The Determination of the Spatial Distribution of Indigenous Lipid Biomarkers in an Immature Jurassic Sediment Using Time-of-Flight–Secondary Ion Mass Spectrometry

Pasterski, M. Joseph; Lorenz, Matthias; Ievlev, Anton V.; Wickramasinghe, Raveendra C.; Hanley, Luke; Kenig, Fabien

doi:10.1089/ast.2022.0145

The Determination of the Spatial Distribution of Indigenous Lipid Biomarkers in an Immature Jurassic Sediment Using Time-of-Flight–Secondary Ion Mass Spectrometry

Journal Article · Mon Jul 17 00:00:00 EDT 2023 · Astrobiology

DOI:https://doi.org/10.1089/ast.2022.0145· OSTI ID:1996649

^[1]; ^[2]; ^[2]; Wickramasinghe, Raveendra C. ^[1]; Hanley, Luke ^[1]; Kenig, Fabien ^[1]

Univ. of Illinois, Chicago, IL (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

The ability to detect and map lipids, including potential lipid biomarkers, within a sedimentary matrix using mass spectrometry (MS) imaging may be critical to determine whether potential lipids detected in samples returned from Mars are indigenous to Mars or are contaminants. Here, we use gas chromatography–mass spectrometry (GC-MS) and time-of-flight–secondary ion mass spectrometry (ToF-SIMS) datasets collected from an organic-rich, thermally immature Jurassic geologic sample to constrain MS imaging analysis of indigenous lipid biomarkers in geologic samples. GC-MS data show that the extractable fractions are dominated by C₂₇–C₃₀ steranes and sterenes as well as isorenieratene derivatives. ToF-SIMS spectra from organic matter-rich laminae contain a strong, spatially restricted signal for ions m/z 370.3, m/z 372.3, and m/z 386.3, which we assign to C₂₇ sterenes, cholestane (C₂₇), and 4- or 24-methyl steranes (C₂₈), respectively, as well as characteristic fragment ions of isorenieratene derivatives, including m/z 133.1, m/z 171.1, and m/z 237.1. We observed individual steroid spatial heterogeneity at the scale of 10's to 100's of microns. The fine-scale heterogeneity observed implies that indigenous lipid biomarkers concentrated within specific regions may be detectable via ToF-SIMS in samples with even low amounts of organic carbon, including in samples returned from Mars.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: National Aeronautics and Space Administration (NASA); USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1996649

Journal Information:: Astrobiology, Journal Name: Astrobiology Journal Issue: 9 Vol. 23; ISSN 1531-1074

Publisher:: Mary Ann Liebert, Inc.Copyright Statement

Country of Publication:: United States

Language:: English

References (58)

Characterization of kerogens by matrix-assisted laser desorption ionization mass spectroscopy Li, Chun-Zhu; Herod, Alan A.; John, Phillip Rapid Communications in Mass Spectrometry, Vol. 8, Issue 10 https://doi.org/10.1002/rcm.1290081006	journal	October 1994
Spectral characterization of ten cyclic lipids using time-of-flight secondary ion mass spectrometry: Characterization of 10 cyclic lipids using ToF-SIMS Leefmann, Tim; Heim, Christine; Siljeström, Sandra Rapid Communications in Mass Spectrometry, Vol. 27, Issue 5 https://doi.org/10.1002/rcm.6483	journal	February 2013
Topography and field effects in secondary ion mass spectrometry Part II: insulating samples Lee, J. L. S.; Gilmore, I. S.; Seah, M. P. Surface and Interface Analysis, Vol. 44, Issue 2 https://doi.org/10.1002/sia.3833	journal	October 2011
Mars 2020 Mission Overview Farley, Kenneth A.; Williford, Kenneth H.; Stack, Kathryn M. Space Science Reviews, Vol. 216, Issue 8 https://doi.org/10.1007/s11214-020-00762-y	journal	December 2020
Topography and Field Effects in Secondary Ion Mass Spectrometry – Part I: Conducting Samples Lee, Joanna L. S.; Gilmore, Ian S.; Seah, Martin P. Journal of the American Society for Mass Spectrometry, Vol. 22, Issue 10 https://doi.org/10.1007/s13361-011-0201-1	journal	July 2011
Development of Laser Desorption Imaging Mass Spectrometry Methods to Investigate the Molecular Composition of Latent Fingermarks Lauzon, Nidia; Dufresne, Martin; Chauhan, Vinita Journal of The American Society for Mass Spectrometry, Vol. 26, Issue 6 https://doi.org/10.1007/s13361-015-1123-0	journal	April 2015
Isomerisation, rearrangement and aromatisation of steroids in distinguishing early stages of diagenesis Brassell, S. C.; McEvoy, J.; Hoffmann, C. F. Organic Geochemistry, Vol. 6 https://doi.org/10.1016/0146-6380(84)90022-6	journal	January 1984
Early diagenetic pathways of steroid alkenes Peakman, Torren M.; Maxwell, James R. Organic Geochemistry, Vol. 13, Issue 4-6 https://doi.org/10.1016/0146-6380(88)90078-2	journal	January 1988
Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence (Vena del Gesso, Italy): III. Stratigraphic changes in the molecular structure of kerogen in a single marl bed as revealed by flash pyrolysis Gelin, François; Sinninghe Damsté, Jaap S.; Harrison, Wayne N. Organic Geochemistry, Vol. 23, Issue 6 https://doi.org/10.1016/0146-6380(95)00041-C	journal	June 1995
Diagenetic and catagenetic products of isorenieratene: Molecular indicators for photic zone anoxia Koopmans, Martin P.; Köster, Jürgen; Van Kaam-Peters, Heidy M. E. Geochimica et Cosmochimica Acta, Vol. 60, Issue 22 https://doi.org/10.1016/S0016-7037(96)00238-4	journal	November 1996
Molecular fossil constraints on the water column structure of the Cenomanian–Turonian Western Interior Seaway, USA Simons, Dirk-Jan H.; Kenig, Fabien Palaeogeography, Palaeoclimatology, Palaeoecology, Vol. 169, Issue 1-2 https://doi.org/10.1016/S0031-0182(01)00222-X	journal	May 2001
TOF-SIMS in cosmochemistry Stephan, Thomas Planetary and Space Science, Vol. 49, Issue 9 https://doi.org/10.1016/S0032-0633(01)00037-X	journal	August 2001
Rearranged steranes in sediments and crude oils. Ensminger, A.; Joly, G.; Albrecht, P. Tetrahedron Letters, Vol. 19, Issue 18 https://doi.org/10.1016/S0040-4039(01)94608-8	journal	January 1978
Time of flight secondary ion mass spectrometry (ToFSIMS) of a number of hopanoids Steele, A.; Toporski, J. K. W.; Avci, R. Organic Geochemistry, Vol. 32, Issue 7 https://doi.org/10.1016/S0146-6380(01)00048-1	journal	July 2001
Novel cyclised and aromatised diagenetic products of β-carotene in the Green River Shale Koopmans, Martin P.; De Leeuw, Jan W.; Damsté, Jaap S. Sinninghe Organic Geochemistry, Vol. 26, Issue 7-8 https://doi.org/10.1016/S0146-6380(97)00025-9	journal	April 1997
A molecular and carbon isotope biogeochemical study of biomarkers and kerogen pyrolysates of the Kimmeridge Clay Facies: palaeoenvironmental implications van Kaam-Peters, Heidy M. E.; Schouten, Stefan; de Leeuw, Jan W. Organic Geochemistry, Vol. 27, Issue 7-8 https://doi.org/10.1016/S0146-6380(97)00084-3	journal	December 1997
Biomarker geochemistry of a foreland basin: the Oligocene Menilite Formation in the Flysch Carpathians of Southeast Poland Köster, J.; Rospondek, M.; Schouten, S. Organic Geochemistry, Vol. 29, Issue 1-3 https://doi.org/10.1016/S0146-6380(98)00182-X	journal	January 1998
Discrimination between biologically relevant calcium phosphate phases by surface-analytical techniques Kleine-Boymann, Matthias; Rohnke, Marcus; Henss, Anja Applied Surface Science, Vol. 309 https://doi.org/10.1016/j.apsusc.2014.04.129	journal	August 2014
Analysis of kerogens and model compounds by time-of-flight secondary ion mass spectrometry (TOF-SIMS) Sjövall, Peter; Bake, Kyle D.; Pomerantz, Andrew E. Fuel, Vol. 286 https://doi.org/10.1016/j.fuel.2020.119373	journal	February 2021
Millimeter-scale concentration gradients of hydrocarbons in Archean shales: Live-oil escape or fingerprint of contamination? Brocks, Jochen J. Geochimica et Cosmochimica Acta, Vol. 75, Issue 11 https://doi.org/10.1016/j.gca.2011.03.014	journal	June 2011
Analysis of single oil-bearing fluid inclusions in mid-Proterozoic sandstones (Roper Group, Australia) Siljeström, Sandra; Volk, Herbert; George, Simon C. Geochimica et Cosmochimica Acta, Vol. 122 https://doi.org/10.1016/j.gca.2013.08.010	journal	December 2013
C27–C30 neohop-13(18)-enes and their saturated and aromatic derivatives in sediments: Indicators for diagenesis and water column stratification Sinninghe Damsté, Jaap S.; Schouten, Stefan; Volkman, John K. Geochimica et Cosmochimica Acta, Vol. 133 https://doi.org/10.1016/j.gca.2014.03.008	journal	May 2014
Stratigraphy and paleohydrology of delta channel deposits, Jezero crater, Mars Goudge, Timothy A.; Mohrig, David; Cardenas, Benjamin T. Icarus, Vol. 301 https://doi.org/10.1016/j.icarus.2017.09.034	journal	February 2018
Methods for full resolution data exploration and visualization for large 2D and 3D mass spectrometry imaging datasets Klinkert, Ivo; Chughtai, Kamila; Ellis, Shane R. International Journal of Mass Spectrometry, Vol. 362 https://doi.org/10.1016/j.ijms.2013.12.012	journal	April 2014
Mars Organic Molecule Analyzer (MOMA) laser desorption/ionization source design and performance characterization Li, Xiang; Danell, Ryan M.; Pinnick, Veronica T. International Journal of Mass Spectrometry, Vol. 422 https://doi.org/10.1016/j.ijms.2017.03.010	journal	November 2017
Inclusive sharing of mass spectrometry imaging data requires a converter for all Race, Alan M.; Styles, Iain B.; Bunch, Josephine Journal of Proteomics, Vol. 75, Issue 16 https://doi.org/10.1016/j.jprot.2012.05.035	journal	August 2012
Characterization of purified biomarker compounds using time of flight-secondary ion mass spectrometry (ToF-SIMS) Toporski, Jan; Steele, Andrew Organic Geochemistry, Vol. 35, Issue 7 https://doi.org/10.1016/j.orggeochem.2004.03.006	journal	July 2004
Compositional differences in biomarker constituents of the hydrocarbon, resin, asphaltene and kerogen fractions: An example from the Jet Rock (Yorkshire, UK) Bowden, Stephen A.; Farrimond, Paul; Snape, Colin E. Organic Geochemistry, Vol. 37, Issue 3 https://doi.org/10.1016/j.orggeochem.2005.08.024	journal	March 2006
Detection of organic biomarkers in crude oils using ToF-SIMS Siljeström, Sandra; Hode, Tomas; Lausmaa, Jukka Organic Geochemistry, Vol. 40, Issue 1 https://doi.org/10.1016/j.orggeochem.2008.08.010	journal	January 2009
Biomarker imaging of single diatom cells in a microbial mat using time-of-flight secondary ion mass spectrometry (ToF-SIMS) Leefmann, Tim; Heim, Christine; Kryvenda, Anastasiia Organic Geochemistry, Vol. 57 https://doi.org/10.1016/j.orggeochem.2013.01.005	journal	April 2013
Occurrence and fate of fatty acyl biomarkers in an ancient whale bone (Oligocene, El Cien Formation, Mexico) Thiel, Volker; Blumenberg, Martin; Kiel, Steffen Organic Geochemistry, Vol. 68 https://doi.org/10.1016/j.orggeochem.2013.12.006	journal	March 2014
A comparative ToF-SIMS and GC–MS analysis of phototrophic communities collected from an alkaline silica-depositing hot spring Siljeström, S.; Parenteau, M. N.; Jahnke, L. L. Organic Geochemistry, Vol. 109 https://doi.org/10.1016/j.orggeochem.2017.03.009	journal	July 2017
Assessing biomarker syngeneity: An in situ approach using monoclonal antibodies Medina Ferrer, Fernando; Bailey, Jake V.; Corsetti, Frank Organic Geochemistry, Vol. 124 https://doi.org/10.1016/j.orggeochem.2018.05.006	journal	October 2018
Femtosecond Laser Desorption Postionization MS vs ToF-SIMS Imaging for Uncovering Biomarkers Buried in Geological Samples Wickramasinghe, Raveendra C.; Pasterski, Michael J.; Kenig, Fabien Analytical Chemistry, Vol. 93, Issue 48 https://doi.org/10.1021/acs.analchem.1c03275	journal	November 2021
Biases from natural sulphurization in palaeoenvironmental reconstruction based on hydrocarbon biomarker distributions Kohnen, Math E. L.; Sinninghe Damste, Jaap S.; De Leeuw, Jan W. Nature, Vol. 349, Issue 6312 https://doi.org/10.1038/349775a0	journal	February 1991
Clay minerals in delta deposits and organic preservation potential on Mars Ehlmann, Bethany L.; Mustard, John F.; Fassett, Caleb I. Nature Geoscience, Vol. 1, Issue 6 https://doi.org/10.1038/ngeo207	journal	May 2008
Fungal colonization of an Ordovician impact-induced hydrothermal system Ivarsson, Magnus; Broman, Curt; Sturkell, Erik Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep03487	journal	December 2013
Visualizing molecular distributions for biomaterials applications with mass spectrometry imaging: a review Paine, Martin R. L.; Kooijman, Pieter C.; Fisher, Gregory L. Journal of Materials Chemistry B, Vol. 5, Issue 36 https://doi.org/10.1039/c7tb01100h	journal	January 2017
A concise tutorial review of TOF-SIMS based molecular and cellular imaging Massonnet, Philippe; Heeren, Ron M. A. Journal of Analytical Atomic Spectrometry, Vol. 34, Issue 11 https://doi.org/10.1039/c9ja00164f	journal	January 2019
Ultra-high-resolution paleoenvironmental records via direct laser-based analysis of lipid biomarkers in sediment core samples Wormer, L.; Elvert, M.; Fuchser, J. Proceedings of the National Academy of Sciences, Vol. 111, Issue 44 https://doi.org/10.1073/pnas.1405237111	journal	October 2014
The Ladder of Life Detection Neveu, Marc; Hays, Lindsay E.; Voytek, Mary A. Astrobiology, Vol. 18, Issue 11 https://doi.org/10.1089/ast.2017.1773	journal	November 2018
Applicability of ToF-SIMS for monitoring compositional changes in bone in a long-term animal model Henss, Anja; Rohnke, Marcus; El Khassawna, Thaqif Journal of The Royal Society Interface, Vol. 10, Issue 86 https://doi.org/10.1098/rsif.2013.0332	journal	September 2013
A micrometer‐scale snapshot on phototroph spatial distributions: mass spectrometry imaging of microbial mats in Octopus Spring, Yellowstone National Park Wörmer, Lars; Gajendra, Niroshan; Schubotz, Florence Geobiology, Vol. 18, Issue 6 https://doi.org/10.1111/gbi.12411	journal	September 2020
Biomarkers at the microscopic range: ToF-SIMS molecular imaging of Archaea-derived lipids in a microbial mat Thiel, V.; Heim, C.; Arp, G. Geobiology, Vol. 5, Issue 4 https://doi.org/10.1111/j.1472-4669.2007.00119.x	journal	December 2007
Analysis of hopanes and steranes in single oil-bearing fluid inclusions using time-of-flight secondary ion mass spectrometry (ToF-SIMS): Analysis of hopanes and steranes in single oil-bearing fluid inclusions SiljestrÃM, S.; Lausmaa, J.; SjÃVall, P. Geobiology, Vol. 8, Issue 1 https://doi.org/10.1111/j.1472-4669.2009.00223.x	journal	January 2010
Organic Geochemical Microanalysis by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) Sjövall, Peter; Thiel, Volker; Siljeström, Sandra Geostandards and Geoanalytical Research, Vol. 32, Issue 3 https://doi.org/10.1111/j.1751-908X.2008.00909.x	journal	September 2008
TOF-SIMS analysis of polycyclic aromatic hydrocarbons in Allan Hills 84001 Stephan, THomas; Jessberger, Elmar K.; Heiss, Christian H. Meteoritics & Planetary Science, Vol. 38, Issue 1 https://doi.org/10.1111/j.1945-5100.2003.tb01049.x	journal	January 2003
TOF-SIMS analysis of cometary matter in Stardust aerogel tracks Stephan, Thomas; Rost, Detlef; Vicenzi, Edward P. Meteoritics & Planetary Science, Vol. 43, Issue 1-2 https://doi.org/10.1111/j.1945-5100.2008.tb00619.x	journal	February 2008
The potential science and engineering value of samples delivered to Earth by Mars sample return: International MSR Objectives and Samples Team (iMOST) Beaty, D. W.; Grady, M. M.; McSween, H. Y. Meteoritics & Planetary Science, Vol. 54 https://doi.org/10.1111/maps.13242	journal	March 2019
SIMS of organics—Advances in 2D and 3D imaging and future outlook Gilmore, Ian S. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 31, Issue 5 https://doi.org/10.1116/1.4816935	journal	September 2013
Organic synthesis on Mars by electrochemical reduction of CO ₂ Steele, A.; Benning, L. G.; Wirth, R. Science Advances, Vol. 4, Issue 10 https://doi.org/10.1126/sciadv.aat5118	journal	October 2018
Aqueously altered igneous rocks sampled on the floor of Jezero crater, Mars Farley, K. A.; Stack, K. M.; Shuster, D. L. Science, Vol. 377, Issue 6614 https://doi.org/10.1126/science.abo2196	journal	September 2022
Intermittent euxinia: Reconciliation of a Jurassic black shale with its biofacies Kenig, Fabien; Hudson, John D.; Sinninghe Damsté, Jaap S. Geology, Vol. 32, Issue 5 https://doi.org/10.1130/G20356.1	journal	January 2004
Isotopic biogeochemistry of the Oxford Clay Formation (Jurassic), UK Kenig, F.; Hayes, J. M.; Popp, B. N. Journal of the Geological Society, Vol. 151, Issue 1 https://doi.org/10.1144/gsjgs.151.1.0139	journal	January 1994
Recognition of tectonic events in undeformed regions: contrasting results from the Midland Platform and East Midlands Shelf, Central England Green, Paul F.; Thomson, Ken; Hudson, John D. Journal of the Geological Society, Vol. 158, Issue 1 https://doi.org/10.1144/jgs.158.1.59	journal	January 2001
Laser Desorption Combined with Laser Postionization for Mass Spectrometry Hanley, Luke; Wickramasinghe, Raveendra; Yung, Yeni P. Annual Review of Analytical Chemistry, Vol. 12, Issue 1 https://doi.org/10.1146/annurev-anchem-061318-115447	journal	June 2019
Using Time-of-Flight Secondary Ion Mass Spectrometry to Study Biomarkers Thiel, Volker; Sjövall, Peter Annual Review of Earth and Planetary Sciences, Vol. 39, Issue 1 https://doi.org/10.1146/annurev-earth-040610-133525	journal	May 2011
A Mineralogical Context for the Organic Matter in the Paris Meteorite Determined by A Multi-Technique Analysis Noun, Manale; Baklouti, Donia; Brunetto, Rosario Life, Vol. 9, Issue 2 https://doi.org/10.3390/life9020044	journal	May 2019

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The Determination of the Spatial Distribution of Indigenous Lipid Biomarkers in an Immature Jurassic Sediment Using Time-of-Flight–Secondary Ion Mass Spectrometry

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