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Single fluid inclusion analysis using ToF-SIMS: Implications for ancient Earth biodiversiy and paleoenvironment studies
Stockholm University, Faculty of Science, Department of Geological Sciences.
2011 (English)Doctoral thesis, comprehensive summary (Other academic)Alternative title
ToF-SIMS-analys av enskilda vätskeinneslutningar : Implikationer för studier av tidiga jordens biodiveristet och paleomiljö (Swedish)
Abstract [en]

When and how life first emerged on the Earth is an area of intense research. Signs of the first life on Earth, including morphological fossils, are scarce and hard to interpret. An alternative approach is to study organic biomarkers, which are molecular fossils commonly considered as bona fide biosignatures.

The main objective of the project is to develop an approach for analysis of single oil-bearing fluid inclusions and most importantly the detection of organic biomarkers in these inclusions. Analysis of oil-bearing fluid inclusions is advantageous since the inclusions may provide an uncontaminated sample source of Precambrian hopanes and steranes, which are key biomarkers for tracing the early evolution of life on Earth. Due to the presence of several inclusion generations, single inclusion analysis is desired in order to constrain biomarkers to specific inclusions. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) could be an excellent tool for analysis of these types of samples.

The development of the approach for analysis of single oil-bearing inclusions was done in a two-step process; i) a number of crude oils were analysed with ToF-SIMS and gas chromatography mass-spectrometry (GC-MS) to facilitate interpretation of ToF-SIMS spectra of these types of samples and, ii) a procedure that combines micrographs with ion etching and ToF-SIMS analysis was developed for analysis of inclusions. The feasibility of the technique was demonstrated for oil inclusions from the Siljan impact crater in which hopanes and steranes where detected. Single oil-bearing fluid inclusions trapped in mid-Proterozoic sandstones from Northern Australia were subsequently analyzed, and steranes and hopanes were detected in these inclusions. If applied on older inclusions this approach may help answer some of the questions regarding the emergence and evolution of life on Earth, and if applied on extraterrestrial samples, also the possibility of life on other planets and moons.

Abstract [sv]

Livets uppkomst och tidiga utveckling på jorden är ett hett forskningsfält. Hur och när livet och dess olika domäner (arkéer, bakterier och eukaryoter) uppstod på jorden är fortfarande oklart vilket beror på att de första tecknen på liv, vilka inkluderar morfologiska fossil, spårfossil och isotoper, är få och svåra att tolka. Ett alternativt sätt att studera det tidiga livet är att studera organiska biomarkörer som är organiska molekyler som anses unika för liv.

Huvudmålet med projektet är att utveckla en metod som kan detektera organiska biomarkörer i enskilda oljebärande vätskeinneslutningar. Vätskeinneslutningar, som är små mängder vätska (picoliter) infångad in en sten, är intressanta då de är en potentiell provkälla för prekambriska (äldre än 500 miljoner år) biomarkörer, som hopaner och steraner, vilka används för att utforska livets tidiga utveckling på jorden. Analys av enskilda inneslutningar är emellertid oftast nödvändigt för att kunna tidsavgränsa biomarkörer. På grund av att de flesta inneslutningar är små (10 µm i diameter) är det inte möjligt att analysera en enskild vätskeinneslutning med standardtekniken gaskromatografi-masspektrometri (GC-MS). Time-of-flight secondary ion mass spektrometri (ToF-SIMS) med sin höga känslighet, höga massupplösning och kapacitet för 2D-representation av analysdata och djupprofilering av prover är en utmärkt teknik för analys av enskilda inneslutningar.

Metoden för analys av enskilda inneslutningar utvecklades i två steg. Först analyserades ett antal råoljor med ToF-SIMS och GC-MS för att underlätta förståelsen av ToF-SIMS-spektra från dessa typer av prover. Därefter utvecklades en metod som bestod av mikroskopering för att lokalisera inneslutningen, jonetsning för att öppna inneslutningen och ToF-SIMS analys av det exponerade innehållet. Metoden testades framgångsrikt på enskilda inneslutningar i hydrotermala vener av flusspat och kalcit i ordovicisk (488-443 miljoner år sedan) kalksten. Därefter användes den utvecklade metoden för att analysera enskilda vätskeinneslutningar i 1,43 miljarder år gammal sandsten från norra Australien, i vilka hopaner och steraner detekterades. De detekterade steranerna visar att trots att havet under denna tid var syrefritt existerade det lokala syrerika miljöer där eukaryoter kunde överleva. Om den utvecklade metoden används på ännu äldre inneslutningar, vilka har daterats till 3,2 miljarder år, kan den komma att svara på några de mest fundamentala frågorna kring livets uppkomst och tidiga utveckling. Om metoden används på utomjordiska prover kan den svara på frågan om det finns liv på andra planeter eller månar.

Place, publisher, year, edition, pages
Stockholm: Department of Geological Sciences, Stockholm University , 2011. , 29 p.
Series
Meddelanden från Stockholms universitets institution för geologiska vetenskaper, 343
Keyword [en]
ToF-SIMS, time-of-flight secondary ion mass spectrometry, fluid inclusions, biomarkers, hopanes, steranes, early life, paleoenvironment, oil, eukaryotes
National Category
Earth and Related Environmental Sciences
Research subject
Geochemistry
Identifiers
URN: urn:nbn:se:su:diva-54909ISBN: 978-91-7447-237-0OAI: oai:DiVA.org:su-54909DiVA: diva2:399498
Public defence
2011-03-25, Nordenskiöldsalen, Geovetenskapens hus, Svante Arrhenius väg 12, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Submitted. Available from: 2011-03-03 Created: 2011-02-21 Last updated: 2011-02-27Bibliographically approved
List of papers
1. Detection of organic biomarkers in crude oils using ToF-SIMS
Open this publication in new window or tab >>Detection of organic biomarkers in crude oils using ToF-SIMS
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2009 (English)In: Organic Geochemistry, ISSN 0146-6380, E-ISSN 1873-5290, Vol. 40, no 1, 135-143 p.Article in journal (Refereed) Published
Abstract [en]

In this study, we show that time of flight-secondary ion mass spectrometry (ToF-SIMS) can be used todetect organic biomarkers, such as hopanes and steranes, in non-fractionated crude oils, without extractionand chemical preparation. Hopanes and steranes may provide valuable information on the history oflife on early Earth, particularly if they are present in fluid inclusions in ancient rocks. Due to the presenceof different generations of inclusions in even very small rock samples, it would be advantageous to find amethod capable of detecting biomarkers in single oil rich fluid inclusions. The capability of ToF-SIMS fordetailed chemical analysis of very small sample amounts makes it a potential technique for such analysis,and in this work this possibility is explored. The presence of hopanes and steranes in four different crudeoils of different ages and stages of biodegradation was investigated using ToF-SIMS and GC–MS. By combininganalyses of biomarker standards, crude oils and chromatographic oil fractions, specific peaks forthe different biomarkers were identified in the ToF-SIMS spectra. The presence of these peaks in the spectrafrom the crude oil samples could be attributed to the biomarkers based on exact mass determinationand by comparison with the spectra from the biomarker containing and biomarker lacking fractions,respectively. In addition, the results show that a significant biomarker signal may be obtained from a 10 µm2 oil sample, demonstrating the potential of ToF-SIMS for analysis of single oil bearing fluid inclusions,which in turn may contribute to a better understanding of the early history of life on Earth.

Keyword
ToF-SIMS, biomarkers, oil, time-of-flight secondary ion mass spectrometry
National Category
Earth and Related Environmental Sciences
Research subject
Geochemistry
Identifiers
urn:nbn:se:su:diva-16184 (URN)10.1016/j.orggeochem.2008.08.010 (DOI)000262806300014 ()
Available from: 2008-12-15 Created: 2008-12-15 Last updated: 2011-02-22Bibliographically approved
2. Analysis of hopanes and steranes in single oil-bearing fluid inclusions using time-of-flight secondary ion mass spectrometry (ToF-SIMS)
Open this publication in new window or tab >>Analysis of hopanes and steranes in single oil-bearing fluid inclusions using time-of-flight secondary ion mass spectrometry (ToF-SIMS)
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2010 (English)In: Geobiology, ISSN 1472-4677, E-ISSN 1472-4669, Vol. 8, no 1, 37-44 p.Article in journal (Refereed) Published
Abstract [en]

Steranes and hopanes are organic biomarkers used as indicators for the first appearance of eukaryotes and cyanobacteria on Earth. Oil-bearing fluid inclusions may provide a contamination-free source of Precambrian biomarkers, as the oil has been secluded from the environment since the formation of the inclusion. However, analysis of biomarkers in single oil-bearing fluid inclusions, which is often necessary due to the presence of different generations of inclusions, has not been possible due to the small size of most inclusions. Here, we have used time-of-flight secondary ion mass spectrometry (ToF-SIMS) to monitor in real time the opening of individualinclusions trapped in hydrothermal veins of fluorite and calcite and containing oil from Ordovician source rocks. Opening of the inclusions was performed by using a focused C60+ ion beam and the in situ content was preciselyanalysed for C27–C29 steranes and C29–C32 hopanes using Bi3+ as primary ions. The capacity to unambiguouslydetect these biomarkers in the picoliter amount of crude oil from a single, normal-sized (15–30 µm in diameter)inclusion makes the approach promising in the search of organic biomarkers for life’s early evolution on Earth.

Keyword
Fluid inclusions, oil, biomarkers, ToF-SIMS, hopanes, sterans
National Category
Earth and Related Environmental Sciences
Research subject
Geochemistry
Identifiers
urn:nbn:se:su:diva-33651 (URN)10.1111/j.1472-4669.2009.00223.x (DOI)000272836600003 ()
Available from: 2009-12-23 Created: 2009-12-23 Last updated: 2011-11-23Bibliographically approved
3. Analysis of single oil-bearing fluid inclusions in mid-Proterozoic sandstones (Roper Group, Australia)
Open this publication in new window or tab >>Analysis of single oil-bearing fluid inclusions in mid-Proterozoic sandstones (Roper Group, Australia)
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(English)Manuscript (preprint) (Other academic)
National Category
Earth and Related Environmental Sciences
Research subject
Geochemistry
Identifiers
urn:nbn:se:su:diva-54597 (URN)
Available from: 2011-02-08 Created: 2011-02-08 Last updated: 2011-02-22Bibliographically approved
4. Structural effects of C60+ bombardment on various natural mineral samples - Application to analysis of organic phases in geological samples
Open this publication in new window or tab >>Structural effects of C60+ bombardment on various natural mineral samples - Application to analysis of organic phases in geological samples
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2011 (English)In: Applied Surface Science, ISSN 0169-4332, E-ISSN 1873-5584, Vol. 257, no 21, 9199-9206 p.Article in journal (Refereed) Published
Abstract [en]

Organic phases trapped inside natural mineral samples are of considerable interest in astrobiology, geochemistry and geobiology. Examples of such organic phases are microfossils, kerogen and oil. Information about these phases is usually retrieved through bulk crushing of the rock which means both a risk of contamination and that the composition and spatial distribution of the organics to its host mineral is lost. An attractive of way to retrieve information about the organics in the rock is depth profiling using a focused ion beam. Recently, it was shown that it is possible to obtain detailed mass spectrometric information from oil-bearing fluid inclusions, i.e. small amounts of oil trapped inside a mineral matrix, using ToF-SIMS. Using a 10 keV C-60(+) sputter beam and a 25 keV Bi-3(+) analysis beam, oil-bearing inclusions in different minerals were opened and analysed individually. However, sputtering with a C-60(+) beam also induced other changes to the mineral surface, such as formation of topographic features and carbon deposition. In this paper, the cause of these changes is explored and the consequences of the sputter-induced features on the analysis of organic phases in natural mineral samples (quartz, calcite and fluorite) in general and fluid inclusions in particular are discussed. The dominating topographical features that were observed when a several micrometers deep crater is sputtered with 10 keV C-60(+) ions on a natural mineral surface are conical-shaped and ridge-like structures that may rise several micrometers, pointing in the direction of the incident C-60(+) ion beam, on an otherwise flat crater bottom. The sputter-induced structures were found to appear at places with different chemistry than the host mineral, including other minerals phases and fluid inclusions, while structural defects in the host material, such as polishing marks or scratches, did not necessarily result in sputter-induced structures. The ridge-like structures were often covered by a thick layer of deposited carbon. Despite the appearance of the sputter-induced structures and carbon deposition, most oil-bearing inclusions could successfully be opened and analysed. However, smaller inclusion (<15 mu m) could potentially become entirely covered by sputter-resistant structures and therefore difficult to open. Therefore, it might become necessary, to for example increase the ion energy and rotate the stage to successfully open smaller inclusions for analysis.

Keyword
SIMS, C60, carbon deposition, topography, mineral, fluid inclusions, geological samples, depth profiling
National Category
Earth and Related Environmental Sciences
Research subject
Geochemistry
Identifiers
urn:nbn:se:su:diva-54594 (URN)10.1016/j.apsusc.2011.06.003 (DOI)000292539700070 ()
Available from: 2011-02-08 Created: 2011-02-08 Last updated: 2013-10-15Bibliographically approved

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