Structural characterization of kerogen in 3.4 Ga Archaean cherts from the Pilbara Craton, Western Australia

Craig P. Marshall, Gordon D. Love, Colin E. Snape, Andrew C. Hill, Abigail C. Allwood, Malcolm R. Walter, Martin J. Van Kranendonk, Stephen A. Bowden, Sean P. Sylva, Roger E. Summons

Research output: Contribution to journalArticle

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Abstract

Hydrogen-lean kerogen (atomic H/C < 0.46) isolated from the 3.4 Ga Strelley Pool Chert in the North Pole area, Pilbara Craton, Western Australia, were studied by vibrational spectroscopy (Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy), nuclear magnetic resonance spectroscopy (solid state C-13 NMR spectroscopy), catalytic hydropyrolysis followed by gas chromatography mass spectrometry (HyPy-GC-MS), and isotope ratio mass spectrometry (IRMS). The kerogen occurs in sedimentary rocks as clasts and clots deposited together with other detrital materials that are finely disseminated throughout a chert matrix. The bulk kerogen delta C-13 values range from -28.3 to -35.8%. Solid-state C-13 NMR spectroscopy and FTIR spectroscopy reveals that the kerogen is highly aromatic (f(a) varying from 0.90 to 0.92) and contains only minor aliphatic carbon or carbon-oxygenated (C-O) functionalities. The Raman carbon first-order spectra for the isolated kerogens are typical of spectra obtained from disordered sp(2) carbons with low 2-D ordering (biperiodic structure). The implications of the Raman results show low 2-D ordering throughout the carbonaceous network indicate the incorrect usage of the term graphite in the literature to describe the kerogen or carbonaceous material in the Warrawoona cherts. Hydropyrolysates contain aromatic compounds consisting of 1-ring to 7-ring polycyclic aromatic hydrocarbons which were covalently bound into the kerogen as well as alkanes (linear, branched and cyclic) which were most probably trapped in the microporous network of the kerogen. These PAHs have mainly C1- and C2-alkylation while C3+-substitued aromatics are low in abundance and do not show a high degree of branched alkylation. For the first time we have shown a correlation between elemental analysis (H/C atomic ratios), Raman spectroscopic parameters (I-DI/I-G, IDI/(I-DI + I-G), and L-a), and the degree of alkylation of bound polyaromatic molecular constituents generated from HyPy for Archaean kerogens. Similarities in molecular profiles exist between HyPy products of Strelley Pool Chert kerogens and an oil-window-mature Mesoproterozoic kerogen from Roper Group (ca. 1.45 Ga), which is biogenic in origin, suggesting that the Strelley Pool Chert kerogens may also be derived from diagenesis and thermal processing of biogenic organic matter. A combination of Raman spectroscopy, for identifying the least metamorphosed kerogens, used together with HyPy for liberating trapped and bound molecular components of these kerogens, offers a powerful strategy for assessing the origins of Earth's oldest preserved organic matter. (C) 2007 Elsevier B.V All rights reserved.

Original languageEnglish
Pages (from-to)1-23
Number of pages23
JournalPrecambrian Research
Volume155
Issue number1-2
DOIs
Publication statusPublished - 5 May 2007

Keywords

  • Archaean kerogens
  • spectroscopy
  • HyPy-GC-MS
  • Pilbara Craton
  • Strelley Pool chert
  • carbon isotopic composition
  • insoluble organic matter
  • Earth's earliest fossils
  • North-Pole area
  • raman-spectroscopy
  • catalytic hydropyrolysis
  • macromolecular material
  • aromatic-hydrocarbons
  • metamorphic rocks
  • Warrawoona group

Cite this

Marshall, C. P., Love, G. D., Snape, C. E., Hill, A. C., Allwood, A. C., Walter, M. R., ... Summons, R. E. (2007). Structural characterization of kerogen in 3.4 Ga Archaean cherts from the Pilbara Craton, Western Australia. Precambrian Research, 155(1-2), 1-23. https://doi.org/10.1016/j.precamres.2006.12.014

Structural characterization of kerogen in 3.4 Ga Archaean cherts from the Pilbara Craton, Western Australia. / Marshall, Craig P.; Love, Gordon D.; Snape, Colin E.; Hill, Andrew C.; Allwood, Abigail C.; Walter, Malcolm R.; Van Kranendonk, Martin J.; Bowden, Stephen A.; Sylva, Sean P.; Summons, Roger E.

In: Precambrian Research, Vol. 155, No. 1-2, 05.05.2007, p. 1-23.

Research output: Contribution to journalArticle

Marshall, CP, Love, GD, Snape, CE, Hill, AC, Allwood, AC, Walter, MR, Van Kranendonk, MJ, Bowden, SA, Sylva, SP & Summons, RE 2007, 'Structural characterization of kerogen in 3.4 Ga Archaean cherts from the Pilbara Craton, Western Australia', Precambrian Research, vol. 155, no. 1-2, pp. 1-23. https://doi.org/10.1016/j.precamres.2006.12.014
Marshall, Craig P. ; Love, Gordon D. ; Snape, Colin E. ; Hill, Andrew C. ; Allwood, Abigail C. ; Walter, Malcolm R. ; Van Kranendonk, Martin J. ; Bowden, Stephen A. ; Sylva, Sean P. ; Summons, Roger E. / Structural characterization of kerogen in 3.4 Ga Archaean cherts from the Pilbara Craton, Western Australia. In: Precambrian Research. 2007 ; Vol. 155, No. 1-2. pp. 1-23.
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T1 - Structural characterization of kerogen in 3.4 Ga Archaean cherts from the Pilbara Craton, Western Australia

AU - Marshall, Craig P.

AU - Love, Gordon D.

AU - Snape, Colin E.

AU - Hill, Andrew C.

AU - Allwood, Abigail C.

AU - Walter, Malcolm R.

AU - Van Kranendonk, Martin J.

AU - Bowden, Stephen A.

AU - Sylva, Sean P.

AU - Summons, Roger E.

PY - 2007/5/5

Y1 - 2007/5/5

N2 - Hydrogen-lean kerogen (atomic H/C < 0.46) isolated from the 3.4 Ga Strelley Pool Chert in the North Pole area, Pilbara Craton, Western Australia, were studied by vibrational spectroscopy (Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy), nuclear magnetic resonance spectroscopy (solid state C-13 NMR spectroscopy), catalytic hydropyrolysis followed by gas chromatography mass spectrometry (HyPy-GC-MS), and isotope ratio mass spectrometry (IRMS). The kerogen occurs in sedimentary rocks as clasts and clots deposited together with other detrital materials that are finely disseminated throughout a chert matrix. The bulk kerogen delta C-13 values range from -28.3 to -35.8%. Solid-state C-13 NMR spectroscopy and FTIR spectroscopy reveals that the kerogen is highly aromatic (f(a) varying from 0.90 to 0.92) and contains only minor aliphatic carbon or carbon-oxygenated (C-O) functionalities. The Raman carbon first-order spectra for the isolated kerogens are typical of spectra obtained from disordered sp(2) carbons with low 2-D ordering (biperiodic structure). The implications of the Raman results show low 2-D ordering throughout the carbonaceous network indicate the incorrect usage of the term graphite in the literature to describe the kerogen or carbonaceous material in the Warrawoona cherts. Hydropyrolysates contain aromatic compounds consisting of 1-ring to 7-ring polycyclic aromatic hydrocarbons which were covalently bound into the kerogen as well as alkanes (linear, branched and cyclic) which were most probably trapped in the microporous network of the kerogen. These PAHs have mainly C1- and C2-alkylation while C3+-substitued aromatics are low in abundance and do not show a high degree of branched alkylation. For the first time we have shown a correlation between elemental analysis (H/C atomic ratios), Raman spectroscopic parameters (I-DI/I-G, IDI/(I-DI + I-G), and L-a), and the degree of alkylation of bound polyaromatic molecular constituents generated from HyPy for Archaean kerogens. Similarities in molecular profiles exist between HyPy products of Strelley Pool Chert kerogens and an oil-window-mature Mesoproterozoic kerogen from Roper Group (ca. 1.45 Ga), which is biogenic in origin, suggesting that the Strelley Pool Chert kerogens may also be derived from diagenesis and thermal processing of biogenic organic matter. A combination of Raman spectroscopy, for identifying the least metamorphosed kerogens, used together with HyPy for liberating trapped and bound molecular components of these kerogens, offers a powerful strategy for assessing the origins of Earth's oldest preserved organic matter. (C) 2007 Elsevier B.V All rights reserved.

AB - Hydrogen-lean kerogen (atomic H/C < 0.46) isolated from the 3.4 Ga Strelley Pool Chert in the North Pole area, Pilbara Craton, Western Australia, were studied by vibrational spectroscopy (Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy), nuclear magnetic resonance spectroscopy (solid state C-13 NMR spectroscopy), catalytic hydropyrolysis followed by gas chromatography mass spectrometry (HyPy-GC-MS), and isotope ratio mass spectrometry (IRMS). The kerogen occurs in sedimentary rocks as clasts and clots deposited together with other detrital materials that are finely disseminated throughout a chert matrix. The bulk kerogen delta C-13 values range from -28.3 to -35.8%. Solid-state C-13 NMR spectroscopy and FTIR spectroscopy reveals that the kerogen is highly aromatic (f(a) varying from 0.90 to 0.92) and contains only minor aliphatic carbon or carbon-oxygenated (C-O) functionalities. The Raman carbon first-order spectra for the isolated kerogens are typical of spectra obtained from disordered sp(2) carbons with low 2-D ordering (biperiodic structure). The implications of the Raman results show low 2-D ordering throughout the carbonaceous network indicate the incorrect usage of the term graphite in the literature to describe the kerogen or carbonaceous material in the Warrawoona cherts. Hydropyrolysates contain aromatic compounds consisting of 1-ring to 7-ring polycyclic aromatic hydrocarbons which were covalently bound into the kerogen as well as alkanes (linear, branched and cyclic) which were most probably trapped in the microporous network of the kerogen. These PAHs have mainly C1- and C2-alkylation while C3+-substitued aromatics are low in abundance and do not show a high degree of branched alkylation. For the first time we have shown a correlation between elemental analysis (H/C atomic ratios), Raman spectroscopic parameters (I-DI/I-G, IDI/(I-DI + I-G), and L-a), and the degree of alkylation of bound polyaromatic molecular constituents generated from HyPy for Archaean kerogens. Similarities in molecular profiles exist between HyPy products of Strelley Pool Chert kerogens and an oil-window-mature Mesoproterozoic kerogen from Roper Group (ca. 1.45 Ga), which is biogenic in origin, suggesting that the Strelley Pool Chert kerogens may also be derived from diagenesis and thermal processing of biogenic organic matter. A combination of Raman spectroscopy, for identifying the least metamorphosed kerogens, used together with HyPy for liberating trapped and bound molecular components of these kerogens, offers a powerful strategy for assessing the origins of Earth's oldest preserved organic matter. (C) 2007 Elsevier B.V All rights reserved.

KW - Archaean kerogens

KW - spectroscopy

KW - HyPy-GC-MS

KW - Pilbara Craton

KW - Strelley Pool chert

KW - carbon isotopic composition

KW - insoluble organic matter

KW - Earth's earliest fossils

KW - North-Pole area

KW - raman-spectroscopy

KW - catalytic hydropyrolysis

KW - macromolecular material

KW - aromatic-hydrocarbons

KW - metamorphic rocks

KW - Warrawoona group

U2 - 10.1016/j.precamres.2006.12.014

DO - 10.1016/j.precamres.2006.12.014

M3 - Article

VL - 155

SP - 1

EP - 23

JO - Precambrian Research

JF - Precambrian Research

SN - 0301-9268

IS - 1-2

ER -