Geochtmrca PI Cosmochrmrco AcIa Vol. 51, pp. 1625-1637 0016-7037/87/$3 00 + .

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8 Pergamon Journals Ltd. 1987. Printed in U.S.A.

Prediction of source rock characteristics based on terpane biomarkers

in crude oils: A multivariate statistical approach
JOHN E. ZUMBERGE
Ruska Laboratories, Inc., 3601 Dunvale, Houston, TX 77063, U.S.A.

(Received July 4, 1986; accepted in revisedform March 17, 1987)

Abstract-The distributions of eight tricyclic and eight pentacyclic terpanes were determined for 2 16 crude
oils located worldwide with subsequent simultaneous RQ-mode factor analysis and stepwise discriminate
analysis for the purpose of predicting source rock features or depositional environments. Five categories of
source rocks are evident: nearshore marine (i.e., paralic/deltaic); deeper-watermarine; lacustrine; phosphatic-
rich source beds; and Ordovician age source rocks. The first two factors of the RQ-mode factor analysis
describe 45 percent of the variation in the data set: the tricyclic terpanes appear to be twice as significant as
pentacyclic terpanes in determining the variation among samples. J_acustrine oils are characterized by greater
relative abundances of CzI diterpane and gammacerane; nearshore marine sources by Cl9 and CrOditerpanes
and oleanane; deeper-water marine facies by Cr4 and CrJ tricyclic and C,, plus Cr2 extended hopanes; and
Ordovician age oils by Cr, and Crs pentacyclic terpanes. Although thermal maturity trends can be observed
in factor space, the trends do not necessarily obscure the source rock interpretations. Also, since bacterial
degradation of crude oils rarely affects tricyclic terpanes, biodegraded oils can be used in predicting source
rock features. The precision to which source rock depositional environments are determined might be
increased with the addition of other biomarker (e.g., steranes) and stable isotope data using multivariate
statistical techniques.

INTRODUCMON approach allows for the prediction of the origin of crude

DURING THE FORMULATIONand execution of an oil
exploration program, it is often critical to answer ques-
tions pertaining to crude oil geochemistry. These in-
clude: I) oil-oil and oil-source rock correlations which
determine the number of oil families in a given basin
and delineate migration pathways; 2) the estimation
of thermal maturities which can help predict the timing
of oil generation; and 3) the determination of the geo-
chemical controls which affect the quality of reservoired
oil (e.g., API gravity and sulphur content). However,
possible source rock samples often are unavailable for
analysis, simply because the drill bit rarely penetrates
deeper than the reservoir facies or the oil has migrated
updip from a basinward source facies. Therefore, in
order to predict migration pathways, the nature and/
or features of the source rock must often be deduced
from the organic geochemistry of available crude oil
samples.
Biomarkers, or geochemical fossils, are defined as
organic compounds found in sedimentary rocks in
which a sufficient part of the carbon skeleton has been
preserved. These compounds can be correlated with
the original biochemical precursor after having un-
dergone accumulation, diagenesis, and even catagen-
esis. Thus, biomarkers are indicators of depositional
environments in the same manner that physical re-
mains of organisms can describe depositional systems.
An excellent recent review on the applications of bio-
logical markers in petroleum geochemistry is given by
MACKENZIE( 1984).
In the present study, the distribution of tricyclic and
pentacyclic terpane biomarkers in crude oils generated
from known or suspected source rocks are compared
using multivariate statistical techniques. This empirical
1625
oils from unknown source rocks without knowing the
precise precursor-biomarker relationship for all bio-
markers considered. Only the terpane biomarkers are
considered in this study for a number of reasons. Most
practically, the tri- and pentacyclic terpanes are rela-
tively easy to define quantitatively and are present in
the vast majority of crude oils. This allows for increased
confidence in the classification of samples during sta-
tistical treatment of the data. In addition, the terpanes
are less susceptible to post-generative biodegradative
effects (especially the tricyclics) and thermal maturity
variations than the steranes (e.g., SEIFERT and MOL-
DOWAN, 1978, 1979; MACKENZIE,1984). However, the
steranes, although more difficult to measure accurately,
contain much information with respect to the thermal
history and origin ofcrude oils (e.g., MACKENZIE,1984;
MOLDOWANef al., 1985). Sterane and bicyclic terpane
(e.g., PHILP ef al., 198 1) data should eventually be in-
corporated into statistical evaluations, along with the
tri- and pentacyclic terpane distributions. In addition,
stable carbon and hydrogen isotope data also need to
be considered, since important source information is
provided (e.g.. SOEER, 1984; PETERSet al., 1985), and
the use of disparate techniques (i.e., biomarkers and
isotopes) is a prerequisite for successful geochemical
correlations (e.g., SOFER and ZUMBERGE, 1985).
Nonetheless, routine determinations of the tri- and
pentacyclic terpane distributions allow for accurate
predictions of various source rock depositional envi-
ronments or other source rock characteristics, as will
be shown below.
The hopane homologs of the pentacyclic triterpanes
are believed to be derived from the structural lipids in
bacterial cell walls (OURISSONet al., 1982). Other pen-
tacyclic terpanes, such as gammacerane and the Cz8
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3.4 7.7 11.3 6.0 22.0 14.8 10.8 1:3 11:o 3.9 ::: 29.6
2.‘ 11.6 19.4 3.1 20.5 16.9 12.3 10.3 7.3 .O .O 18.5

1.1 6.8 11.3 4.5 5.2 22.5 12.9 16.3 13.6 10.1 .o 4.7 I*drim. f 1961)
1.3 6.2 9.5 5.8 5.3 22.8 15.7 17.2 12.9 9.2 .o 5.7 ,*.c,orro a* carrl*on~1981~
2.5 8.0 4.6 5.4 15.9 11.4 17.1 16.3 13.6 .fJ 4.3 7w.e 11964)
2.7 6.7 i:: 4.5 5.0 16.6 22.8 17.7 16.0 14.3 curtal* lt ‘1. (19851
1.4 5.9 8.1 1t.2 14.1 13.9 12.2 1:: :,:
2.7 II.6 8.8 .o 31.2 ::*: 23.1 10.8 :o
3.3 13.2 32.‘ 17:4 27.8 11.9 :i _I .a6 YllliR9 (19841
2.0 7.9 ::: 28.5 le.4 2.9 .o 7:;
1.6 7.6 9.3 27.8 16.9 IO.6 .O 6.9 Cl~yPod lt al. (1978)
2.3 6.8 8.8 ____.._ ._ 19.8 15.8 .O 6.1
1.4 6.8 9.4 9.8 42.6 11.2 9.6 ii:: 22.3 13.5 1::: .o 2.8 ?a11 *I ll. (1975)
2.0 6.5 9.4 8.8 40.8 1o.s 12.3 17.8 21.1 23.4 9.2 .o 4.e l,*“r ml6 Yhtt. Wlu)

11.. 9.2 18.2 6.8 20.3 10.5 P.? 5.9 13.5 19.6
i.9 21.1 16.4 12.2 .5 6.4
19.1 15.9 14.2 10.5 15.7 8.6 9.2 4.0 12.6 19.5
.O 26.9 i9.1 11.5 .O 2.3
IS.0 14,s 14.5 7.6 11.2 10.2 8.4 3.8 10.9 ‘7.‘ 25.7 20.0 13.3 .o 1.3
20.5 14.9 I‘.3 9.9 8.5 15.4 :: 19.9 25.8 Il.2 9.3
21.3 15.7 il.1 1.3 10.3 ::; 10.8 .O 20.0 26.0 19.1 Q-7
_.. :i :.‘:
21.7 15.3 13.7 4:s
:.: 12.1
:::‘: 13.6 0.7 5.3 10.6 .O 11.2 23.2 19.0 11.2 .O 2:3
10.9 10.9 16.6 7.3 20.9 12.0 9.8 4.3 16.5 .9 22.0 24.2 13.4 10.2 .o 3.1
9.0 8.9 18.2 7.2 13.7 12.8 10.3 5.6 13.7 I.4 19.9 21.2 16.2 Il.9 .O 6.8
19.6 11.9 17.8 7.0 14.3 6.7 3.7 3.0 21.6 3.6 24.9 16.5 11.1 8.7 .o 1.5
12.6 10.0 14.4 5.3 16.0 6.7 3.9 2.2 14.9 .O 24.7 14.7 18.4 10.4 .o .o me1.r *I l1.<19811
29.6 17.4 13.3 5.1 lb.3 12.2 1.0 ‘0.6 .o 25.8 14.8 11.7 7.0 .o .o Y1111~~19?‘~2~?p~19831
4.0 9.0 13.6 5.9 15.4 15.1 14.8 ::!: 13.4 7.1 17.3 24.0 10.2 .o 1.3
7.2 9.8 17.6 7.‘ 21.4 13.9 11.9 6.2 13.8 3.3 19.9 24.5 :::: 11.3 .o 2.7
4.2 13.2 12.6 14.2 12.4 6.5 9.6 .6 22.6 23.6 17.‘ 11.3 .o 2.1
3.1 12.9 17.6 15.2 6.6 14.6 4.4 17.1 27.3 15.4 10.1
3.7 ::: 13.2 16.5 14.9 11.7 9.8 3.5 20.5 26.0 15.4 8.8 :; 4::
 9’,
O’S
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S.01 “....,.d
5’8
O’W C’IZ “.R.,.d
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1630 J. E. Zumberge
bisnorhopane, have a more nebulous origin (PALMER,
pers. commun.; MACKENZIE,1984; GRANTHAMet al.,
1981), although oleanane appears to be derived from
higher land plant sources (EKWEOZOR et al., 1979).
The origins of the tricyclic terpanes commonly found
in oil also are not well known. The lower molecular
weight tricyclic diterpanes (i.e., Ct9 and C,) can be
derived from vascular land plants (e.g., REED, 1977;
SIMONEIT, 1977; RICHARDSONand MIILLER, 1981).
The terrestrial source, however, is not unique, since
low molecular weight diterpanes are relatively abun-
dant in crude oils generated from Ordovician sediments
deposited prior to the evolution of land plants (ZUM-
BERGE, 1983; PALMER, 1985). AQUINO NETO et al.
(1983) suggested that the tricyclic terpan& have a mi-
crobial or algal origin. MOLDOWANet al. (1983) re-
ported a series of tricyclic terpanes from Cl9 to C& in
petroleum and concurred with OUR~SSONet al. (1982)
that these compounds can be derived From bacterial
membranes.
The sample’ set used in this study consists of 2 16
crude oils from 27 countries and 14 states; sample
documentation is listed in Table 1. Since oils from the
same source rock can vary in composition due to or-
ganic facies changes, many of the oils used in this study
represent oils from different fields but from the same
geologic source. Only a few are from the same reservoir.
The source rocks for many of these oils are not known
and some are only suspected. Oils with known source
horizons are referenced in Table 1 or have been de-
duced from unpublished in-house studies, and are
based on geochemical oil/source correlations and/or
geological considerations. The oils are grouped into
five categories based on the known or suspected de-
positional environments or other characteristics of the
source rocks. The categories are: 1) deeper-water ma-
rine facies; 2) nearshore marine (i.e., paralic/deltaic);
3) lacustrine (both rift and continental tectonic set-
tings); 4) phosphate-rich source rocks; and 5) oils from
Ordovician-age source rocks. A sixth category includes
the oils with origins unknown to the author.
EXPERIMENTAL AND STATISTICAL METHODS
Crude oil samples were deasphalted in n-pentane followed
by separation into aliphatic hydrocarbon, aromatic hydro-
carbon, and NSO fractions using either a Perkin Elmer Series
4 HPLC (25 cm X 9.4 mm amino-cyano/lO pm silica column)
or mixed aluminum/silica liquid chromatography columns.
Aliphatic hydrocarbon fractions wets analyzed by gas chrc+
matography/mass spectrometry using a Kratos MS25 GC/
MS system with ion monitoring of m/r = 19 I to determine
terpane distributions. The SE-54 coated capillary column
(fused silica, 30 m x 0.3 mm) was temperature programmed
from 100” to 2QO’Ca1 2.5”C/min. and held at 290°C until
the CJshopanes eluted. Peak areas of the terpane components
were recorded based on the m/r = 19 1 mass chromatograms
using a Hewlett Packard 3357 Lab Automation System and
retention times were compared to standards for identification.
Combined R- and Q-mode factor analysis, based on the
principal components method and computer program of
ZHOUet al. (1983), was applied to the complete sample set
subsequent to data standardization(i.e., the mean is subtmcted
from each corresponding terpane value and divided by the
standarddeviation). Factor analysis is a multivariate statistical
technique that creates new indepe&ent variaW (i.e., factor)
that are linear combinations of the original variables (i.e., nl-
ative terpane abundances). The primary objective of the sta-
tistical analysis is to reduce the dimensionality of the data to
a few important components or factors that best explain the
variation in the data. In simultaneous RQ-mode factor anal-
ysis, both the variables and observations are scaled so they
can be plotted on the same set of factor axis; thus, the asso-
ciations between both variables (R-mode) atid samples (Q
mode)canbeeasilyvisualized(ZH~~ etal., 1983). Themethod
of principal components rather than correspondence analysis
was employed. In factor analysis, none of the oil samples are
preclassified (i.e., into lacustrine, deepwater marine origins,
etc.) prior to the statistical treatment; oils with similar terpane
distributions are grouped together in factor space and specific
variables which are important in distinguishing the groups of
oils are determined.
Stepwise discriminant atiysis also can be used to classify
the oil samples (e.g.. DIXON,1981). Samples are preclassified
into known groups. The variables of unknown samples are
subsequently compared to the groups of known samples with
an associated probability on the goodness of fit with any given
category. Recently, SHAW and JOHNS(1985), SOUR and
ZUMBERGE (1985), MACCARTHY ef al. (1985), and HUGH=
et al. ( 1985) have applied factor analysis to organic geochem-
ical problems, while PETERSef al. (1985) have used discrim-
inate analysis to determine origins of crude oils.
RESULTS AND DISCUSSION
Separately, normalized distributions of eight tricyclic
(C1+&) and eight pentacyclic (C&&, oleanane and
gammacerane) terpanes from 2 16 oils are given in Ta-
ble 1. Figure I illustrates the m/z = 19 1 mass chro-
matogram of a standard mixture of crude oil aliphatic
fractions which contain the terpane components (la-
beled in Fig. 1) used in this study. The eight tricyclic
components are, for the most part, single compounds,
although they do not completely sum to 100 percent
(Table l), since other minor components were included
in the normalization, such as the common tetracyclic
terpane (M. W. = 330), which elutes immediately prior
to the two CX stereoisomers at about 63 min. retention
time (Fig. 1). However, the eight tricyclic terpanes listed
in Table 1 average 93 percent of the m/z = 191 peak
areas between 42 and 64 min. retention time. These
eight tricyclic terpanes, which are used in subsequent
multivariate analysis, yielded the most reliable quan-
titative results due to the lack of significant coelution
(e.g., the second eluting Cz6 isomer was used because
of the partial coelution of the first Cz6 isomer with the
tetracyclic terpane).
Eight pentacyclic terpane components also were
normalized with respect to the total m/z = 191 peak
area between 72 and 88 min. retention time (Fig. 1).
In contrast to the tricyclics, some of the pentacyclic
compounds were combined and used as single vari-
ables. These include C2, isomers (i.e., a combination
of the Ts and Tm trisnorhopanes to minimize thermal
maturity effects; SEIFERTand MOLDOWAN,1978) and
the 22s and 22R stereoisomers of the CjI and CJt ex-
tended hopanes which have thermally equilibrated in
the vast majority of crude oils (MACKENZIE, 1984).
The area of the shoulder on the major Cm norhopane
component (Fig. 1) was included in the Cz9 variable.
The peak labeled GA in Fig. 1 consists primarily of
 Terpane biomarkers in crude oils 1631

m/r = 191

FIG. 1. Mass chromatogram (m/z = 19 1) of the ahphatic fraction from a standard mixture of crude oils
showing the 16 terpane variables used for factor analysis. Cl9 through Cz6am tiicyclic terpanes with molecular
weights of 262 to 360, respectively. Cr, consists of l&(H) and 17n(H) trisnohopanes; Cz8 is 17a(H),
18a(H),2 l@(H)-28,30_bisnorhopane; CB is 3Onorhopane; OL is 18cu(H)-oleanane; Ca is hopane; CN consists
of the 22s and 22R stereoisomers of homohopane; GA is gammacerane; and CJ2 is the 22s and 22R isomers
of bishomohopane. Experimental conditions are given in the text.

gammacerane, although other
such as extended tricyclic terpanes, may coelute. These
eight pentacyclic terpane variables used in subsequent
multivariate analyses averaged 88 percent of the m/z
= 19 1 peak areas between 72 and 88 min. retention
time (Fig. 1). Variables which relate the relative abun-
dance of the tricyclic to pentacyclic terpanes were not
used, because nongenetic factors such as maturity, mi-
gration, and bacterial degradation can affect the relative
abundance between these two classes of terpanes and
could affect the results of the statistical analysis.
Table 2 lists the mean and absolute standard devia-
tions of the 16 terpane variables from the 2 16 oils tab-
ulated in Table 1. The CZ~and COO(hopane) compo-
nents are, on the average, the largest tricyclic and pen-
tacyclic compounds, respectively, and their standard
deviations are the smallest on a percentage basis. The
C19, Cr8, oleanane (OL), and gammacerane (GA) ter-
tetpane components, panes have the largest relative percent standard devia-
tions.
The correlation matrix (Table 3) for the 16 terpane
variables gives the linear correlation coefficients for
each combination of variables. The Cl9 and Cm tricyclic
terpanes have a relatively high positive correlation
coefficient (+0.63). Both of these lower molecular
weight terpanes, however, show a high negative cor-
relation with the Cz, through Cz6 tricyclics. Perhaps
this reflects a predominantly terrestrial origin for the
C,9 and CZOditerpanes (e.g., REED, 1977) and a pre-
dominantly marine origin for the Cz3 through Cz6 tri-
cyclic terpanes (e.g., OURISSONet al., 1982). The Cz4,
Cz5, and Cz6tricyclics correlate positively to each other,
with Cz4 and CZshaving the largest coefficient (+0.67).
Regarding the pentacyclic terpanes, C3, and Csz have
the strongest correlation (+0.72) between any two
variables studied, which is not surprising considering

TABLE 2

Mean and Standard Deviations of the 16 Terpane

Variables from the 216 Oils Listed in Table 1

C C C C C C C OL GA'
19 20 %l sz ‘23 24 '25 '26 '27 '28 79 30 31 32
I I
; (I) 7.4’. 10.5 13.3 5.5 23.1 14.0 12.2 7.0 11.2 2.3 19.8 24.5 13.9 8.8 2.0 4.9

10 8.7 4.4 3.5 1.9 6.5 3.1 3.9 2.1 4.3 4.3 4.3 4.7 4.1 2.8 5.9 5.3

Min. 0.3 3.5 5.6 0.0 5.0 2.4 1.0 1.0 5.0 0.0 9.8 11.2 4.8 1.0 0.0 0.0

M*X. 52.0 31.7 25.8 11.8 42.6 20.5 21.3 13.0 40.6 22.8 40.4 36.3 27.8 15.3 36.5 31.2

I*=* 2.4 1.6 0.7 0.6 0.6 -0.7 -0.1 -0.2 2.3 2.6 0.7 -0.3 -0.1 -0.2 3.9 2.1

l Terpane identifications are shwm in Figure 1.

l * Values are separately normalized percentages for tricycllc and pentacyclic variables.

l ** Moment coeffic<ent of skewness = (3rd moment)/(Znd moment)3/2.

1632 J. E. Zumberge

TABLE 3

Correlation Hatrlr of Terpane Varllblts.

Absolute Llnaar Correlations >0.40 WC Highlighted

Cl9

C20

C2l

C22

C23

C24

C25

C26

C27

C28

C29

C30

C31

C32

OL

64

their likely common origin. These same two higher
molecular weight terpanes correlate negatively with
oleanane. Norhopane (Czg) and the trisnorhopanes
(C,,) exhibit the second most positive correlation
among the pentacyclics. Gammacerane and the Cr,
diterpane are the only variables from the two separate
terpane groups that show an absolute correlation of at
least 0.40 (arbitrary value).
Figure 2 illustrates the results of the simultaneous
RQmode factor analysis of the terpane data in Table
1. Together, the first two factors account for over 45
percent of the total variation in the data set (factor 1,
25% factor 2,20%). Factors 3,4, and 5 describe 12,
9, and 7 percent of the variation, respectively. Table
4 lists the relative contribution from each of the 16
terpanes to factors 1 through 5. A high relative factor
loading for a particular variable (Table 4) is reflected
in Fig. 2a as a vector paralleling the factor axis (e.g.,
variables Crg and Cr5 for factor 1), whereas variables
with low relative factor loadings tend toward the per-
pendicular. Tricyclic terpane variables CIg, Cm, Cr4
and Crs account for most of the loadings (66%) on
factor 1, while Cz , , Cz2, Cz3, and the extended hopanes
comprise most (67%) of factor 2. Considering only fac-
tors 1 and 2, the tricyclic terpanes are more than twice
as important as the pentacyclic terpanes in describing
the variations in the data (Le., tricyclics = 67.5%. pen-
tacyclics = 32.5% of factor 1 and 2 loadings). Factor
3 is made up primarily of Cm, C3, , C32, and oleanane,
while factor 4 is comprised mostly of Cr8 and Crg.
Gammacerane is by far the primary component of fac-
tor 5. Since the variables are normal&l to one-another,
“closure effects” may possibly occur during multivar-
iate analyses (DAVIS, pem. commun.) where a degree
of freedom is lost. Although few of the variables have
very high linear correlation coefficients (Table 3), clo-
sure problems may possibly affect the interpretations.
In Fig. 2a, the 16 terpane variables are related to
factor 1 and 2 space. For example, Cig and Cr) are
major loadings on factor 1 (Table 4) with a high neg-
ative correlation (Table 3); CZ~has approximately equal
loadings between factor 1 and 2. The length of the
terpane vectors in Fig. 2a correspond to the importance
of the variables in describing the variation in the data.
Figure 2b shows a plot of the oil samples in the same
factor space as Fig 2a (ZHOU et al.. 1983). Although
all 2 16 oils were used in the factor analysis, only the
172 samples with known or deduced source rock de
positional features are plotted. The numbering system
used in Fig. 2 is the same as the numbering system in
Table 1 (e.g., oils from Ordovician-age source rocks
= 5). As can be seen from Fig. 2b, a rather remarkable

FIG. 2a. R-mode factor analysis showing the intetrelationship of the 16 terpane variables (shown in Fig.
1) in factor I and 2 space. The compositions of factors I and 2 are given in Table 4; these factors account
for 45 percent of the variation in the data.
FIG. 2b. Q-mode factor analysis showing the interrelationship of the crude oil samples with known or
suspected source rock features characteristics (Table I) in factor I and 2 spacx. These are the same factors
as in Fig. 2a and account for 45 percent of the variation in the data. The small hatched area repmsents the
range of triplicate terpane analyses of a single sample over a three year period. The arrows indicate thermal
maturity trends. The three marine-sourced oils with asterisks repmsent biodegraded seep and rese~oired
oils as well as a nondegraded oil from the Middle Magdallena Valley,Colombia (ZUMBERGE, 1984).
 Terpane homarkers in crude oiis 1633

o(, c21

=b CA
% C26 \ a

< FAC 2 >

1634 J. E. Zumberge

TABLE 1 field indicates the range of variation for a single sample

A-bladeRclatlve Contrlbutlons to Factor Loadings (named WB5; Table 1) that was analyzed for terpanes
by GC/MS over a period of three years. This repro-
F4ctor 1 Factor 2 Factor 3 Fwtor 4 Factor 5 ducibility appears acceptable, considering the much
Cl9 0.70 0.00 0.06 0.13 0.01 larger variation between oil types. Second, the three
C20 0.63 0.13 0.01 0.00 0.00 small arrows in Fig. 2b represent thermal maturity
:: C21 0.00 0.47 0.02 0.19 0.05 . trends from oils presumably from the same source for
; C22 0.03 0.39 0.03 0.03 0.15
each of the three examples. These include the low ma-
U C23 0.29 0.33 0.14 0.02 0.02
0.61 0.05 0.03 0.02 0.07
turity Walker Hollow and the corresponding high ma-
e c24
C25 0.72 0.00 0.00 0.02 0.04 turity Altamont oils generated from the Eocene lacus-
c26 0.32 0.22 0.04 0.08 0.02 trine Green River Formation, Utah; a pair of Missis-
sippian oils from the Williston Basin (sample ID:
c27 0.25 0.04 0.09 0.14 0.02
0.13 0.36 0.01
D2353 and D2354, Table 1; LEENHEER and ZUM-
C28 0.16 0.01

:: C29 0.09 0.17 0.09
2 C30 0.00 0.10 0.45
C31 0.01 0.56 0.2e
::
z c32 0.05 0.38 0.31
OL 0.12 0.08 0.27
64 0.06 0.26 0.00
discrimination of the oils is achieved using factor anal-
ysis on these 16 terpane variables. There is some over-
lap between the source rock domains, but thii is not
surprising considering that many oils are mixtures of
hydrocarbons generated from different source f&es or
from a source rock containing the chemical remains
of organisms living in different environments. Nev-
ertheless, the terpane distributions in crude oils can be
used to estimate the nature of their respective source
rocks. The results of this study also show that more
information on source rock characteristics, other than
just marine versus nonmarine, can be derived from
the terpane biomarker distributions by using factor
analysis. Oils generated from different nonmarine or-
ganic sources can be distinguished (e.g., lacustrine ver-
sus nearshore marine), and oils derived from phos-
phate-rich beds are distinguishable from those sourced
from the more common marine source rocks. Even
oils generated from sediments deposited prior to the
evolution of land plants (e.g., Ordovician-age crudes)
can be grouped into a separate category based only on
terpane distributions. No obvious distinction between
carbonate and shale source rocks can be made.
In comparing Figs. 2a and 2b, it becomes apparent
that the variables (terpanes) responsible for the various
source rock classifications can be ascertained. Lacus-
nine oils contain relatively abundant amounts of C2,
diterpane and gammacerane while paralic/deltaic oils
are usually characterized by high concentrations of Cl9
and Czo diterpanes plus, sometimes, oleanane. Crude
oils generated from phosphate-rich source rocks are
characterized by abundant Cz2 and Cz3 tricyclics as
well as the bacterial hopanes (C,, and Csl). The typical
deeper-water marine-derived oils alten contain rela-
tively greater quantities of Cz4, Cz3, and Cza tricyclic
terpanes. Ordovician oils may be distinguished by the
CX and Cz9 pentacyclic terpanes.
Two other points of interest are noted on Fig. 2b.
First, the small hatched area within the paralic/deltaic
0.37 0.06 BERGE, 1986) and oils from the Peru Oriente Basin
0.04 0.10 (SOFER and ZUMBERGE, 1985). Again, these maturity
0.00 0.00 trends do not obscure the source rock predictions, es-
0.03 0.02
pecially considering the degree of maturity difference
0.04 0.04
0.01 0.51
the arrows represent (i.e., equivalent to 10” to 15” API
gravity). It appears that the lower molecular weight
diterpanes (Cl9 and C,) increase relative to the C23+
tricyclic terpanes with increasing thermal maturity.
This same trend has been observed during simulated
oil generation experiments using hydrous pyrolysis
techniques (ZUMBERGEet al., 1984). Lastly, only ex-
treme biodegradation may alfect the source rock pre-
dictions since two-thirds of factors 1 and 2 are repre-
sented by the tricyclic terpanes which, as mentioned
above, are very resistant to bacterial degradation. The
three marine-derived oils (denoted with asterisks in
Fig. 2b) from the Middle Magdallena Valley, Colombia,
represent a heavily biodegraded surface seep oil, a
moderately biodegraded reservoired oil, and a non-
degraded reservoired oil, all generated from the same
source rock (ZUMBERGE,1984). Biodegraded oils from
the Alberta tar sands and North Slope, Alaska, show
an even closer relationship in factor space to their re-
spective nondegraded counterparts.
Figure 3 shows the same source rock domains as
Fig. 2b, plus the 44 oils from unknown source rocks
(refer to Table 1 for sample identification). For ex-
ample, the Ecuadorian oils from the Oriente Basin plot
in the Deeper Marine field (as do the Peru Oriente
oils), while the coastal Ecuadorian oils from the Sta.
Elena Basin (#449 and #451) plot in the Lacustrine
field as do the oils from offshore Peru (#625 and #626).
Also, some of the oils from the Paradox Basin, Utah,
may have originated in phosphate-rich source beds
based on their factor loadings.
In order to determine the confidence level associated
with the placement of an oil sample from an unknown
source into one of the five categories, stepwise discrim-
inate analysis was used (DIXON, 1981). The average
terpane values for each known source rock domain
(Table 5) were compared with unknown oil samples
using discriminate multivariate analysis. In this man-
ner, a probability value can be assigned to the unknown
sample, and may possibly be used to determine the
goodness of fit to any given source characteristic. For
example, sample #60 1 (Fig. 3; Canadian Williston Ba-
sin, Table 1) is given a 100 percent probability as being
 Terpane biomarkers in crude oils 1635

< FAC 2 >

4l

I < FAC
-.4

FIG. 3. Q-mode factor analysis showing the same source rock domains as in Fig. 2b. Crude oils with
unknown source rocks are plotted; identifications are given in Table 1.

sourced from phosphate-rich m&s. Sample #I441, from paring terpane distributions from unknown oils with
the Kaiparowits Basin, Utah, is given a probability of those of known origin.
either being derived from deeper marine or phosphate-
CONCLUSIONS
rich rocks (69% and 3 I%, respectively). A sample from
the Llanos Basin, Colombia (#58 l), is predicted to have 1. Combined RQ-mode factor analysis allows for
a marine source (100% probability), while the origin both the relationships that exist between variables (i.e.,
of sample #536 (Paradox Basin, Utah) is much less 8 tricyclic and 8 pentacyclic terpanes) and samples (i.e.,
clear: 10 percent Lacustrine, 38 percent Ordovician, 2 I6 crude oils) to be visualized in the same factor space.
and 52 percent Deeper Marine. Discriminate analysis, 2. Factors 1 and 2 account for 45 percent of the
consequently, may be useful in quantitatively com- variation in the data set. Factor 1 is composed primarily

TABLE 5

Average Terpane Percentages (*lo) for Each Known Source Rock Domain

1. Deep Water Marine 2. Para;it/;eqltaic 3. Lacustrine 4. Phosphatic 5. Ordovician

" = 89 n = 31 " = 12 n = 16

4.4 * 2.4 24.0 * 12.1 3.9 t 4.2 2.0 f 0.7 13.5 * 8.1
8.8 * 2.0 17.2 t 5.1 12.4 * 4.6 8.0 f 2.3 12.0 t 3.2
12.7 * 2.1 11.4 t 2.8 18.8 f 2.4 9.4 * 0.1 14.8 * 2.2
5.2 t 1.5 5.0 * 2.1 4.3 * 1.0 7.2 * 1.B 6.6 t 1.4
23.0 t 4.0 15.2 * 5.0 2fl.2 f 2.6 37.6 e 3.9 18.6 . 5.0
15.5 f 1.7 10.1 * 3.4 14.2 e 2.3 12.1 * 1.9 11.8 * 3.3
14.3 * 2.8 7.1 t 2.7 10.5 f 2.0 11.6 $2.7 9.5 f 4.0
7.2 * 1.2 5.4 * 2.4 9.1 t 1.9 5.0 * 0.R 6.0 t 2.9
----________________~_~~~~~~~__________________~~~~~~~_~~~~~~~~~~__~~_~~~~~~~______~~~~~______
11.0 t 3.6 12.0 * 3.7 9.6 t _2.5 10.0 t 4.6 15.1 f 7.4
2.9 f 4.4 0.9 f 1.8 0.4 * 0.9 8.2 + 9.9 1.6 e 2.2
19.4 f 4.2 19.5 f 2.6 lE.9 = 4.4 21.4 t 7.9 20.6 + 2.7
24.0 t4.1 26.7 1 3.9 27.0 * 5.3 16.7 f 2.0 23.6 . 3.6
14.6 t 3.7 12.6 t 4.3 10.8 f 2.9 17.6 * 4.7 16.6 ; 2.7
9.3 * 2.4 7.5 , 3.7 6.7 e 2.2 10.3 f 2.9 10.4 f 1.5
0.4 t 1.2 7.2 211.9 0.5 f 1.3 0.0 f 0.0 0.0 * 0.0
3.4 t 3.0 1.9 * 2.1 12.4 f 7.8 4.3 = 2.4 2.4 * 2.0
1636 J. E. Zumbeqe
of C19, C2,,, C2.,, and Cr5 terpanes, while factor 2 con-
sists of C2, , Cr2, Czs terpanes and the extended hopanes.
3. The tricyclic terpanes appear to be twice as sig-
nificant as the pentacyclic terpanes in determining the
variation among samples.
4. Factor analysis was able to separate the oil sam-
ples into five different categories, an improvement over
the traditional marine versus nonmarine categories.
Terpanes characteristic of the five’source rock features
are gii en below.
Lacustrine: Cr, diterpane; gammacerane
Neat-shore marine: Cl9 and Go diterpanes; oleanane
Deeper water marine: Cr4 and CZ~tricyclic terpanes
Phosphate-rich: Cz3 tricyclic terpane; Crr and Csz
extended hopanes
Ordovician: Cr7 and Cr9 pentacyclic terpanes
5. Although small thermal maturity trends are ob
served in factor space, the trends do not obscure the
source rock interpretations. The Cl9 and Cm diterpanes
increase. slightly, relative to the higher molecular weight
tricyclic terpanes, with increasing thermal maturity.
6. Since bacterial degradation of crude oils rarely
affects the tricyclic terpanes (which are also the most
important terpanes for classifying oils) bi&graded oils
can he used to predict source rock characteristics.
Acknowledgements-1 thank Shirley Sellers, Janet Williamson,
and Fred Balch for statistical and analytical help, Susan Palmer
for critical comments, John Davis for statistical discussions,
Maggie Draughon and Peggy Gilley for typing the manuscript
and Cities Service Oil and Gas Corporation for permission to
publish.
Editorial handling: R. P. Philp
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