Restricted accessResearch articleFirst published online 2020-03
Detection of Potential Lipid Biomarkers in Oxidative Environments by Raman Spectroscopy and Implications for the ExoMars 2020-Raman Laser Spectrometer Instrument Performance
The aim of the European Space Agency's ExoMars rover mission is to search for potential traces of present or past life in the swallow subsurface (2 m depth) of Mars. The ExoMars rover mission relies on a suite of analytical instruments envisioned to identify organic compounds with biological value (biomarkers) associated with a mineralogical matrix in a highly oxidative environment. We investigated the feasibility of detecting basic organics (linear and branched lipid molecules) with Raman laser spectroscopy, an instrument onboard the ExoMars rover, when exposed to oxidant conditions. We compared the detectability of six lipid molecules (alkanes, alkanols, fatty acid, and isoprenoid) before and after an oxidation treatment (15 days with hydrogen peroxide), with and without mineral matrix support (amorphous silica rich vs. iron rich). Raman and infrared spectrometry was combined with gas chromatography–mass spectrometry to determine detection limits and technical constraints. We observed different spectral responses to degradation depending on the lipid molecule and mineral substrate, with the silica-rich material showing better preservation of organic signals. These findings will contribute to the interpretation of Raman laser spectroscopy results on cores from the ExoMars rover landing site, the hydrated silica-enriched delta fan on Cogoon Vallis (Oxia Planum).
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References
1.
AtreyaS.K., WongA.-S., RennoN.O., FarrellW.M., DeloryG.T., SentmanD.D., CummerS.A., MarshallJ.R., RafkinS.C.R., and CatlingD.C. (2006) Oxidant enhancement in martian dust devils and storms: implications for life and habitability. Astrobiology, 6:439–450.
2.
BandfieldJ.L. (2008) High-silica deposits of an aqueous origin in western Hellas Basin, Mars. Geophys Res Lett, 35 doi: 10.1029/2008GL033807
3.
BernardS., BeyssacO., BenzeraraK., FindlingN., TzvetkovG., and BrownG.E. (2010) XANES, Raman and XRD study of anthracene-based cokes and saccharose-based chars submitted to high-temperature pyrolysis, Carbon, 9:2506–2516.
4.
BlakeD.F., MorrisR.V., KocurekG., MorrisonS.M., DownsR.T., BishD., MingD.W., EdgettK.S., RubinD., GoetzW., MadsenM.B., SullivanR., GellertR., CampbellI., TreimanA.H., McLennanS.M., YenA.S., GrotzingerJ., VanimanD.T., ChiperaS.J., AchillesC.N., RampeE.B., SumnerD., MeslinP.Y., MauriceS., ForniO., GasnaultO., FiskM., SchmidtM., MahaffyP., LeshinL.A., GlavinD., SteeleA., FreissinetC., Navarro-GonzálezR., YingstR.A., KahL.C., BridgesN., LewisK.W., BristowT.F., FarmerJ.D., CrispJ.A., StolperE.M., Des MaraisD.J., SarrazinP.; MSL ScienceTeam. (2013) Curiosity at Gale crater, Mars: characterization and analysis of the Rocknest sand shadow. Science, 341:1239505.
5.
BuzgarN., ApopeiA., DiaconuV., and BuzatuA. (2013) The composition and source of the raw material of two stone axes of Late Bronze Age from Neamț County (Romania) A Raman study. Analele științifice ale Universității “Al. I. Cuza” din Iași, Seria Geologie, 59:5–22.
6.
CarrizoD, Sánchez-GarcíaL., MenesR.J., and García-RodríguezF. (2019) Discriminating sources and preservation of organic matter in surface sediments from five Antarctic lakes in the Fildes Peninsula (King George Island) by lipid biomarkers and compound-specific isotopic analysis. Sci Tot Environ, 672:657–668.
7.
ChristensenP.R., BandfieldJ.L., HamiltonV.E., RuffS.W., KiefferH.H., TitusT.N., MalinM.C., MorrisR.V., LaneM.D., ClarkR.L., JakoskyB.M., MellonM.T., PearlJ.C., ConrathB.J., SmithM.D., ClancyR.T., KuzminR.O., RoushT., MehallG.L., GorelickN., BenderK., MurrayK., and DasonS. (2001) The Mars Global Surveyor Thermal Emission Spectrometer experiment: Investigation description and surface science results. J Geophys Res, 106:23823–23871.
8.
ClancyR.T., SandorB.J., and Moriarty-SchievenG.H. (2004) A measurement of the 362 GHz absorption line of Mars atmospheric H2O2. Icarus, 168:116–121.
9.
DartnellL.R., DesorgherL., WardJ.M., and CoatesA.J. (2007) Martian sub-surface ionizing radiation: biosignatures and geology. Biogeosciences, 4:545–558.
10.
DavilaA.F., FairénA.G., Gago-DuportL., StokerC., AmilsR., BonaccorsiR., ZavaletaJ., MilD., Schulze-MakuchD., and McKayC.P. (2008) Subsurface formation of oxidants on Mars and implications for the preservation of organic biosignatures. Earth Planet Sci Lett, 272:456–463.
11.
de FariaD.L.A. and LopesF.D.N. (2007) Heated goethite and natural hematite: Can Raman spectroscopy be used to differentiate them?. Vib Spectrosc, 45:17–121.
12.
de SousaF.F., NogueiraC.E.S., FreireP.T.C., MoreiraS.G.C., TeixeiraA.M.R., de MenezesA.S., Mendes-FilhoJ., and SaraivaG.D. (2016) Conformational change in the C form of palmitic acid investigated by Raman spectroscopy and X-ray diffraction. Spectrochim Acta A Mol Biomol Spectrosc, 161:162–169.
13.
DelanoG., Ian JarvisH., GillmoreG., StephensonM., and EmmingsJ.F. (2018) Assessing low-maturity organic matter in shales using Raman spectroscopy: effects of sample preparation and operating procedure. Int J Coal Geol, 191:135–151.
14.
EigenbrodeJ.L., SummonsR.E., SteeleA., FreissinetC., MillanM., Navarro-GonzálezR., SutterB., McAdamA.C., FranzH.B., GlavinD.P., ArcherP.D.Jr., 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.
15.
EncrenazT., GreathouseT.K., LefèvreF., and AtreyaS.K. (2012) Hydrogen peroxide on Mars: observations, interpretation and future plans. Planet Space Sci, 68:3–17.
16.
ESA. (2013) ExoMars Science Management Plan (draft). Doc. No.: EXM-MS-PL-ESA-00002, Issue: 6, Rev.0, 66 pp.
17.
FornaroT., SteeleA., and BrucatoJ.R. (2018) Catalytic/protective properties of martian minerals and implications for possible origin of life on Mars. Life, 8, 56.
18.
FoucherF., Lopez-ReyesG., BostN., Rull-PerezF., RüßmannP., and WestallF. (2013) Effect of grain size distribution on Raman analyses and the consequences for in situ planetary missions. J Raman Spectrosc, 44:916–925.
19.
Gil-LozanoC., DavilaA.F., Losa-AdamsE., FairénA.G., and Gago-DuportL. (2017) Quantifying Fenton reaction pathways driven by self-generated H2O2 on pyrite surfaces. Sci Rep, 7:43703.
20.
GrimaltJ.O. and AlbaigésJ. (1987) Sources and occurrence of C12 C22n-alkane distributions with even carbon-number preference in sedimentary environments. Geochim Cosmochim Acta, 51:1379–1384.
21.
HaneschM. (2009) Raman spectroscopy of iron oxides and (oxy)hydroxides at low laser power and possible applications in environmental magnetic studies. Geophys J Int, 177:941–948.
22.
HenryD.G., JarvisI., GillmoreG., StephensonM., and EmmingsJ.F. (2018) Assessing low-maturity organic matter in shales using Raman spectroscopy: Effects of sample preparation and operating procedure. International Journal of Coal Geology, 191:135–151.
23.
HorganB.H.N., CloutisE.A., MannP., and BellJ.F. (2014) Near-infrared spectra of ferrous mineral mixtures and methods for their identification in planetary surface spectra. Icarus, 234:132–154.
24.
HurowitzJ.A., ToscaN.J., McLennanS.M., and SchoonenM.A.A. (2007) Production of hydrogen peroxide in Martian and lunar soils. Earth Planet Sci Lett, 255:41–52.
25.
HurowitzJ.A., FischerW.W., ToscaN.L., and MillikenR.E. (2010) Origin of acidic surface waters and the evolution of atmospheric chemistry on early Mars. Nat Geosci, 3:323–326.
26.
JubbA.M. and AllenH.C. (2010) Vibrational spectroscopic characterization of hematite, maghemite, and magnetite thin films produced by vapor deposition. Appl Mater Interfaces, 2:2804–2812.
27.
KumarS. (2014) Selective laser sintering/melting. In Comprehensive Materials Processing, edited by HashmiS., FerreiraG. Batalha, VanC.J. Tyne, and B. Yilbas. Elsevier, Amsterdam, pp 93–134.
28.
MeyersP.A. and IshiwatariR. (1993) Lacustrine organic geochemistry: an overview of indicators of organic matter sources and diagenesis in lake sediments. Org Geochem, 20:867–900.
29.
MillikenR.E., SwayzeG.A., ArvidsonR.E., BishopJ.L., ClarkR.N., EhlmannB.L., GreenR.O., GrotzingerJ.P., MorrisR.V., MurchieS.L., MustardJ.F., and WeitzC. (2008) Opaline silica in young deposits on Mars. Geology, 36:847–850.
30.
MorrisR.V., GoldenD.C., Bell IIIJ.F., ShelferT.D., ScheinostA.C., HinmanN.W., FurnissG., MertzmanS.A., BishopJ.L., MingD.W., AllenC.C., and BrittD.T. (2000) Mineralogy, composition, and alteration of Mars Pathfinder rocks and soils: evidence from multispectral, elemental, and magnetic data on terrestrial analogue, SNC meteorite, and Pathfinder samples. J Geophys Res, 105:1757–1817.
31.
MorrisR.V., VanimanD.T., BlakeD.F., GellertR., ChiperaS.J., RampeE.B., MingD.W., MorrisonS.M., DownsR.-T., TreimanA.H., YenA.S., GrotzingerJ.P., AchillesC.N., BristowT.F., CrispJ.A., Des MaraisD.J., FarmerJ.D., FendrichK.V., FrydenvangJ., GraffT.G., MorookianJ.M., StolperE.M., and SchwenzerS.P. (2016) Silicic volcanism on Mars evidenced by tridymite in high-SiO2 sedimentary rock at Gale crater. Proc Natl Acad Sci USA, 113:7071–7076.
32.
PavlovA.K., OstryakovV.M., PavlovA.A., VasilyevG.I., and VdovinaM.A. (2013) Influence of cosmic rays on biomarkers on the Mars. Bull Russ Acad Sci Phys, 77:596–598.
33.
PereiraM.C., OliveiraL.C.A., and MuradE. (2018) Iron oxide catalysts: Fenton and Fentonlike reactions—a review. Clay Miner, 47:285–302.
34.
ReichenbacherM. and PoppJ. (2012) Challenges in Molecular Structure Determination. Springer-Verlag, Berlin Heidelberg.
35.
RuffS. and FarmerJ. (2016) Silica deposits on Mars with features resembling hot spring biosignatures at El Tatio in Chile. Nat Commun, 7:13554. doi:10.1038/ncomms13554
36.
RullF., MauriceS., HutchinsonI., MoralA., PerezC., DiazC., ColomboM., BelenguerT., Lopez-ReyesG., SansanoA., ForniO., ParotY., StriebigN., WoodwardS., HoweC., TarceaN., RodriguezP., SeoaneL., SantiagoA., Rodriguez-PrietoJ.A., MedinaJ., GallegoP., CanchalR., SantamaríaP., RamosG., VagoJ.L.; on behalf of the RLSTeam. (2017) The Raman Laser Spectrometer for the Exomars Rover Mission to Mars. Astrobiology, 17:627–654.
37.
SalzerR. (2008) Book review: Practical Guide to Interpretive Near-Infrared Spectroscopy. By Jerry Workman, Jr. and Lois Weyer. Angew Chem, 120:4706–4707.
38.
Sánchez-GarcíaL., AeppliC., ParroV., Fernandez-RemolarD., García-VilladangosM., Chong-DíazG., BlancoY., and CarrizoD. (2018) Molecular biomarkers in the subsurface of the Salar Grande (Atacama, Chile) evaporitic deposits. Biogeochemistry, 144:31–52.
39.
SchuergerA.C., RichardsJ.T., NewcombeD.A., and VenkateswaranK. (2006) Rapid inactivation of seven Bacillus spp. under simulated Mars UV irradiation. Icarus, 181:52–62.
40.
SquyresS.W., ArvidsonR.E., RuffS., GellertR., MorrisR.V., MingD.W., CrumplerL., FarmerJ.D., MaraisD.J., YenA., McLennanS.M., CalvinW., BellJ.F., ClarkB.C., WangA., McCoyT.J., SchmidtM.E., and de SouzaP.A. (2008) Detection of silica-rich deposits on Mars. Science, 320:1063–1067.
41.
ten KateI.L., GarryJ.R.C., PeetersZ., QuinnR., FoingB., and EhrenfreundP. (2005) Amino acid photostability on the Martian surface. Meteorit Planet Sci, 40:1185–1193.
42.
VagoJ.L., GardiniB., KminekG., BaglioniP., GianfiglioG., SantovincenzoA., BayónS., and van WinnendaelM. (2006) ExoMars—searching for life on the Red Planet. ESA Bull, 126:16–23.
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