Early diagenesis of bacteriohopanepolyol derivatives: Formation of fossil homohopanoids

Jaap S. Sinninghe Damsté, Adri C.T. Van Duin, David Hollander, Math E.L. Kohnen, Jan W. De Leeuw

Research output: Contribution to journalArticle

97 Citations (Scopus)

Abstract

Diagenetic pathways of bacteriohopanepolyol derivatives are proposed based on the concentrations and 13C contents of homohopanes, homohop-17(21)-enes, benzohopanes, hopanoid thiophenes and sulphides, and macromolecularly S-bound homohopanes present in the extracts of twelve composite one metre samples from a 120 m core recovered from the Upper Cretaceous Jurf ed Darawish Oil Shale (Jordan). A large part (>80-95%) of the pentakishomohopane skeleton occurs in a S-bound form. This reveals the selective preservation of the C35 hopane skeleton by sulphur sequestration and provides a theoretical basis for the homohopane index as an indicator of anoxia in past depositional environments. A smaller part (>50-80%) of the total extended hopane skeletons (C31-C35) occurs in a S-bound form. Of the non-sulphur-containing hopanoids the homohop-17(21)-enes dominate. These latter components show a gradual increase of 22S epimers with depth (45-52%) towards the thermodynamic equilibrium (52-53%) as calculated by molecular mechanics. Molecular mechanic calculations indicate that this increase can be explained by either isomerisation of 22R hop-17(21)-enes or by isomerisation of double bonds of homohopenes formed by dehydration of bacteriohopanepolyols "en passant" isomerising the chiral centre at C-22. A combination of these two pathways is also possible and provides an explanation for different δ13C values of pairs of 22R and 22S epimers. Isomerisation of 17β,21β(H)-homohopane to 17α,21,β(H)-homohopane carbon skeletons occurs for all compound classes in a very narrow depth span (ca. 20 m) and is probably induced by small differences in thermal history. Compound-specific carbon isotope analyses indicated that the series of homohop-17(21)-enes have in some cases significant differences in 13C content, indicating that at least two different sources have contributed to this series of components. Differences with macromolecularly S-bound C35 hopane skeletons and free C31 hopanes 13C contents are in some cases even larger. These data show that the diagenetic pathways of bacteriohopanepolyol derivatives are more complex than previously recognized and reveal that multiple precursor bacteriohopanepolyol derivatives prone to different diagenetic pathways have to be envisaged to account for the differences observed.

Original languageEnglish (US)
Pages (from-to)5141-5157
Number of pages17
JournalGeochimica et Cosmochimica Acta
Volume59
Issue number24
DOIs
StatePublished - Dec 1995

Fingerprint

skeleton
diagenesis
Isomerization
fossil
Derivatives
Molecular mechanics
hopanoid
mechanics
Carbon Isotopes
Thiophenes
Oil shale
Sulfides
Dehydration
Sulfur
oil shale
anoxia
Carbon
dehydration
depositional environment
Thermodynamics

All Science Journal Classification (ASJC) codes

  • Geochemistry and Petrology

Cite this

Sinninghe Damsté, Jaap S. ; Van Duin, Adri C.T. ; Hollander, David ; Kohnen, Math E.L. ; De Leeuw, Jan W. / Early diagenesis of bacteriohopanepolyol derivatives : Formation of fossil homohopanoids. In: Geochimica et Cosmochimica Acta. 1995 ; Vol. 59, No. 24. pp. 5141-5157.
@article{27527d55383f48b784c31eb625cc6854,
title = "Early diagenesis of bacteriohopanepolyol derivatives: Formation of fossil homohopanoids",
abstract = "Diagenetic pathways of bacteriohopanepolyol derivatives are proposed based on the concentrations and 13C contents of homohopanes, homohop-17(21)-enes, benzohopanes, hopanoid thiophenes and sulphides, and macromolecularly S-bound homohopanes present in the extracts of twelve composite one metre samples from a 120 m core recovered from the Upper Cretaceous Jurf ed Darawish Oil Shale (Jordan). A large part (>80-95{\%}) of the pentakishomohopane skeleton occurs in a S-bound form. This reveals the selective preservation of the C35 hopane skeleton by sulphur sequestration and provides a theoretical basis for the homohopane index as an indicator of anoxia in past depositional environments. A smaller part (>50-80{\%}) of the total extended hopane skeletons (C31-C35) occurs in a S-bound form. Of the non-sulphur-containing hopanoids the homohop-17(21)-enes dominate. These latter components show a gradual increase of 22S epimers with depth (45-52{\%}) towards the thermodynamic equilibrium (52-53{\%}) as calculated by molecular mechanics. Molecular mechanic calculations indicate that this increase can be explained by either isomerisation of 22R hop-17(21)-enes or by isomerisation of double bonds of homohopenes formed by dehydration of bacteriohopanepolyols {"}en passant{"} isomerising the chiral centre at C-22. A combination of these two pathways is also possible and provides an explanation for different δ13C values of pairs of 22R and 22S epimers. Isomerisation of 17β,21β(H)-homohopane to 17α,21,β(H)-homohopane carbon skeletons occurs for all compound classes in a very narrow depth span (ca. 20 m) and is probably induced by small differences in thermal history. Compound-specific carbon isotope analyses indicated that the series of homohop-17(21)-enes have in some cases significant differences in 13C content, indicating that at least two different sources have contributed to this series of components. Differences with macromolecularly S-bound C35 hopane skeletons and free C31 hopanes 13C contents are in some cases even larger. These data show that the diagenetic pathways of bacteriohopanepolyol derivatives are more complex than previously recognized and reveal that multiple precursor bacteriohopanepolyol derivatives prone to different diagenetic pathways have to be envisaged to account for the differences observed.",
author = "{Sinninghe Damst{\'e}}, {Jaap S.} and {Van Duin}, {Adri C.T.} and David Hollander and Kohnen, {Math E.L.} and {De Leeuw}, {Jan W.}",
year = "1995",
month = "12",
doi = "10.1016/0016-7037(95)00338-X",
language = "English (US)",
volume = "59",
pages = "5141--5157",
journal = "Geochmica et Cosmochimica Acta",
issn = "0016-7037",
publisher = "Elsevier Limited",
number = "24",

}

Early diagenesis of bacteriohopanepolyol derivatives : Formation of fossil homohopanoids. / Sinninghe Damsté, Jaap S.; Van Duin, Adri C.T.; Hollander, David; Kohnen, Math E.L.; De Leeuw, Jan W.

In: Geochimica et Cosmochimica Acta, Vol. 59, No. 24, 12.1995, p. 5141-5157.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Early diagenesis of bacteriohopanepolyol derivatives

T2 - Formation of fossil homohopanoids

AU - Sinninghe Damsté, Jaap S.

AU - Van Duin, Adri C.T.

AU - Hollander, David

AU - Kohnen, Math E.L.

AU - De Leeuw, Jan W.

PY - 1995/12

Y1 - 1995/12

N2 - Diagenetic pathways of bacteriohopanepolyol derivatives are proposed based on the concentrations and 13C contents of homohopanes, homohop-17(21)-enes, benzohopanes, hopanoid thiophenes and sulphides, and macromolecularly S-bound homohopanes present in the extracts of twelve composite one metre samples from a 120 m core recovered from the Upper Cretaceous Jurf ed Darawish Oil Shale (Jordan). A large part (>80-95%) of the pentakishomohopane skeleton occurs in a S-bound form. This reveals the selective preservation of the C35 hopane skeleton by sulphur sequestration and provides a theoretical basis for the homohopane index as an indicator of anoxia in past depositional environments. A smaller part (>50-80%) of the total extended hopane skeletons (C31-C35) occurs in a S-bound form. Of the non-sulphur-containing hopanoids the homohop-17(21)-enes dominate. These latter components show a gradual increase of 22S epimers with depth (45-52%) towards the thermodynamic equilibrium (52-53%) as calculated by molecular mechanics. Molecular mechanic calculations indicate that this increase can be explained by either isomerisation of 22R hop-17(21)-enes or by isomerisation of double bonds of homohopenes formed by dehydration of bacteriohopanepolyols "en passant" isomerising the chiral centre at C-22. A combination of these two pathways is also possible and provides an explanation for different δ13C values of pairs of 22R and 22S epimers. Isomerisation of 17β,21β(H)-homohopane to 17α,21,β(H)-homohopane carbon skeletons occurs for all compound classes in a very narrow depth span (ca. 20 m) and is probably induced by small differences in thermal history. Compound-specific carbon isotope analyses indicated that the series of homohop-17(21)-enes have in some cases significant differences in 13C content, indicating that at least two different sources have contributed to this series of components. Differences with macromolecularly S-bound C35 hopane skeletons and free C31 hopanes 13C contents are in some cases even larger. These data show that the diagenetic pathways of bacteriohopanepolyol derivatives are more complex than previously recognized and reveal that multiple precursor bacteriohopanepolyol derivatives prone to different diagenetic pathways have to be envisaged to account for the differences observed.

AB - Diagenetic pathways of bacteriohopanepolyol derivatives are proposed based on the concentrations and 13C contents of homohopanes, homohop-17(21)-enes, benzohopanes, hopanoid thiophenes and sulphides, and macromolecularly S-bound homohopanes present in the extracts of twelve composite one metre samples from a 120 m core recovered from the Upper Cretaceous Jurf ed Darawish Oil Shale (Jordan). A large part (>80-95%) of the pentakishomohopane skeleton occurs in a S-bound form. This reveals the selective preservation of the C35 hopane skeleton by sulphur sequestration and provides a theoretical basis for the homohopane index as an indicator of anoxia in past depositional environments. A smaller part (>50-80%) of the total extended hopane skeletons (C31-C35) occurs in a S-bound form. Of the non-sulphur-containing hopanoids the homohop-17(21)-enes dominate. These latter components show a gradual increase of 22S epimers with depth (45-52%) towards the thermodynamic equilibrium (52-53%) as calculated by molecular mechanics. Molecular mechanic calculations indicate that this increase can be explained by either isomerisation of 22R hop-17(21)-enes or by isomerisation of double bonds of homohopenes formed by dehydration of bacteriohopanepolyols "en passant" isomerising the chiral centre at C-22. A combination of these two pathways is also possible and provides an explanation for different δ13C values of pairs of 22R and 22S epimers. Isomerisation of 17β,21β(H)-homohopane to 17α,21,β(H)-homohopane carbon skeletons occurs for all compound classes in a very narrow depth span (ca. 20 m) and is probably induced by small differences in thermal history. Compound-specific carbon isotope analyses indicated that the series of homohop-17(21)-enes have in some cases significant differences in 13C content, indicating that at least two different sources have contributed to this series of components. Differences with macromolecularly S-bound C35 hopane skeletons and free C31 hopanes 13C contents are in some cases even larger. These data show that the diagenetic pathways of bacteriohopanepolyol derivatives are more complex than previously recognized and reveal that multiple precursor bacteriohopanepolyol derivatives prone to different diagenetic pathways have to be envisaged to account for the differences observed.

UR - http://www.scopus.com/inward/record.url?scp=0029477019&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0029477019&partnerID=8YFLogxK

U2 - 10.1016/0016-7037(95)00338-X

DO - 10.1016/0016-7037(95)00338-X

M3 - Article

AN - SCOPUS:0029477019

VL - 59

SP - 5141

EP - 5157

JO - Geochmica et Cosmochimica Acta

JF - Geochmica et Cosmochimica Acta

SN - 0016-7037

IS - 24

ER -