninghe DamstéJ.S. (1996b) Impact of dia- and catagenesis on sulphur and oxygen sequestration of biomarkers as revealed by artificial maturation of an immature sedimentary rock. Org Geochem, 25:391–426.
36.
LeifR.N. and SimoneitB.R.T. (1995) Ketones in hydrothermal petroleums and sediment extracts from Guaymas Basin, Gulf of California. Org Geochem, 23:889–904.
37.
LeifR.N. and SimoneitB.R.T. (2000) The role of alkenes produced during hydrous pyrolysis of a shale. Org Geochem, 31:1189–1208.
38.
LiX., DanellR.M., BrinckerhoffW.B., PinnickV.T., van AmeromF., ArevaloJr., R.D., GettyS.A., MahaffyP.R., SteiningerH., and GoesmannF. (2015) Detection of trace organics in Mars analog samples containing perchlorate by laser desorption/ionization mass spectrometry. Astrobiology, 15:104–110.
39.
LiX., DanellR.M., PinnickV.T., GrubisicA., van AmeromF.H.W., ArevaloJr., R.D., GettyS.A., BrinckerhoffW.B., SouthardA.E., GonnsenZ.D., and AdachiT. (2017) Mars Organic Molecule Analyzer (MOMA) laser desorption/ionization source design and performance characterization. Int J Mass Spectrom, 422:177–187.
40.
LoveG.D., StalviesC., GrosjeanE., MeredithW., and SnapeC.E. (2008) Analysis of molecular biomarkers covalently bound within Neoproterozoic sedimentary kerogen. In From Evolution to Geobiology: Research Questions Driving Paleontology at the Start of a New Century, edited by KelleyP.H., andR.K. Bambach, Paleontological Society Papers, New. Haven, pp 67–83.
41.
LvG. and WuS. (2012) Analytical pyrolysis studies of corn stalk and its three main components by TG-MS and Py-GC/MS. J Anal Appl Pyrolysis, 97:11–18.
42.
MarshallC.P., LoveG.D., SnapeC.E., HillA.C., AllwoodA.C., WalterM.R., Van KranendonkM.J., BowdenS.A., SylvaS.P., and SummonsR.E. (2007) Structural characterization of kerogen in 3.4 Ga Archaean cherts from the Pilbara Craton, Western Australia. Precambrian Res, 155:1–23.
43.
McCollomT.M., SimoneitB.R.T., and ShockE.L. (1999) Hydrous pyrolysis of polycyclic aromatic hydrocarbons and implications for the origin of PAH in hydrothermal petroleum. Energy Fuels, 13:401–410.
44.
McDonaldG.D., de VanssayE., and BuckleyJ.R. (1998) Oxidation of organic macromolecules by hydrogen peroxide: implications for stability of biomarkers on Mars. Icarus, 132:170–175.
45.
MingD.W., ArcherJr., P.D., GlavinD.P., EigenbrodeJ.L., FranzH.B., SutterB., BrunnerA.E., SternJ.C., FreissinetC., McAdamA.C., MahaffyP.R., CabaneM., CollP., CampbellJ.L., AtreyaS.K., NilesP.B., BellIII, J.F., BishD.L., BrinckerhoffW.B., BuchA., ConradP.G., Des MaraisD.J., EhlmannB.L., FairénA.G., FarleyK., FleshG.J., FrancoisP., GellertR., GrantJ.A., GrotzingerJ.P., GuptaS., HerkenhoffK.E., HurowitzJ.A., LeshinL.A., LewisK.W., McLennanS.M., MillerK.E., MoerschJ., MorrisR.V., Navarro-GonzálezR., PavlovA.A., PerrettG.M., PradlerI., SquyresS.W., SummonsR.E., SteeleA., StolperE.M., SumnerD.Y., SzopaC., TeinturierS., TrainerM.G., TreimanA.H., VanimanD.T., VasavadaA.R., WebsterC.R., WrayJ.J., YingstR.A., and the MSL ScienceTeam. (2014) Volatile and organic compositions of sedimentary rocks in Yellowknife Bay, Gale Crater, Mars. Science, 343:e1245267.
46.
MißbachH., SteiningerH., ThielV., and GoetzW. (2019) Investigating the effect of perchlorate on flight-like gas chromatography–mass spectrometry as performed by MOMA on board the ExoMars 2020 Rover. Astrobiology, 19:1339–1352.
47.
MoldoveanuS.C. (2010) Pyrolysis of Organic Molecules with Applications to Health and Environmental Issues, Elsevier, Amsterdam, p 724.
48.
NishiharaM. and KogaY. (1995) Two new phospholipids, hydroxyarchaetidylglycerol and hydroxyarchaetidylethanolamine, from the Archaea Methanosarcina barkeri. Biochim Biophys Acta, 1254:155–160.
49.
PavlovA.A., VasilyevG., OstryakovV.M., PavlovA.K., and MahaffyP. (2012) Degradation of the organic molecules in the shallow subsurface of Mars due to irradiation by cosmic rays. Geophys Res Lett, 39:L13202.
50.
QuantinC., CarterJ., ThollotP., BroyerJ., LozachL., DavisJ., GrindrodP., PajolaM., BarattiE., RossatoS., AllemandP., BultelB., LeyratC., FernandoJ., and OdyA. (2016) Oxia Planum, the landing site for ExoMars 2018. In 47th Lunar and Planetary Science Conference Abstracts, The Woodlands, Texas.
51.
RegtopR.A., EllisJ., CrispP.T., EkstromA., and FookesC.J.R. (1985) Pyrolysis of model compounds on spent oil shales, minerals and charcoal: implications for shale oil composition. Fuel, 64:1640–1646.
52.
ReinhardtM., DudaJ.-P., BlumenbergM., Ostertag-HenningsC., ReitnerJ., HeimC., and ThielV. (2018) The taphonomic fate of isorenieratene in Lower Jurassic shales—controlled by iron?. Geobiology, 16:237–251.
53.
ReinhardtM., GoetzW., DudaJ.-P., HeimC., ReitnerJ., and ThielV. (2019) Organic signatures in Pleistocene cherts from Lake Magadi (Kenya)—implications for early Earth hydrothermal deposits. Biogeosciences, 16:2443–2465.
54.
ScrimaD.A., YenT.F., and WarrenP.L. (1974) Thermal chromatography of Green River Oil Shale I. Bitumen and Kerogen. Energy Sour, 1:312–336.
SephtonM.A., LoveG.D., WatsonJ.S., VerchovskyA.B., WrightI.P., SnapeC.E., and GilmourI. (2004) Hydropyrolysis of insoluble carbonaceous matter in the Murchison meteorite: new insights into its macromolecular structure. Geochim Cosmochim Acta, 68:1385–1393.
57.
SephtonM.A., LoveG.D., MeredithW., SnapeC.E., SunC.-G., and WatsonJ.S. (2005) Hydropyrolysis: a new technique for the analysis of macromolecular material in meteorites. Planet Space Sci, 53:1280–1286.
58.
Sinninghe DamstéJ.S. and de LeeuwJ.W. (1990) Analysis, structure and geochemical significance of organically-bound sulphur in the geosphere: state of the art and future research. Org Geochem, 16:1077–1101.
59.
SteinbeissS., SchmidtC.M., HeideK., and GleixnerG. (2006) δ13C values of pyrolysis products from cellulose and lignin represent the isotope content of their precursors. J Anal Appl Pyrolysis, 75:19–26.
60.
SteiningerH., GoesmannF., and GoetzW. (2012) Influence of magnesium perchlorate on the pyrolysis of organic compounds in Mars analogue soils. Planet Space Sci, 71:9–17.
61.
SummonsR.E. and PowellT.G. (1986) Chlorobiaceae in Palaeozoic seas revealed by biological markers, isotopes and geology. Nature, 319:763–765.
62.
SutterB., McAdamA.C., MahaffyP.R., MingD.W., EdgettK.S., RampeE.B., EigenbrodeJ.L., FranzH.B., FreissinetC., GrotzingerJ.P., SteeleA., HouseC.H., ArcherP.D., MalespinC.A., Navarro-GonzálezR., SternJ.C., BellJ.F., CalefF.J., GellertR, GlavinD.P., ThompsonL.M., and YenA.S. (2017) Evolved gas analyses of sedimentary rocks and eolian sediment in Gale Crater, Mars: results of the Curiosity rover's sample analysis at Mars instrument from Yellowknife Bay to the Namib Dune. J Geophys Res Planets, 122:2574–2609.
63.
TannenbaumE. and KaplanI.R. (1985) Role of minerals in the thermal alteration of organic matter—I: generation of gases and condensates under dry condition. Geochim Cosmochim Acta, 49:2589–2604.
64.
TissotB.P. and WelteD.H. (1984) Petroleum Formation and Occurrence, Springer, Berlin, p 699.
65.
UenoY., YurimotoH., YoshiokaH., KomiyaT., and MaruyamaS. (2002) Ion microprobe analysis of graphite from ca. 3.8 Ga metasediments, Isua supracrustal belt, West Greenland: relationship between metamorphism and carbon isotopic composition. Geochim Cosmochim Acta, 66:1257–1268.
66.
VagoJ.L., WestallF., Pasteur InstrumentTeams, Landing Site Selection WorkingGroup, and OtherContributors. (2017) Habitability on early Mars and the search for biosignatures with the ExoMars Rover. Astrobiology, 17:471–510.
67.
van de MeentD., BrownS.C., PhilpR.P., and SimoneitB.R.T. (1980) Pyrolysis-high resolution gas chromatography and pyrolysis gas chromatography-mass spectrometry of kerogens and kerogen. Geochim Cosmochim Acta, 44:999–1013.
68.
WakehamS.G., Sinninghe DamstéJ.S., KohnenM.E.L., and de LeeuwJ.W. (1995) Organic sulfur compounds formed during early diagenesis in Black Sea sediments. Geochim Cosmochim Acta, 59:521–533.
69.
WestallF., FoucherF., BostN., BertrandM., LoizeauD., VagoJ.L., KminekG., GaboyerF., CampbellK.A., BréhéretJ.-G., GautretP., and CockellC.S. (2015) Biosignatures on Mars: what, where, and how? Implications for the search for martian life. Astrobiology, 15:998–1029.
70.
van ZuilenM.A., LeplandA., TeranesJ., FinarelliJ., WahlenM., and ArrheniusG. (2003) Graphite and carbonates in the 3.8 Ga old Isua Supracrustal Belt, southern West Greenland. Precambrian Res, 126:331–348.
71.
van ZuilenM.A., MathewK., WopenkaB., LeplandA., MartiK., and ArrheniusG. (2005) Nitrogen and argon isotopic signatures in graphite from the 3.8-Ga-old Isua Supracrustal Belt, Southern West Greenland. Geochim Cosmochim Acta, 69:1241–1252.
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