Biomarker and n-alkane isotope profiles for Tertiary oils: relationship to source rock depositional setting

doi:10.1016/0146-6380(94)90124-4

Organic Geochemistry

Volume 22, Issues 3–5, December 1994, Pages 521-542, IN5-IN6

https://doi.org/10.1016/0146-6380(94)90124-4 Get rights and content

Abstract

Biomarker and n-alkane isotope profiles have been measured for 29 Late Cretaceous/Tertiary oils from SE Asia, China, Papua New Guinea, New Zealand and the U.S.A. The results are interpreted with respect to six kinds of source rock depositional setting: fluvio-deltaic (FD), freshwater transitional (TR), lacustrine (LAC), saline lacustrine (SAL), marine deltaic (MD) and marine carbonate (MC). A comparison of biomarker and n-alkane isotope results suggests that parameters such as the oleanane/hopane ratio may overestimate the higher plant contribution to marine oils. The abundance of bicadinanes is much more variable than that of oleanane, probably because of a specific association with the highly resinous, dipterocarp hardwoods of SE Asia. However, traces do occur in an oil from outside the paleogeographic range of the dipterocarp family, confirming that there is also a more general angiosperm source. The bicadinane isomeric distribution is shown to depend on maturity, leading to new maturity parameters which are resistant to even very heavy biodegradation. Retention indices based on the regular hopane series are provided for the main bicadinane and methyl bicadinane isomers and for a group of oleanane-related triterpanes of unknown structure. The presence of the latter compounds may indicate locally deposited as opposed to transported higher plant matter in the source. Source rock depositional setting is the primary control on the shape of the n-alkane isotope profile, with negatively sloping curves being characteristic of FD and TR oils and flat or positively sloping curves typical of marine oils. The difference is probably related to the bacterial reworking of higher plant matter in the FD environment. A slight isotopic anomaly at n-C₁₇ correlates with the abundance of algal-derived steranes and may indicate a minor marine contribution to the source of an FD oil.

References (100)

B.G.K. van Aarssen et al.
A cadinene biopolymer present in fossil and extant dammar resins as a source for cadinanes and bicadinanes in crude oils from Southeast Asia
Geochim. Cosmochim. Acta
(1990)
B.G.K. van Aarssen et al.
Cis-cis-trans-bicadinane, a novel member of an uncommon triterpane family isolated from crude oils
Tetrahedron Lett.
(1990)
B.G.K. van Aarssen et al.
A comparative study of three different pyrolysis methods used to characterise a biopolymer isolated from fossil and extant dammar resins
J. Anal. Appl. Pyrol.
(1991)
B.G.K. van Aarssen et al.
The occurrence of polycyclic sesqui-, tri- and oligoterpenoids derived from a resinous polymeric cadinene in crude oils from Southeast Asia
Geochim. Cosmochim. Acta
(1992)
B.G.K. van Aarssen et al.
An unusual distribution of bicadinanes, tricadinanes and oligocadinanes in sediments from the Yacheng Gasfield, China
Org. Geochem.
(1992)
B.G.K. van Aarssen et al.
Occurrence of polycadinene in fossil and recent resins
Geochim. Cosmochim. Acta
(1994)
M. Alam et al.
Bicadinanes in oils from the Surma Basin, Bangladesh
Org. Geochem.
(1990)
C. Armanios et al.
Fractionation of sedimentary higher-plant derived pentacyclic triterpanes using molecular sieves
Org. Geochem.
(1994)
A.J. Bakel et al.
Carbon isotopic analysis of individual n-alkanes: evaluation of accuracy and application to marine particulate organic material
Org. Geochem.
(1994)
M. Bjorøy et al.
Carbon isotope variations in n-alkanes and isoprenoids of whole oils
Chem. Geol.
(1991)

M. Bjorøy et al.

Variation in stable carbon isotope ratios of individual hydrocarbons as a function of artificial maturity

Org. Geochem.

(1992)

C.J. Boreham et al.

Chemical, molecular and isotopic differentiation of organic facies in the Tertiary lacustrine Duaringa oil shale deposit, Queensland, Australia

Org. Geochem.

(1994)

C.J. Clayton

Effect of maturity on carbon isotope ratios of oils and condensates

Org. Geochem.

(1991)

C.J. Clayton et al.

Effect of maturity on ¹³C/¹²C ratios of individual compounds in North Sea oils

Org. Geochem.

(1994)

C.G. Clifton et al.

Hydrothermal petroleums from Yellowstone National Park, Wyoming, U.S.A.

Appl. Geochem.

(1990)

J.W. Collister et al.

An isotropic biogeochemical study of the Green River oil shale

Org. Geochem.

(1992)

J.A. Curiale et al.

Tertiary deltaic and lacustrine facies: comparison of biomarker and kerogen distributions

Org. Geochem.

(1991)

J.A. Curiale et al.

The Central Myanmar (Burma) oil family—composition and implications for source

Org. Geochem.

(1994)

Z. Czochanska et al.

Geochemical application of sterane and triterpane biomarkers to a description of oils from the Taranaki Basin in New Zealand

Org. Geochem.

(1988)

L.I.P. Dzou et al.

Geochemistry of oils and condensates, K field, offshore Taiwan: a case study in migration fractionation

Org. Geochem.

(1993)

C.M. Ekweozor et al.

The oleananes: origin, maturation and limits of occurrence in Southern Nigeria sedimentary basins

C.M. Ekweozor et al.

Oleanane parameter: verification by quantitative study of the biomarker occurrence in sediments of the Nigeria delta

Org. Geochem.

(1990)

I. Gilmour et al.

The carbon isotopic composition of individual petroleum lipids

Org. Geochem.

(1984)

P.J. Grantham

Sterane isomerisation and moretane/hopane ratios in crude oils derived from Tertiary source rocks

Org. Geochem.

(1986)

J.M. Hayes

Factors controlling ¹³C contents of sedimentary organic compounds: principles and evidence

Mar. Geol.

(1993)

J.M. Hayes et al.

Compound-specific isotopic analysis: A novel tool for reconstruction of ancient biogeochemical processes

Org. Geochem.

(1990)

C.F. Hoffmann et al.

A biological marker study of coals, shales and oils from the Mahakam Delta, Indonesia

Chem. Geol.

(1984)

W.Y. Huang et al.

Sterols as ecological indicators

Geochim. Cosmochim. Acta

(1979)

G. Klink et al.

A new source for 4-methyl sterols in freshwater sediments: Utricularia neglecta L. (Lentibulariaceae)

Org. Geochem.

(1992)

E.A. Lichtfouse et al.

Tracing molecular links of natural organic substances at the molecular level with stable carbon isotopes: n-alkanes and n-alkanoic acids from sediments

Tetrahedron Lett.

(1992)

D.M. McKirdy et al.

Molecular fossils in coastal bitumens from southern Australia: constraints on precursor biota and source rock environments

Org. Geochem.

(1994)

M.R. Mello et al.

Organic geochemical characterisation of depositional palaeoenvironments of source rocks and oils in Brazilian marginal basins

Org. Geochem.

(1988)

D.C. Mildenhall

New Zealand Late Cretaceous and Cenozoic plant biogeography: a contribution

Palaeogeogr. Palaeoclim. Palaeoecol.

(1980)

A.P. Murray et al.

Oceanic transport of fossil dammar resin—the chemistry of coastal resinites from South Australia

Geochim. Cosmochim. Acta

(1994)

R.A. Noble et al.

Petroleum generation and migration from Talang Akar coal and shales offshore N.W. Java, Indonesia

Org. Geochem.

(1991)

M.J. Pearson et al.

Bicadinanes and other terrestrial terpenoids in immature Oligocene sedimentary rocks and a related oil from the Surma Basin, N.E. Bangladesh

Org. Geochem.

(1993)

A. Riva et al.

Recognition of 18β(H)-oleanane in several crudes and Cainozoic-Upper Cretaceous sediments. Definition of a new maturity parameter

Org. Geochem.

(1988)

A. Saliot

Natural hydrocarbons in seawater

M. Schoell

Recent advances in petroleum isotope geochemistry

Org. Geochem.

(1984)

W.K. Seifert

Steranes and terpanes in kerogen pyrolysis for correlation of oils and source rocks

Geochim. Cosmochim. Acta

(1978)

W.K. Seifert et al.

Paleoreconstruction by biological markers

Geochim. Cosmochim. Acta

(1981)

M.G. Strachan et al.

Constraints upon the use of 24-ethylcholestane diastereomer ratios as indicators of the maturity of petroleum

Org. Geochem.

(1989)

E. Tannenbaum et al.

Steranes and triperpanes generated from kerogen pyrolysis in the absence and presence of minerals

Geochim. Cosmochim. Acta

(1986)

P. Ungerer

State of the art in kinetic modelling of oil formation and expulsion

Org. Geochem.

(1990)

J.K. Volkman et al.

A new source of 4-methyl sterols and 5α(H)-stanols in sediments: Prymnesiophyte microalgae of the genus Pavlova

Org. Geochem.

(1990)

R.J. Weston et al.

Sesquiterpanes, diterpanes and other higher terpanes in oils from the Taranaki basin of New Zealand

Org. Geochem.

(1989)

G.A. Wolff et al.

The origin and fate of 4-methyl steroid hydrocarbons I. 4-Methyl sterenes

Geochim. Cosmochim. Acta

(1986)

J.E. Zumberge

Prediction of source rock characteristics based on terpane biomarkers in crude oils: a multivariate statistical approach

Geochim. Cosmochim. Acta

(1987)

P.S. Ashton

Dipterocarpaceae, Flora Malesiana

(1982)

A.A. Bal

Paleogeography, hydrocarbon source rock quality, rank and maturity of coals in the Puponga Coal Measures, Pakawau Group, northwest Nelson

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Climate changes and palaeoenvironmentsBiomarker and n-alkane isotope profiles for Tertiary oils: relationship to source rock depositional setting

Abstract

Geochim. Cosmochim. Acta

Tetrahedron Lett.

J. Anal. Appl. Pyrol.

Geochim. Cosmochim. Acta

Org. Geochem.

Geochim. Cosmochim. Acta

Org. Geochem.

Org. Geochem.

Org. Geochem.

Chem. Geol.

Org. Geochem.

Org. Geochem.

Org. Geochem.

Org. Geochem.

Appl. Geochem.

Org. Geochem.

Org. Geochem.

Org. Geochem.

Org. Geochem.

Org. Geochem.

Org. Geochem.

Org. Geochem.

Org. Geochem.

Mar. Geol.

Org. Geochem.

Chem. Geol.

Geochim. Cosmochim. Acta

Org. Geochem.

Tetrahedron Lett.

Org. Geochem.

Org. Geochem.

Palaeogeogr. Palaeoclim. Palaeoecol.

Geochim. Cosmochim. Acta

Org. Geochem.

Org. Geochem.

Org. Geochem.

Org. Geochem.

Geochim. Cosmochim. Acta

Geochim. Cosmochim. Acta

Org. Geochem.

Geochim. Cosmochim. Acta

Org. Geochem.

Org. Geochem.

Org. Geochem.

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Climate changes and palaeoenvironments
Biomarker and n-alkane isotope profiles for Tertiary oils: relationship to source rock depositional setting