Org. Geochem. Vol. 17, No. 1, pp. 63-74, 1991 0146-6380/91 $3.00 + 0.00
Printed in Great Britain. All rights reserved Copyright © 1991 Pergamon Press plc
Maturity of kerogen and asphaltenes determined by
partial-least-squares (PLS) calibration and target projection of
diffuse reflectance Fourier transformed infrared spectra
ALFRED A. CHRISTY 1, OLAV M. KVALHEIM 1, KJELL ~YGARD 2, BIRGERDAHL 3 and
TERJE V. KARSTANG 1
Department of Chemistry, University of Bergen, 5007 Bergen, Norway
2Geolab, Statoil, P.O. Box 300, 4001 Stavanger, Norway
3Norsk Hydro Research Centre, P.O. Box 4313, 5001 Bergen, Norway
(Received 27 November 1989; accepted in revised form 14 June 1990)
Abstract--Maturation of sedimentary organic matter expressed as: (1) vitrinite reflectance; (2) depth
within the same geological formation; and (3) pyrolysis temperature in hydrous pyrolysis experiments is
assessed by diffuse reflectance i.r. spectroscopy either using an index defined from intensities of specific
peaks or through a multivariate calibration of the spectral profiles with their respective maturation
indicators as dependent variables.
The samples were of three kinds: (a) kerogen samples (46) of varying maturity from the North Sea;
(b) asphaltene samples (108) prepared from sediments obtained from two different wells and a reservoir
from the North Sea; and (c) asphaltene samples prepared from hydrous pyrolysate of a sediment
containing type II kerogen.
The spectra show that the following chemical processes take place during maturation: (i) elimination
of carbonyl groups; (ii) depletion of aliphatic chains; and (iii) increase in aromatic content.
The univariate index, although sensitive to changes in organic facies, seems applicable within the oil
window with the best results obtained for type III kerogen.
Multivariate calibration of kerogen samples reveals the capability of the PLS method for predicting
vitrinite reflectance. Target projections of the PLS components provide validated spectral profiles, related
to the collective changes taking place during both natural and simulated evolution.
Key words--diffuse reflectance, i.r. spectroscopy, multivariate calibration, target projection, maturity
factor, kerogen, asphaltenes
INTRODUCTION
Determination of the type and maturity of kerogens
is important in petroleum exploration. Typing is
done by, inter alia, determining the elemental com-
position of kerogen, and the maturity level is gener-
ally determined by means of vitrinite reflectance
measurements. Maturity determination by vitrinite
reflectance measurements has its origin in rank deter-
mination of coals, where vitrinite is generally abun-
dant, thus leading to reliable results. For sedimentary
organic matter, where the total organic content of the
sediment is low, vitrinite particles are scarce. Further-
more, the organic matter is generally finely dispersed
in a mineral matrix which affects the vitrinite reflec-
tance measurements in a negative way. Demineraliz-
ation of the rock to release the organic matter
requires treatment with concentrated hydrofluoric
and hydrochloric acids. Low temperatures are necess-
ary, otherwise changes in the kerogen structure are
possible making vitrinite reflectance measurements
less reliable (Beny-Bassez and Rouzaud, 1985). Many
other maturity parameters have been proposed to
complement the vitrinite reflectance measurements,
for instance, biomarker analysis (McKenzie et al.,
1984; Philp, 1985), and indices derived from aromatic
hydrocarbon distributions (Radke et al., 1986;
Kvalheim et al., 1987a).
The use of spectroscopic techniques to study coals
and kerogen is not new. However, with the invention
of the Fourier-transform i.r. spectrometer, and the
development of new sampling techniques, the number
of applications has increased dramatically (Painter
et al., 1981, 1983; Tooke et al., 1983; Fuller et al.,
1982). Data handling by the use of computers and
the availability of multivariate software packages
(Kvalheim and Karstang, 1987b), have made it poss-
ible to analyse spectroscopic data for correlations and
trends. Thus, Christy et al. (1987) calibrated diffuse
reflectance Fourier transform i.r. profiles against
vitrinite reflectance measurements, of well-character-
ized whole coal samples, and demonstrated the ability
of the resulting multivariate calibration model for
predicting vitrinite reflectance. In this paper, a similar
approach is used to obtain a regression model for
predicting the vitrinite reflectance of kerogen
samples.
The structural similarity between kerogens, and
their associated asphaltenes, has been established by
several authors (Pfeiffer and Van Doormaal, 1936;
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