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Geochemical and biological marker assessment

of depositional environments using Brazilian


offshore oils*
M. R. Mello t and P. C. Gaglianone
Petrobras/Cenpes/Divex, Ilha do Fund~o, CEP: 21910, Rio de Janeiro, RJ, Brazil

and S. C. Brassell
Department of Geology, School of Earth Sciences, Stanford University, Stanford,
California, CA 94305, USA

and J. R. Maxwell
Organic Geochemistry Unit, University of Bristol, School of Chemistry, Bristol BS8 ITS,
UK

Received 14 August 1987; accepted 23 October 1987


A combined geochemical and molecular characterization of a wide selection of oils from the
major Brazilian offshore basins has been undertaken. The elemental (sulphur, nickel and
vanadium) and bulk (API and ~13C) properties of each sample have been considered, together
with its molecular composition determined using liquid and gas chromatography, and
quantitative biological marker investigations using gas chromatography-mass spectrometry for
alkanes.
The results reveal significant differences in the chemical features of the various oils which
enable them to be divided into five groups. The distinction of the groups appears to reflect
differences in the depositional environment of the source rocks of the oils. Each group is
correlated tentatively with source rocks laid down in a specific depositional regime, namely
lacustrine freshwater, lacustrine saline water, marine evaporitic, marine carbonate or marine
deltaic. The diagnostic features that allow this classification are: the relative abundance and
carbon number distributions of n-alkanes; pristane/phytane ratios; sulphur, nickel and vanadium
contents; carbon isotope data; the absolute concentrations of hopanes and steranes, and their
abundance relative to 4-methylsteranes and, also the occurrence and abundance of several
specific biological markers, including 18o~(H)-oleanane, gammacerane, 13-carotane, tricyclic
terpanes, higher acyclic isoprenoids, 28, 30-bisnorhopane and 25, 28, 30-trisnorhopane. This
investigation shows the value of a combined geochemical and molecular approach in the
assessment of the palaeoenvironment of deposition of the source rocks which gave rise to the
oils.
Keywords: geochemical characterization; molecular characterization; depositional environments; offshore
oils; Brazil

Introduction
The assessment and differentiation of the depositional
palaeoenvironments of petroleum source rocks using
molecular parameters is increasing in importance and
application. Both geochemical evidence and biological
marker distributions enable the characterization and
distinction of ancient marine and non-marine
petroleum source rocks (e.g. Mackenzie et al., 1984;
Moldowan et al., 1985; McKirdy et al., 1986; Peters et
al., 1986). In addition, recent evidence shows that such
features provide diagnostic criteria for the distinction of
oils derived from source rocks deposited in different
environments, such as lacustrine freshwater and
hypersaline in China (e.g. Powell, 1986; Brassell et al.,
* Paper presented at the meeting 'Advances in Petroleum
Geochemistry' 19 May 1987, Geological Society, London, UK
t Present address: Organic Geochemistry Unit, University of
Bristol, School of Chemistry, Bristol BS8 1TS, UK

1988; Fu Jiamo et al., 1986), marine carbonate in


Venezuela, Australia and Florida (Talukdar et al.,
1986; McKirdy et al., 1984; Palacas et al., 1984) and
lacustrine freshwater in Australia (McKirdy et al.,
1986; Philp and Gilbert, 1986). It is evident that the
components of a particular sediment extract or oil are a
reflection of the precursor compounds in the organisms
which contributed organic matter at the time of
sediment deposition, and thereby can provide valuable
information about the prevailing environmental
conditions.
Molecular properties for use in
palaeoenvironmental assessment should ideally be
diagnostic of specific types of organisms with
ubiquitous and documented occurrence in recent and
ancient well described depositional environments
(Brassell and Eglinton, 1986). In addition, such
molecular features can be affected by diagenetic
processes and may reflect evolutionary changes in the
sources of sedimentary organic matter.

0264-8172/88/030205-19 $03.00
1988 Butterworth & Co. (Publishers) Ltd
Marine and Petroleum Geology, 1988, Vol 5, August

205

Depositional environment characterization." M. R. Mello et al.

q8o

Cassipore

Foz Do Amazonas

~
""

0 o --

Par~/'M aranhao
~

Ceara

Potiguar

BRAZIL
Sergipe/Alagoas

.i

Bahia Su{
Espirito Santo

Campos

Santos

Figure 1 Location map of Brazilian marginal basins

UPPER
CRETACEOUS
TO
TERTIARY
SLOPE
SYSTEM

ALBIANCENOM.
APTIAN
UPPER NEOC.
LOWER NEOC
UPPER JURAS.

BASEMENT

EX~

[Tg%~

EvAPo.,TEs

r~%-'l

.AL,TE

VOLCANIC ROCKS

CONGLOMERATE

~AS~MENT

o,L

ACCU~ULAT,O.S

Figure 2 Idealized geological section with general stratigraphic and structural features for the Brazilian marginal basins
206

M a r i n e a n d P e t r o l e u m G e o l o g y , 1988, Vol 5, A u g u s t

Depositional environment characterization: M. Ft. Mello et al.


tectonic quiescence, topographical barriers and arid
In this study we employ a combination of geological
climate led to a low elastic influx and restrictions
and geochemical data for a number of oil samples in an
appropriate for deposition of mixed carbonate and
attempt to characterize and assess the environments of
siliciclastic sediments together with evaporites in
deposition of the source rocks that gave rise to them. A
coastal, shallow continental to marine environments
succession of putative source rocks deposited in
(Asmus, 1975).
distinct, well-defined environments exists within the
As a consequence of sea floor spreading and the
Brazilian marginal basins (Figures I and 2; Mello et al.,
subsidence of the Brazilian continental margin, the
1984, 1988). Specifically, the elemental and bulk
proto-South Atlantic Ocean maintained an almost
properties, and biological marker distributions of about
uniform palaeogeographic setting during the Albian.
fifty oil samples recovered from reservoirs ranging from
At this time, mainly carbonate sediments were
lower Neocomian to Oligocene within the major
accumulated in a neritic environment in an
Brazilian offshore basins (Figure 1) were investigated.
epicontinental sea (Koutsoukos, 1987). The marine
In order to minimize differences due to the effects of
platform and slope carbonates were deposited under
maturation, and the effects of biodegradation, water
conditions of tectonic quiescence, with some
washing, gravity segregation and loss of volatiles, only
adiastrophic tectonism often associated with detached
oils which were comparatively unaffected by such
listric faults soling out on the Aptian salt. The late
processes and with medium to high API values were
Cretaceous to Holocene marine shelf-slope succession,
selected (as far as possible). Sixteen of the oils (Table
characterized by carbonate and mainly siliciclastic
1), chosen to be representative of the total, were
sediments, represents the open marine stage in the
selected for a more detailed g.c.-m.s, study to measure
Brazilian marginal basins, with basin subsidence,
the concentrations of specific biological marker
seaward tilting, large adiastrophic growth-faulting
compounds by addition of a deuteriated sterane
structures and local volcanic events. Important in this
standard.
context is the deposition of widespread sapropelic
sediments, such as calcareous mudstones and black
Geology of Brazilian offshore basins
shales with high organic carbon contents, in almost all
the offshore basins, during late Cenomanian to
The Brazilian marginal basins are directly related to the
Santonian times. This pattern of sedimentation in the
rupture of the African and South American plates.
Brazilian basins is consistent with a global oceanic
They are classified as components of a typical
anoxic event (e.g. Schlanger and Jenkyns, 1976).
divergent, rifted continental margin (Ponte and Asmus,
Oxygenated conditions have prevailed in most of the
1978; Estrella et al., 1984). In general, they can be
Brazilian marginal basins since the Campanian, with
linked to a single evolutionary geological history
deposition of mixed elastic and carbonate sediments.
(Figure 2). They were formed during an Early
Cretaceous (Neocomian) rifting phase when a thick
succession comprising continental,
fluvial and
Experimental and analytical procedures
lacustrine siliciclastic and carbonate sediments was
All the oil samples were submitted to bulk and
deposited. The section is mainly composed of fine to
elemental analyis according to procedures described
coarse clastics and carbonates deposited in freshwater
previously (Mello et al., 1984). Samples were
to saline lacustrine environments (Bertani and Carozzi,
fractionated into saturated, aromatic and polar
1985). In some areas the section overlies, and is
fractions using thin layer chromatography (silica gel G;
intercalated with, volcanic rocks, which are mainly
hexane developer). The aliphatic hydrocarbons were
basalts. After rifting, tectonic activity appears to have
analysed by gas chromatography (g.c.) employing a
been restricted to subsidence and basinward tilting,
Carlo Erba Mega chromatograph, equipped with
with the development of gravity sliding features
on-column injector and a 50m OV-1 column. Hydrogen
(Falkenhein, 1981) and localized reactivations of faults
was employed as carrier gas with a programme of
(Ponte and Asmus, 1978).
50-310C at 5C min -1. Peak areas were used for
The first marine incursions into the coastal basins
comparative quantitation. G.c.-m.s. analyses were
occurred during the Aptian. The combination of
Table 1 Selected oil samples for which analytical data are shown in Table 3
Reservoir

Oil sample

API

Group

Depth (m)

Age

Lithology

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

39
30
30
36
29
32
30
30
19
20
29
30
22
30
42
44

I
I
I
I
II
II
II
II
III
III
III
III
IV
IV
V
V

1696
2780
2340
1841
3166
2857
2815
1524
1953
1475
1998
2764
1107
2889
4289
4288

Aptian
Neocomian
Neocomian

Sandstone
Sandstone
Sandstone
Sandstone
Carbonate
Coquina
Coquina
Sandstone
Sandstone
Sandstone
Sandstone
Sandstone
Carbonate
Sandstone
Carbonate
Carbonate

Marine

Neocomian
AIbian
Neocomian
Neocomian
Palaeocene
Albian
Aptian

Aptian
Aptian
Eocene
Maastrichtian
Eocene
Eocene

and Petroleum

Geology,

1 9 8 8 , Vol 5, A u g u s t

207

Depositional environment characterization: M. R. Mello et al.


Table 2 Bulk and elemental properties of Brazilian offshore oils
Property

Group I

Group II

Group III

Group IV

Group V

h~3C %o ~
% Sulphur 2
V/Ni 3
% Saturates 4
n-Alkanes
dominance
odd/even s
Pristane/phytane 6
Inferred depositional
environment

<-28.0
Low
Low
High

23.0 to - 2 5 . 6
Medium
High/Medium
High

- 2 5 . 4 to --26.6
High
Medium
Low/medium

- 2 6 . 8 to 27.6
High
High
Low/medium

-24.4, -25.1
Medium
High
High

023-025
High
High
Lacustrine/
freshwater

017-021
High
High
Lacustrine/
saline w a t e r

C17-019
Low
Low
Marine
evaporitic

018-020
Low
Low
Marine
carbonate

020-022
Low
Low
Marine
deltaic

4 Low < 50%, m e d i u m ca. 55%, high > 60%


5 Low < 1, high > 1
6 L o w < 1, high > 1

For w h o l e oil
2 Low < 0.1, m e d i u m ca, 0.3, high > 0.5
3 Low < 0.07, m e d i u m ca. 0.2, high /> 0.3

carried out using a Finnigan 4000 spectrometer coupled


to a Carlo Erba 5160 gas chromatograph equipped with
on-column injector, and fitted with a 60m DB-1701
column. Helium was employed as carrier gas and a
programme of 50-310C at 4C rain -] was used. Data
were acquired and processed using an Incos 2300 data
system. Quantitative data on biological marker
concentrations were obtained from selected oil samples
(Table 1) by adding a fixed amount of internal standard
(2,2,4,4-d4, 5o~(H), 14o~(H), 17o~(H)-cholestane) to
each alkane fraction; steranes were quantitated by
comparing peak areas in m/z 217 chromatograms with
the peak area of the standard in m/z 221
chromatograms. Other components were quantitated
by comparison of peak areas with that of the standard
in the Reconstituted Ion Chromatogram (RIC) traces.
To confirm the order of concentrations of specific
biological markers, quantitation was also carried out
using mass chromatograms (e.g. by comparison of m/z
221 for the standard with m/z 191 to obtain relative
concentrations of C ~ 0~f3 hopane). To ensure
comparable results, all the analyses were performed
sequentially, under similar conditions. Peak identities
were established by mass spectral examination, g.c.
retention time and, in a number of cases coinjection of
standards. The presence and absence of C3o regular
steranes was checked by metastable linked scan
techniques using a VG-70E instrument at Norsk Hydro
Research Centre, Norway (of. Moidowan et al., 1985).
Stable isotope analyses for carbon on whole oils and
their fractions were undertaken using a vacuum
combustion line linked to a high resolution Varian
MAT-230 instrument, at Petrobras research centre,
Brazil. The data are presented in delta-notation

relative to Pee Dee Belemnite (PDB).

Results
The results reveal significant differences in the
geochemical characteristics of the oils, best described in
terms of a classification into five groups (I to V). Table
2 lists the range of bulk, elemental and alkane
properties for each group of oils. The n-alkane
distributions
and
pristane/phytane
ratios were
determined from g.c. analysis of the saturate fractions.
Tables 3 and 4 similarly show molecular properties,
based on the distributions and abundances of acyclic
isoprenoids (C25 and C3,), [~-carotane, sterane and
terpane families, determined by g.c.-m.s, analysis. In
the following sections, each group of oils is considered
in turn.

Group I oils
These oils are confined to the Ceara, Potiguar,
Sergipe/Alagoas and Bahia Sul basins (Figure 1). They
are pooled mainly in sandstone reservoirs belonging to
lacustrine freshwater facies with ages ranging from
lower Neocomian to Aptian (Table 1). The bulk and
elemental data reveal a set of common characteristics,
such as low sulphur concentrations (~<0.1%), high wax
contents (saturates > 6 0 % ) , n-alkane distributions with
odd and high molecular weight predominance, pristane
dominant over phytane (values >1.2), low n-Cly/n-C3l
(<3.0) and V/Ni ratios (~<0.06). All the oils have 6 ]3C
(9~) values lighter than - 2 8 . 0 for the whole oil, - 2 8 . 5
for the saturate fraction and - 2 7 . 0 for the aromatic
fraction (Table 2 and Figure 3).

Table 3 Biological marker concentration properties of Brazilian offshore oils

Property*

Group I

Group II

Group III

Group IV

Group V

~i-C2s+ i-C3o
2l~-carotane
3C21Jc022 steranes
4027 steranes
5030 steranes
6030 hopane
7Oleanane
Inferred depositional
environment

N
n.d.
tr.

n.d.
~
n.d.
Lacustrine/
freshwater

~
00

00
n.d.
00000
n.d.
Lacustrine/
saline w a t e r

~
000
00
~
~,'
~
n.d.
Marine
evaporitic

0000
00
~
~

tr.

0000
n.d.
Marine
carbonate

,/
Marine
deltaic

*For details, see Table 5


n.d. - not detected
tr. = trace
~/ = present

208

N
000
~

< 50 p p m

50-200 ppm
200-300 ppm
300-800 ppm
800-2500 ppm

Marine and Petroleum Geology, 1988, Vol 5, August

Depositional

environment

characterization:

114. R. M e l l o

et al.

Table 4 Biological marker ratios* for Brazilian offshore oils


Ratio**

Group I

Group II

Group III

Group IV

Group V

8Diasterane Index
94-Me sterane Index
lHopane/steranes
11Tricyclic Index
12Tetracyclic Index
13Bisnorhopane Index
14Gammacerane Index
1sC34/C3s hopanes

~
4)
O

O
000
09)0
~
00

O0

(10

O910
~

OOe

ca. 0

000

INN}

000

ca. 0
ca. 0

~6Ts/Tm

> 1

< 1

< 1

< 1

> 1

Inferred depositional
environment

Lacustrine/
freshwater

Lacustrine/
saline water

Marine
evaporitic

Marine
carbonate

Marine
deltaic

*For range of values, see Table 5


** For details of measurements, see Table 5

Low
Medium
High

The specific biological markers addressed in this


study are mainly represented by the long chain acyclic
isoprenoids, sterane and terpane families (Tables 3 and
4). Representative g.c. and g.c.-m.s, traces of a typical
example of this consistent oil group are shown in Figure
4. The presence of C25 and C3o acyclic isoprenoids was
confirmed by mass chromatography using m/z 183,239
and 253, since they were present in low abundance.
Thus, the C25 (2,6,10,14,18 and/or 2,6,10,15,19
pentamethyleicosanes) and C3o (squalane) components
were identified in the RIC traces (cf. Figure 4) and
quantified (Table 3).
The
steranes
were
assigned
by
mass
chromatography, using m/z 217, 231 and 259 for
steranes including C21 and C22 components (peaks 1 to
3 and 5), 4-methylsteranes and diasteranes,
respectively. In general, the oils have very low
concentrations of steranes, with 4-methyl steranes (40c,
20 R and S, mainly C3o not shown) present in
concentrations similar to those of steranes (Tables 3, 4
and Figure 4). Diasteranes, and the low molecular

weight steranes are in low or trace abundance. The


sterane distributions, represented mainly by C27, C28
and C29 homologues present as (50c(H), 14o~(H),
170fill) and 5offH), 1413(H), 17~(H), 20 R and S
isomers), show the C27 components always higher than
C29 (Table 3 and Figure 4). Remarkable is the absence
of the C3o components in all the oils of this group
(checked using metastable g.c.-m.s.; Table 3; Moldwan
et al., 1985). The extents of isomerization of the C29
steranes at C-20(S/S+R), and at C-14 and C-17
(ocf313/o~[3~+o~ao0 tend to be low for oils (<48% and
52% respectively, Figure 4).
The terpanes (Tables 3, 4 and Figure 4), observed by
m/z 191, show a series of tricyclics from C2o to C29,
which are present, albeit in low concentrations, in
higher abundance than the C24 tetracyclic terpane. The
abundances of hopanes are high relative to the steranes
with the C3o 170(H), 2113(H) component dominant in
the typical CaTtO C35 range (C28 absent and C31 to C35
with 22 S and R isomers). Minor amounts of Cz9 and
C3o 1713(H), 210(H) hopanes (moretanes), are also

GROUP
V

GROUP
iV

GROUP
III

GROUP
II

GROUP
I
-2'3

'

DELTA

- - 2'5

C13

'

(9oo)

- 2 7~

29

PDB

'

-31

SATURATE

~ AROMATIC
Figure

3 Saturate and aromatic carbon

isotopic data

o f o i l s f r o m Brazilian o f f s h o r e basins

M a r i n e and P e t r o l e u m G e o l o g y , 1988, Vol 5, A u g u s t

209

Depositional environment characterization: M. R. Mello et al.


n23
Saturates : 65%
Pr/Ph : 18
Sulphur: 0.09%

10

m/z 217

V/Ni: 0.05
Carbon
isotope -28%o

16

ti
35

m/z 191

33

28

39
30

19

20 21

22

2324

41

25~ 26~.~L

43
....

44

45
i

Figure 4 Gas c h r o m a t o g r a m of total alkanes, bulk and elemental parameters, and partial m/z 217 and m/z 191 c h r o m a t o g r a m s for
oil (n 1) typical of group I; (for peak assignments see appendix I)

present: the C27 hopanes Ts and Tm(18o~(H)


22,29,30-trisnorneohopane and 17(x(H) 22,29,30trisnorhopane, peaks 28 and 30), are present with
Ts/Tm ratios always >1 Table 4 and Figure 4).
A peculiar feature is the presence, albeit in low
abundance, of gammacerane (peak 40). The use of a
standard and an efficient g.c. column (DB-1701,60 m),
allowed its identification, with complete separation
from the hopanes. Another feature in some of the oils
is the presence, also in very low concentrations, of a
series of C27 3~ 8,14-secohopanes (assigned using m/z
123 chromatograms, see structures).

Group II oils
The oils belonging to group II are confined to the
eastern and southern areas of the margin, in Espirito
Santo and Campos basins, respectively (Figure 1). They
occur in reservoir rocks deposited in non-marine and
marine facies which range from Neocomian to Miocene
in age (Table 1). Their geochemical features (Tables 2,
3. 4 and Figure 5) include medium sulphur contents
(0.25-0.32%), higher V/Ni ratios (0.3-0.5), and 6
13C(~)/N~) values spanning a narrow range of relatively
heavy values of - 2 3 . 0 to - 2 5 . 6 for the whole oil, - 2 3 . 7
to - 2 5 . 8 for the saturate fraction and between - 2 2 . 3
and - 2 4 . 4 for the aromatics (Table 2; Figure 3). The
compositional data show a small reduction in saturates
content (around 60%) relative to the group I oils, as
well as a slight dominance of aromatics over NSO
compounds.
The
n-alkane
carbon
number
210

predominance, around Ct7 to C2~, increases the


n-Cr/n-C31 ratios (around 3.5). For all the oils the
pristante/phytane ratios are high (around 1.5) and are
accompanied by an odd over even preference in the
n-alkanes.
These oils have higher relative abundances and
concentrations of the long chain acyclic C25 and C30
isoprenoids than the oils in group I (Table 3; Figures 4
and 5). That the i-C25 component is mainly
2,6,10,14,18- pentamethyleicosane was confirmed using
m/z 253 chromatograms (as well as m/z 239 and 183).
[3-carotane occurs, although in low concentration, in
most of the samples from this group (Table 3 and Figure
5). Its identity was confirmed by the m/z 125
chromatograms. Steranes are present in slightly higher
concentrations than in the group I oils (Table 3), with
steranes (o~0~c~ and 0~[313, 2(1 R and S) and
4-methylsteranes (4e, mainly C 3 0 ; not shown)
occurring in similar relative abundance, with the
former predominant in most of the samples.
Diasteranes, mainly 1313(H), 17o~(H) 20 S and R
isomers, are also present, in smaller amounts than
steranes but with a similar carbon number distribution
dominated by the C27 components. As for the group I
oils no C3o steranes were detected (Table 3). Low
molecular weight C2j and C22 steranes and
4-methylsteranes (peaks 1-5), with a dominance of the
latter, are present in significant concentrations relative
to the steranes (Table 3, Figure 5). Once again, the
extent of C29 sterane isomerisation at C-20 (S/S+R)

Marine and Petroleum Geology, 1988, Vol 5, A u g u s t

Depositional environment characterization: M. R. Mello et al.


from 35% to 55% with NSO components higher than
and C-14 and C-17 (0~1313/0~1313+0~o0),tends to show low
values for oils (Figure 5).
aromatics. A close examination of the relative
abundances of normal and branched alkanes shows a
The m/z 191 mass chromatograms show that the oils
dominance of low molecular weight n-alkanes (around
contain high relative abundances of tricyclic terpanes
C15-C17), a slight even/odd n-alkane dominance, low
extending from C20 to C35, with the exception of C22,
pristane/phytane ratios (<0.6) and n-C]7/n-C31 ratios
C27 and C32 members (Figure 5). Moderate abundances
<5.0 (Table 2 and Figure 6).
of the C24 tetracyclic terpane (peak 24; Figure 5) were
The distributions and concentrations of long chain
detected in all the oils of this group (Table 4). The
isoprenoids (C20+), steranes and terpanes are similar
hopanes occur in higher concentrations than in the
within the group, but differ significantly from the other
group I oils (Table 3). The Ts/Tm ratio is always < 1
oil groups, for example in terms of the concentrations
(Table 4 and Figure 5). The presence, albeit in low
of their biological markers (Tables 3, 4 and Figure 6). A
amounts, of 170(H),2113(H)-28,30-bisnorhopane (peak
32) and 25,28,30-trisnorhopane
is noteworthy,
high abundance of the C25, and C30 (squalane)
isoprenoids is typical of these oils. The assignment of
especially as they are not present in the group 1 oils.
The identity of the latter compound was confirmed by
the i-C25 component as mainly 2,6,10,14,18mass chromatography using m/z 177 and m/z 370, since
pentamethyleicosane
('regular')
was made by
it gives no response in the m/z 191 chromatogram.
coinjection of a synthesized standard. The 2,6,10,15,19
isomer ('irregular'), which could only be partly
Gammacerane (peak 40; Figure 5) is also present in all
separated from the 'regular' isomer, also appeared to
the samples in relative abundances comparable to those
observed in the group I oils (Table 4 and Figure 5).
be present but in low abundance. Noteworthy is the
presence, in high amounts, of components with
Group III oils
carotenoid skeletons, i.e. mainly 13-carotane with
Oils in this group occur in Bahia sul, Sergipe/Alagoas,
y-carotane in lower abundance (Figure 6; Table 3).
Potiguar and Ceara basins, being pooled in reservoirs
Steranes occur in the highest concentrations of all the
ranging from Aptian to Palaeocene (Table I and Figure
groups (Table 3). The oils contain low concentrations
1). Their geochemical characteristics include high
of diasteranes (mainly C27, peaks 6 and 7), and medium
sulphur contents (0.5-1.5%), medium V/Ni ratios
abundance of 4-methyl steranes (mainly 40 C30; not
(--0.2), and 6 13C(O~x)) values within the narrow range
shown; Table 4). All the samples show a dominance of
of -25.4 to -26.6 for whole oil, -26.4 to -27.3 for
C27 components over their C28 and C29 counterparts.
saturates and - 2 5 . 4 to - 2 6 . 4 for the aromatic fraction
Most of these samples show an unusually high
(Table 2; Figure 3). The amounts of saturates range
abundance - - for oils - - of the 20 R 000components

!1o

m/z 217

Saturates: 60%
Pr/Ph: 1.6
SuLphur: 03%
V/Ni: 0"~

n23

Carbon
isotope: -25%o

3
1
. . . . . . . .

r . . . . . . . . .

T . . . . . . . .

T .

--T

. . . . . . .

T.

13 15 16

'211 J

4
5

35

m/z 191

33

20

30

41

. . . .

,oi'

,3
r

Figure 5 Gas chromatogram of total alkanes, bulk and elemental parameters, and partial m/z 217 and m/z 191 chromatograms
f o r oil (n 61 t y p i c a l o f g r o u p II; (for peak a s s i g n m e n t s see a p p e n d i x I1

Marine and Petroleum Geology, 1988, Vol 5, August

211

Depositional environment characterization: M. R. Mello et al.


10

m/z 217

Saturates: 50%
Pr/Ph : 0-5
Sutphuc: 0.7%
V/Ni: 0.2
Carbon
isotope : -26%0

16
8

13
15

35

4o

m/z 191

33

39

18

19

20 21

22

2324

22 26 L__i

j] i11

A ~

L t

I[~'k

Figure 6 Gas chromatogram of total alkanes, bulk and elemental parameters, and partial m/z 2 17 and m/z 191 chromatograms for
oil (n 10) typical of group III; (for peak assignments see appendix I)

(e.g. peak 10) relative to 20 S (e.g. peak 8) plus low


abundances of the 0~[313 components (e.g. peaks 9;
Figure 6). Also notable is the occurrence, although only
in low concentrations, of C~o steranes which were not
detected in samples of groups I and II (Table 3). In
addition, the oils contain relatively high concentrations
of low molecular weight steranes and 4-methylsteranes,
although in low abundance relative to the C27-C2,)
steranes (cf. Table 3 and Figure 6).
Like the steranes, the terpanes are present in high
concentrations. The distributions of the tricyclic
terpanes differ from groups II and IV, since they are
present in lower relative abundance and contain no
homologues higher
than
C2,). Overall, the
characteristics of the m/z 191 mass fragmentograms for
these oils include: a high concentration of
gammacerane (sometimes the major peak; peak 40),
C3~ ~> C34 hopanes (peaks 45 and 44, respectively), the
presence of significant amounts of 28,30-bisnorhopane
(peak 32) and high abundances of C2,) to C~
17o~(H),2113(H) hopanes relative to their 1713(H),
21cx(H) counterparts (Table 3 and Figure 6). Like group
lI, the Ts/Tm ratios (peaks 28 and 30) are always < 1, in
contrast to group I (Table 4 and Figures 4, 5 and 6). In
addition, high amounts of another C~7 hopane
(25,28,30-trisnorhopane, see structures)are observed
(m/z 177 and m/z 370 mass chromatograms),

Group IVoils
These oils are found only in Cassipor6 and Maranhfio
basins in the extreme northern part of the continental
212

margin (Figure l). They are accumulated in reservoirs


ranging from Maastrichtian to Tertiary age (Table 1).
The bulk geochemical properties of these oils are, in
most respects, similar to those of the group III oils
(Table 2) with high sulphur contents and V/Ni ratios
(0.5-0.76% and 0.3 to 0.5 respectively). Their saturate
fractions range from 46% to 54%, with aromatics
around 20% and NSO components around 30% (Table
2). The 6 13C (0/~)) values of the whole oils range from
-26.8 to -27.6, around -27.5 for the saturate and
-26.7 to -27.1 for the aromatic fraction (Table2; and
Figure3). These oils, like those of group III, show a
predominance of low molecular weight n-alkanes
around Cls-2o, with a slight predominance of even
numbered homoiogues and a dominance of phytane
over pristane (Table 2 and Figure 7). The distribution
of the long chain C25 and C30 (squalane) isoprenoids
and carotanes ([3 and ) is also similar to that of the
group III oils, where high concentrations of both
compound types are found (Table 3; cf. Figures 6 and
7).
Steranes are present in high abundance, second only
to their concentrations in the group III oils (Table 3). A
significant feature of their distributions is the high
relative abundance of low molecular weight
components and the low relative abundance of
diasteranes, mainly represented by C27 homologues
(Table 3," Figure 7). The steranes show a slight
dominance of C 2 v , 50~,14o~(H),170~(H) 20 R
components over their C29 counterparts (Figure 7).
High concentrations of C3o steranes were recognized

Marine and Petroleum Geology, 1988, Vol 5, August

Depositional environment characterization: 114.R. Mello et al.


predominance of n-alkanes around C18_22"with a slight
using metastable reaction monitoring (Moldowan et al.,
even/odd preference. Their pristane/phytane ratios are
1985; Table 3).
close to/or <1 (Table 2 and Figure 8).
The terpane distributions in the m/z 191 mass
Steranes occur in relatively high concentrations,
chromatograms resemble those of the group II oils (cf.
considering
the
maturity
of the oils, but
Figures 5 and 7). In particular, they show a marked
4-methylsteranes (not shown) are present in low
similarity both in concentration and carbon number
abundance (Tables 3 and 4). Low molecular weight
range of C19 to C35 tricyclics (Table 4 and Figures 5 and
steranes and 4-methylsteranes are abundant, relative to
7). Other features common to these two oil groups are
the C27_C29steranes (Figure 8). One significant feature
the presence of gammacerane, 28,30-bisnorhopane and
is the presence of diasteranes in higher relative
25,28,30-trisnorhopane (not shown in m/z 191), with
abundances than in all the other oils (Table 4 and
the last two components tending to occur in higher
Figures 4 - 8). Typically, steranes show a slight
relative abundance in the group IV oils (Table 4).
dominance of C27 over the C29 components (Figure 8).
Other hopanes are also present in high concentrations
C30 steranes are observed in these oils (Table 3).
with 17et(H),210~(H)
components (mainly C30)
dominant and with minor amounts of 17[~(H), 21ct(H)
The terpanes include the tricyclic series C20 to C31
hopanes. As for the group III oils, Ts/Tm is always <1
and C27 to C35 hopanes, mainly 170~(H),21~(H), with a
and in most samples, C35 x[3 hopanes dominate over
maximum at C30, and with 1713(H), 21~(H)
their C34 counterparts (Table 4 and Figures 6 and 7).
counterparts only present in trace amounts. A
significant feature of the m/z 191 chromatograms is the
Group V oils
abundance of biological markers diagnostic of higher
plant
inputs i.e. 180(H)-oleanane (peak X; Figure 8)
These oils are pooled in Tertiary reservoirs, being
and C24 and C26 tetracyclic terpanes (peaks 24 and 27;
confined to the northern part of the continental margin
Figure 8). The Ts/Tm ratios show values >1 (Table 4
(Figure 1 and Table 1). They possess sulphur contents
and Figure 8).
varying from 0.25 to 0.40% and high V/Ni ratios
(around 1). Their saturates are high in abundance
(>60%), compared with the aromatic and NSO
fractions (Table 2).
Discussion
The 8 13C(%0) values are -24.4 and -25.1 for the
The application of biological marker compounds to the
whole oils, -25.1 and -26.2 for the saturates, and
assessment of depositional environment should be
-23.6 and -24.3 for the aromatic fraction (Table 2 and
made with caution. It is important to stress the need to
Figure 3). The saturate fraction of these oils shows a
Saturates : 50%

m/z

10

217

Pr/Ph : 0 7
Sutphur : 0 5 %
V / N i : 0.3
Carbon
isotope : -2?%0

, ..L_

12
-1

9
8n

13 15 16

ji

35

rn/z 191

33

20
21
22

18

.......

~. . . . . . .

23

r~ r-~
f
I
24

.~L,

......

..

L ,~L, a

29
N

31

27

L.

38 1
34

J,

41

43

40

J~ .....

m ....

L_.

,~L..

A..~

i
i
i
,

7 Gas c h r o m a t o g r a m o f t o t a l alkanes, b u l k a n d e l e m e n t a l p a r a m e t e r s , a n d partial m/z 217 a n d m/z 191 c h r o m a t o g r a m s


oil (n 14) t y p i c a l o f g r o u p IV; (for p e a k a s s i g n m e n t s see a p p e n d i x I)

Figure

Marine and Petroleum Geology, 1988, Vol 5, August

for

213

Depositional environment characterization: M . R. Mello et al.


n23

m/z 217

Saturates : 60%
Pr/Ph 0-7
Sulphur : 0.35%

'
. . . .
,i=
I~-

10

15

V/Ni : 1-0
Carbon
isotope - 2 5 ~
3

,k..,,J..
35

m/z 191

33

39
-1

~ 27

2830.

34

i 411 .....

....
l

Figure 8 Gas c h r o m a t o g r a m of total alkanes, bulk and elemental parameters, and partial m/z 217 and m/z 191 c h r o m a t o g r a m s for
oil (n 15) typical of g r o u p V; (for peak assignments see a p p e n d i x I)

understand and disentangle the effects of source,


maturity and biodegradation on bulk, elemental and,
principally, biological marker properties. It is well
recognized that variations in several molecular
parameters occur with an increase in maturity, with the
relative abundances and concentrations of specific
compounds increasing or decreasing. In this study we
only consider molecular properties which although, to
some extent are maturity dependent, are principally
source related. This approach was confirmed by
biological marker data obtained from immature and
mature samples of the source rocks that gave rise to the
oils (Mello et al., 1988). In the following section each
oil group defined above is discussed separately.
G r o u p 1 oils

The high wax content and odd/even n-alkane


predominance plus the bias towards high molecular
weight n-alkanes (>C~3) in the oils of this group
indicate major contributions of long chain lipids from
higher plants and freshwater algae (Lijmbach, 1975;
Didyk et al., 1978; McKirdy et al., 1986) to the
depositional environment of their source rocks. The
high pristane/phytane ratios (Table 2 and Figure 4) for
these oils, probably reflect the relationship between
their precursors and the chemistry of the environment
(cf. ten Haven et al., 1987), e.g. low salinity, rather
than simply the anoxic/oxic condition of sedimentation
(Didyk et al., 1978). It is accepted that pristane
originates from phytol (Didyk et al., 1978) and/or
214

tocopherols (Goossens et al., 1984) of photosynthetic


organisms, whereas phytane may arise in part from
phytol or more likely from archaebacteria lipids in
organisms such as methanogens and halophiles (Kaplan
and Baedecker, 1970; Risatti et al., 1984; ten Haven et
al., 1985). In a freshwater environment, photosynthetic
organisms containing phytol and tocopherols would be
expected to be abundant. With an increase in salinity
(higher Eh), however, the archaebacterial population
might be expected to increase in abundance, Thus, the
more saline the environment, the greater the potential
for an increase in the concentration of phytane
precursors. This may help explain the high
predominance of pristane in freshwater environments
compared with dominance of phytane in hypersaline
environments (see below: ('.t~ ten Haven et al., 1985 and
1987).
The low values of sulphur and V/Ni ratios (Table 2)
in the group I oils, are in agreement with their
freshwater origin, since such properties are primarily a
function of the Eh-pH conditions and sulphide activity
of the depositional environment in sediments (Tissot
and Welte, 1984; Orr, 1986: Lewan, 1984).
The isotopically light values of 6 '3C (always
< - 2 8 % o for the whole oils) also suggest their
freshwater origin, since the principal lipid constituents,
originating from terrestrial plants and freshwater algae,
are depleted in 13C relative to those of marine or saline
plants (Galimov, 1973; Tissot and Welte, 1984).
Moldowan et al. (1985) found carbon isotopes and

Marine and Petroleum Geology, 1988, Vol 5, August

Depositional environment characterization: M. R. Mello et al.


pristane/phytane ratios to be ineffective for
Recently, Moldowan et al. (1985) have stated that
distinguishing non-marine and marine environments on
gammacerane cannot be used to distinguish between
a global basis. Taken together, the carbon isotope
marine and non-marine samples, since it occurs in
values (6 ~3C) and pristane/phytane ratios in the
several different environments. Such evidence suggests
present study do, however, discriminate between these
the possibility of a bacterial origin for gammacerane,
distinct groups (Table 2), and can be considered a
given its widespread occurrence in time and space.
useful geochemical measure for the differentiation of
Hence, our results (Table 4 and Figures 4-8) suggest
non-marine and marine related oils found in the
that the value of gammacerane as an environmental
Brazilian offshore basins.
indicator lies in its relative abundance (and
The biological marker distributions (Tables 3 and 4)
concentration), rather than its mere presence (see
also show characteristic features, based in the
group III below).
occurrence or absence of specific compounds, that
Integration of the data given in Tables 2, 3 and 4 and
suggest a lacustrine freshwater origin for the group I
illustrated in Figure 4 shows a set of bulk, elemental
oils. The comparatively low relative abundances of C25
and molecular data for this group that suggests an
and C30 isoprenoids are consistent with a freshwater
origin from source rocks deposited in a lacustrine
origin, since their biological sources are held to be
freshwater environment. Similar data have been
archaebacteria, which might be expected to be
reported for oils sourced by such sediments in China,
relatively more abundant in marine or more saline
Sudan, Chad and Australia (Wang Tieguan et al., 1988;
waters (Waples et al., 1974; Albaiges, 1980; Brassell
Moldowan et al., 1985; Powell, 1986 and McKirdy et
and Eglinton, 1986). In general, the group I oils have a
al., 1986).
low concentration of steranes, and an absence of C30
Group H oils
steranes held to be diagnostic of marine environments
The higher sulphur contents and V/Ni ratios relative to
(Moldowan et al., 1985). Moldowan et al. (1985) and
the group I oils (Table 2), may reflect the more saline
McKirdy et al. (1986), also reported a paucity of
character (high Eh) of the depositional environment of
steranes in lacustrine freshwater oils from Brazil,
the source rocks of the group II oils. Enhanced salinity
China, Sudan and Australia. This characteristic may be
might also explain why the oils from this group are
due to the organisms living in such a habitat, using
isotopically heavy (613C values around -25%0). Plants
lipids other than sterols as rigidifiers and protectors of
from saline environments can preferentially utilize
cell wall materials. A possible explanation for such a
carbonate complexes as their carbon source for
phenomenon could be that terrestrial and freshwater
photosynthesis. These are richer in a3C than
plants live under higher oxygen conditions than their
atmospheric carbon dioxide, which is enhanced in 12C
saline counterparts and therefore require greater
(Tissot and Welte, 1984).
protection for their cells. The dominance of C27
The predominance of pristane over phytane and the
steranes (Figure 4), contrasts with previous reports
odd/even n-alkane preference is somewhat unexpected,
(Huang and Meinschein, 1979; Mackenzie et al., 1984;
since oils derived from saline lakes generally show
Hoffmann et al., 1984 and Moldowan et al., 1985) of a
opposite characteristics (ten Haven et al., 1988;
predominance of C29 steranes in non-marine
Moldowan et al., 1985 and Fu Jiamo et al., 1986). Such
environments. Such environments may be expected to
differences may reflect the establishment of a lake with
receive major contributions of higher plant material,
moderate salinity rather than hypersaline conditions. A
whose precursor sterols are mainly C29. None of the
more saline environment might increase the abundance
oils of group I show such a feature. Hence,
of phytane precursors (archaebacteria) over pristane
interpretation of a predominance of C29 steranes as an
precursors (Table 2 and Figure 5). Alternatively, the
indication of higher plant input, or as characteristic of a
differences could simply reflect relative input from
non-marine environment must be made with caution.
The apparently diverse, but bacterial, precursors for
higher plants, since the wax content and bimodal
the hopanes and tricyclic terpanes is well documented
n-alkane distribution (maxima at C~6 and Czs; Figure 5)
(Ourisson et al., 1979 and 1982).
of the group II oils clearly indicates the importance of
The main significance of these widespread bacterial
such contributions.
markers lies in their abundance, rather than
The group II oils show higher concentrations and
distribution pattern. The lower concentrations of these
greater relative abundances of the regular C25
compounds in the group I oils relative to the groups II
isoprenoid and i-C30 (squalane) than the oils of group I
and IV indicate a lower bacterial input (Tables 3 and 4),
(Table 3, Figures 4 and 5). This may reflect an increase
perhaps related to salinity differences.
in the salinity of the depositional environment (Brassell
A feature of all the group I samples is the presence of
et al., 1988; see also group III below). A further
gammacerane, but in low concentration (Table 4;
characteristic of the saline nature of group II oils is the
Figure 4). This compound was first identified in the
occurrence, albeit in small concentrations, of
Green River shale (Hills et al., 1966), and was initially
[3-carotane. This compound was first identified in saline
considered a diagnostic marker of lacustrine
sediments of the Green River formation (Murphy et al.,
environments (Seifert and Moldowan, 1981). Many
1967), and more recently, Hall and Douglas (1983),
authors (Rohrback, 1983; Mello et al., 1984; McKirdy
suggested that its presence might be related to a
et al., 1986 and Fu Jiamo et al., 1986), have since
lacustrine saline environment. Moldowan et al. (1985)
reported it in marine carbonate and hypersaline
regarded [3-carotane as a terrestrial marker because it
environments.
The
only biologically-occurring
had not been reported from sources of marine origin.
compound with a gammacerane-type structure is
Its abundance in samples from lacustrine saline and
tetrahymanol, a constituent of protozoa, although their
hypersaline environments (Shi Ji-Yang et al., 1982;
precursor/product relationship has not been verified
Jiang and Fowler, 1986) supported by the evidence
from sediment data (Brassell and Eglinton, 1986).
from this study suggests that salinity is the controlling
Marine and Petroleum Geology, 1988, Vol 5, August

215

Depositional environment characterization: M. R. Mello et al.


been suggested that they originate from a similar
characteristic of [3-carotane concentrations.
natural precursor, perhaps in anaerobic bacteria in
The group II oils, like group I, show low
strongly anoxic conditions (Grantham et al., 1980; Katz
concentrations of steranes and an absence of C30
and Elrod, 1983; Rullk6tter et al., 1982). Recent
steranes (Table 3). These features have been
evidence indicates that they occur as free hydrocarbons
considered characteristic of non-marine oils from
rather than being released from kerogen (Noble et al.,
Australia, Sudan, Chad, China, Brazil and U.S.A.
1984). Their presence in the group II oils may indicate
(McKirdy et al., 1986; Moldowan et al., 1985). A
that salinity at the time of sediment deposition (and
significant feature is the presence of higher
consequent increase in anoxicity) plays a role in
concentrations of low molecular weight C2~ and C22
determining the occurrence of these compounds.
steranes, and 4-methylsteranes (Figure 5; Table 3) than
Similarly, the variable, but significant, concentrations
in the group I oils. These compounds appear to be
of gammacerane are a measure of the enhanced salinity
associated
with
carbonate
and
hypersaline
of the environment of deposition of the source rocks of
environments (ten Haven et al., 1985, 1988; Connan et
the group II oils (ten Haven et al., 1985; Fu Jiamo et al.,
al., 1986; Fu Jiamo et al., 1986). The predominance of
1986).
C27 steranes over Cz9 steranes (Figure 5) in all the
Overall, the bulk, elemental and molecular features
samples again demonstrates that a C29 sterane
of the group II oils (Tables 2-4, Figure 5) are in
predominance is not always diagnostic of non-marine
agreement with, and extend, previous evidence for oils
environments.
The
concentrations
of
the
and source rocks from lacustrine saline environments in
bacterially-derived hopanes in these oils are extremely
China and the Green River Formation (Reed, 1977;
high (Table 3), perhaps reflecting the importance of
Wang Tieguan et al., 1988; Powell, 1986). Hence,
bacterial lipids in saline lakes. In addition, the
deposition of the source rocks that gave rise to the oils
prominence of tricyclic components ranging from
of this group is believed to have occurred in a saline
C2(~.35 (Table 4; Figure 5) may be a result of the specific
lacustrine environment.
saline conditions of such lakes. Similar features occur in
oils derived from a non-marine environment in Angola
Group I I I oils
(Connan et al., 1988). Tricyclic terpanes have been
The high sulphur contents and medium V/Ni ratios of
recognised in oils from various origins (e.g. Aquino
these oils (Table 2), together with medium amount of
Neto et al., 1982 and 1983) and it has become evident
saturates, the dominance of low molecular weight
that they arise from bacterial precursors, perhaps
n-alkanes with a slight even/odd preference and the
specific membrane lipids (Ourisson et al., 1982). The
predominance of phytane over pristane (Figure 6) are
low Ts/Trn ratios, typically <1 (Table 4 and Figure 5,
all consistent with a hypersaline environment of
cf. Seifert et al., 1980) may reflect a specific source
deposition (e.g. Fu Jiamo et al., 1986; ten Haven et al.,
input or mineral matrix in the depositional
1985 and 1988; Connan et al., 1986; Albaiges et al.,
environments of the source rocks of group II oils.
1986). The origin of an even n-alkane dominance has
The triterpanes 170(H),2113(H) 28,30-bisnorhopane
been suggested to result from reduction of precursor
(Table 4; Figure 5) and 25,28,30-trisonorhopane (not
lipid (fatty acids and alcohols), under anoxic conditions
present in m/z 191) have been recognized in many oils
(Grimalt et al., 1985; Connan et al., 1986), being always
(Grantham et al., 1980; Volkman et al., 1983). It has
Table 5 Measurement procedures for data in Tables 3 and 4*
1 Sum of i-C25 and i-C3o peak areas in RIC trace and normalized to added sterane standard
2
3

Peak area (B) in RIC trace and normalized to added sterane standard
Sum of peak areas (1 + 2 + 3 + 5 ) in m/z 217 chromatogram and normalized to added sterane standard (m/z 221 chromatogram)

Sum of peak areas of 20R and 20S 5(~, 14(x, 17(~(H)-cholestane (8+10) in m/z 217 chromatogram and normalized to added sterane
standard (m/z 221 chromatogram)

5
6

Monitored using linked scan techniques (cf. Moldowan et aL, 1985)


Peak area of 35 measured in RIC and normalized to added sterane standard

7
8

Presence or absence of X monitored using m/z 191


Sum of peak areas of C27 20R and 20S 1313, 17cdH)-diasteranes (6+7) in m/z 217 chromatogram over sum of peak areas of C27 20R
and 20S 5(~,14(~,17(~(H)-cholestane (8+10)x100. Low < 30, Medium 30-100, High > 100
Sum of peak areas of all C3o 4-methyl steranes in m/z 231 chromatogram (recognized using mass spectra and m/z 414
chromatogram) over sum of peak areas of C27 2OR, 20S 5(~,14~,17~(H)-cholestane (8+ 10)x100. Low < 60, Medium 60-80, High > 80

10 Peak area of C3o 17(~,2113(H)-hopane (35) in m/z 191 chromatogram over sum of peak areas of C2720R and 20S 5(~,14~,17~(H) cholestane (8+10) in m/z 217 chromatogram. Low < 4, Medium 4-7, High > 7
11 Sum of peak areas of C19 to C29 (excluding Cz2, C27) tricyclic terpanes (18-23, 25, 26) in m/z 191 chromatogram over peak area of C3o
17e, 21~(H)-hopane (35) x 100. Low < 50, Medium 50-100, High > 100
12 Peak area of C24 tetracyclic terpane (24) in m/z 191 chromatogram over peak area of C3o 17(~, 2113(H)-hopane (35) x 100. Low < 5,
Medium 5-10, High > 10
13 Peak area of C2e 28,30-bisnorhopane (32) in m/z 191 chromatogram over peak area of 17~,2113(H)-hopane (35) x 100. Low < 10,
Medium 10-50, High > 50
14 Peak area of gammacerane (40) in m/z 191 chromatogram over peak area of 17,2113(H)-hopane (35) x 100. Low < 50, Medium
50-60, High > 60
15 Peak areas of C34 22R and 22S 17,2113(H)-hopanes (44) in m/z 191 chromatogram over peak areas of C3s counterparts (45). Low
< 1, High > 1
16 Peak areas of 18~(H)-22,29,30-trisnorhopane (Ts) over 17(x(H)-22,29,30-trisnorhopane (Tm) in m/z 191 chromatograms
*See Figures 4 - 8 and Appendices.

216

Marine and Petroleum Geology, 1988, Vol 5, August

Depositional environment characterization: 114.R. Mello et al.


increase bacterial contributions to the sediments. Thus,
linked with a low pristane/phytane ratio. This ratio is
the bacterially derived hopanes are present in high
directly related to the salinity of the environment of
concentrations (cf. group II). The difference in the
deposition. Low ratios (<1), appear to be associated
distribution pattern of tricyclic terpanes compared to
with hypersaline conditions (cf. ten Haven et al., 1988;
those in group II oils (cf. Figures 5 and 6) could,
Mello et al., 1988).
perhaps, reflect a response of the bacteria producing
The abundant presence of long chain isoprenoids,
the tricyclics precursor to hypersalinity. Connan et al.,
mainly the regular i-C25 and i-C30 (squalane)
(1986), also report low abundances of tricyclics in rock
components is also a consistent feature of the
samples from Guatemalan hypersaline environments.
hypersaline origin of the group III oils (Table 3 and
The high relative abundance of gammacerane
Figure 6). Waples et al. (1974) first suggested that the
(sometimes the major triterpane) in all the group III
regular i-C25 isoprenoid is a biological marker for saline
oils (Figure 2 and Table 3), demonstrates that this
environments. Its high abundance, with squalane, is
compound may be a good indicator of the salinity of a
also found in oils related to hypersaline environments
depositional environment. Indeed, the more saline the
in South Florida and China (Palacas et al., (1984), Fu
environment, the higher appears to be the abundance
Jiamo et al., (1986). The present study (Table 3) further
of gammacerane. Extremely high gammacerane
suggests that the abundances of the C25 (regular) and
abundances have been reported for oils from
C30 isoprenoids increase with an increase in salinity and
hypersaline environments; for example, Jianghan
maximlse in oils derived from an evaporitic
basin, China (Fu Jiamo et al., 1986), Green River,
environment (Table 3). The presence of high
USA and Prinos, Italy (Moldowan et al., 1985). Like
abundances of ~-carotane (Table 3 and Figure 6) is also
the group II oils, the oils of group III typically show
significant. Such abundances appear to be associated
Ts/Tm ratios <1 (Table 4 and Figure 6), suggesting
with highly anoxic saline environments (Hall and
again a source input/or mineral matrix dependence for
Douglas, 1983). Indeed, 13-carotane has been reported
this ratio. Another important feature of these oils is the
sometimes as a major component in several oil samples
derived from saline and hypersaline environments,
presence of high abundances of 170(H),2113(H)28,30-bisnorhopane
and
25,28,30-trisnorhopane,
such as Green River formation (Moldowan et al.,
presumably originating from anaerobic bacteria in
1985), Shengli oilfield (Shi Ji-Yang et al., 1982), and
highly anoxic depositional environments (cf. group II
Kalamayi oilfield (Jiang and Fowler, 1986).
oils; Rullkrtter and Wendisch, 1982; Katz and Elrod,
The C27_29steranes and C28_304-methyl steranes are
1983). A further unusual feature is the occurrence of
present in the highest concentrations for all of the oils
(Table 3 and Figure 6). Such high relative abundances
C35 013hopanes significant abundance relative to the
C34homologue~ (Table 4 and Figure 6), a characteristic
of these compounds are commonly observed in oils of
of many samples from marine carbonate and
hypersaline origin (Rullkrtter et al., 1984; ten Haven et
al., 1985; Fu Jiamo et al., 1986; Connan et al., 1986). A
hypersaline environments (ten Haven et al., 1985 and
1988; Brassell et al., 1988; Fu Jiamo et al., 1986;
striking feature of the C27-29 sterane distributions is the
relative abundances, in most of the samples in this
Albaiges et al., 1986).
The oils belonging to group III are characterized by a
group, of 20 S and 20 R 5~(H),1413(H),1713(H ) and 20 S
particular set of bulk, elemental and molecular features
50(H),140c(H),170~(H)
steranes,
which
are
(Tables 2-4; Figure 6) that are diagnostic of oils derived
anomalously low for crude oils (cf. Mackenzie et al.,
from source rocks deposited in a hypersaline (marine
1980; Table 3 and Figure 6). Clearly, these ratios are
evaporitic) environment. The biota in such an
not solely maturity
dependent,
and
source
environment are expected to be largely restricted to a
input/mineral matrix effects may play an important role
few species of salinity-tolerant aquatic organisms.
in the distribution pattern of these components. Hence,
These organisms can bloom due to lack of competition
care must be exercised in the use of sterane
for the available nutrients. Clearly, the effect of these
isomerization ratios as maturity parameters in samples
phenomena on the biological marker distributions
from some specific environments.
would be expected to be dramatic, leading to the
All the oils contain a low abundance of the C3o
dominance of specific compounds (Table 3; cf. Brassell
steranes considered to be a definitive indicator of a
et al., 1988); for example, those derived from
contribution to the source from marine-derived organic
precursors biosynthesised by microorganisms such as
matter (Moldowan et al., 1985). The precise origin of
archaebacteria (including halophiles), certain green
such compounds is not established, but it is thought
algae, cyanobacteria and sulphur-bacteria (Boon et al.,
that they arise from C30 sterol constituents of marine
1983; Goossens et al., 1984; Connan et al., 1986). The
algae (Djerassi, 1981). The presence of abundant C21
biological markers concentrations shown in Table 3
and C22 steranes and 4-methylsteranes (not seen in
supports these ideas, and must be considered a key
Figure 6 because of their low relative abundance;
feature in the assessment of hypersaline environments.
(Table 3), is in keeping with a hypersaline environment
(cf. group II oils). The low relative abundance of
Group I V oils
diasteranes (the lowest of all the groups) in the group
In many respects the group IV oils show features which
III oils (Table 3 and Figure 6) can be explained in terms
are similar to those of group III. In general, they
of a low availability of acidic clay minerals in
possess similar compositional and elemental data
hypersaline environments to catalyse the sterene
including high values for sulphur and V/Ni ratios, low
rearrangement process (Rubinstein et al., 1975).
to medium content of saturates, a dominance of
Similar features have been observed in sediments and
phytane over pristane and a slight even/odd
oils from both evaporitic and carbonate environments
predominance in the n-alkanes (Table 2), features
(McKirdy et al., 1984; Fu Jiamo et al., 1986).
The features of the terpanes in this group are quite
typically associated with oils derived from marine
hypersaline and carbonate environments, for example,
distinctive, since hypersaline conditions appear to
Marine and Petroleum Geology, 1988, Vol 5, August

217

Depositional environment characterization: M. R. Meflo et al.


oils generated from the La Luna and Querencual
marine carbonate influence on the depositional
formations (Venezuela), Sunniland oils (South
environment of their source rocks (el. group IV).
Florida), Aquitaine basin oils (France), and oils from
Further features which point to such an influence are
the Magdalena Valley (Colombia) (Palacas et al., 1984:
the dominance of C~5 over the Cs4 hopanes, and the
Moldowan et al., 1985; Cassani, 1986; Talkudar et al.,
presence of high relative abundances of low molecular
1986; Connan et al., 1983). The 6 ~-~Cvalues for the
weight steranes (~f. group IV, Figures 7 and 8).
The heavy 6 ISC values for the whole oil and the
whole oils, and their saturate and aromatic fractions
other fractions (Table 2," Figure 3), are typical of highly
(Figure 3) are typical of oils of marine carbonate origin,
mature oils derived from marine environments (Tissot
being significantly heavier than the values of the group
IlI oils (Figure 3," Sofer, 1984: Tissot and Welte, 1984:
and Welte, 1984; Fuex, 1988).
Diasteranes are present m the highest relative
Palacas et al., 19841.
abundances of all the oil groups ( Table 4 and Figure 8),
The distributions of the C2s and Cso isoprenoid
components, and [~-carotane in these oils (Table 3 and
perhaps reflecting high maturity or the high amounts of
Figure 7), are consistent with the enhanced salinities in
clay minerals in their source rocks, consistent with high
terrigenous input (q/~ above). The presence of (;,~o
the environment during carbonate deposition. The
steranes indicates a marine depositional environment
presence of [3-carotane is further evidence of its value
(Table 3," Moldowan el al., 1985).
as a diagnostic indicator of salinity in both marine (this
The main feature which distinguishes the group V
work) and lacustrine (Hall and Douglas, 1984)
oils lies in their terpane distributions, which include
environments, rather than a terrestrial marker (of.
biological markers diagnostic of higher plant inputs,
Moldowan et al., 1985).
notably high abundances of 1804H)-oleanane (peak X;
The sterane concentrations are high, only lower than
Figure 8): this compound was first identified (Hills and
those of the group II1 oils, suggesting that salinity ma>
Whitehead, 19661 in an oil from the Niger delta.
also influence the biological marker distributions in
Further work by several authors has suggested an origin
marine
carbonate
sediments.
Similarly,
high
from precursors in higher plants of the angiosperm
concentrations of low molecular weight steranes are
family (Ekweozor el al., 1979a and 1979b). More
present (Table 3 and Figure 7), as in other carbonate
recently, it has been reported to occur in an increasing
oils (ten Haven et al., 1985: Talukdar et al., 19861. As
number of oil samples, but always appears to be linked
for the group III oils, diasteranes are present in low
to terrestrial inputs in predominantly Tertiary basins,
abundance, a feature commonly observed for oils
mainly of deltaic nature (Taranaki delta, New Zealand:
derived from carbonate sediments in Australia,
Beaut'oft-Mackenzie delta. Canada: Po Basin, Italy:
Venezuela, Tunisia and France (McKirdy et al., 1984:
Niger delta, Nigeria; Grantham et al., 1983; Philp and
Cassani, 1986; Connan el al., 19831. As for the other
Gilbert, 1986: Riva et al., 1986: Brooks, 1986). The
marine oils, C~o steranes are present, and in higher
occurrence of high abundances of the Ce4-tetracyclic
relative abundance than in the oils of group Ili (Table
terpanc relative to the tricyclic terpanes (Figure 8)
3). Perhaps this increase reflects the establishment of
appears to be an indicator of a significant input of
wholly marine conditions.
higher plant material (Trendel el al., 19821. This
In contrast to the steranes, the relative abundances
compound has also been reported in high relative
and distributions of the tricyclic terpanes differ from
abundance in coals and oils derived predominantly
the group Ill oils and show a similar pattern to those of
from terrigenous source material, an observation that
the group II oils (Table 4 and Figures 5 and 7),
suggests its use as a marker of higher plant input (Philp
suggesting indirectly that their precursors are
and Gilbert, 1986; Abdullah et al., 1988). Hence, the
suppressed by hypersalinity (q'~ group lll). Examples
presence of high abundances of 1804H)-oleanane and
of well-documented carbonate oils with comparable
the Ce4 tetracyclic terpane in the group V oils, with an
features occur in Venezuela (Cassani, 1986; Talukdar et
abundance of high molecular weight n-alkanes
al., 1986), South Florida (Palacas et al.. 1984), and
indicates their deltaic origin. In addition, these oils
Colombia (Zumberge, 19841. The presence of
possess other geochemical characteristics (Tables 2-4;
28,30-bisnorhopane,
25,28,30-trisnorhopanc
and
Figure 8) consistent with an origin from source rocks
gammacerane in significant arnounts, like the group II
deposited during the development of a marine deltaic
oils (Table 3 and Figures 5 and 7) presumably reflects
system over a carbonate platform. Well-documented
the similar salinity and chemical characteristics of the
examples of oils derived from deltaic environments
two environments (Table 4).
include those from the Tertiary Niger delta (Hills and
The assignment of a marine carbonate environment
Whitehead, 1966; Ekweozor et al., 1979a), the
for the group IV oils is based on the similarities
Mahakam delta in Indonesia (Schoell et al., 1983:
between their specific chemical features and those of
Grantham et al., 1983; Hoffmann et al., 1984), and the
well defined carbonate oils (see above). In summary,
Beaufort-Mackenzie delta in Canada (Brooks, 1986).
these marine carbonate oils share some characteristics
with evaporitic oils, and others with lacustrine saline
oils.
Conclusions
G r o u p V oils
This investigation confirms the value of a combined
geological, geochemical and biological marker
The predominance of medium to high molecular weight
approach, using oil samples, in the assessment and
n-alkanes suggest that the group V oils are derived, in
differentiation of depositional environments of
part, from a terrestrial input of higher plants (Figure 8).
petroleum source rocks. The results (Tables 2-4,"
On the other hand, the high sulphur contents and V/Ni
Figures 4-8) reveal signifcant differences within the
ratios of these oils, together with pristane/phytane
oils from Brazilian offshore basins enabling their
ratios close to/or < 1, linked with slight even over odd
classification into five distinct groups. These groups
n-alkane preference (Table 2 and Figure 8), suggest a
218

Marine and Petroleum Geology, 1988, Vol 5, August

D e p o s i t i o n a l e n v i r o n m e n t c h a r a c t e r i z a t i o n : M. R. M e l l o et al.

correlate with source rocks laid down in five different


depositional regimes; namely, I-lacustrine fresh water;
II-lacustrine saline water; III-marine evaporitic;
IV-marine carbonate, and V-marine deltaic.
A quantitative approach using the concentrations of
biological marker compounds has been shown to be
valid and useful. For example, the paucity of steranes
and absence of C3o steranes in the oils from non-marine
environments (groups I and II), versus their markedly
higher concentration in the marine-related ones
(groups III and IV; see discussion for group V) is
important (cf. Rullk6tter et al., 1984; Moldowan et al.,
1985). Also, the abundance of the bacterially-derived
hopanoids appears to be salinity dependent and reaches
a maximum in the oils derived from group II (lacustrine
saline) and group III (marine evaporitic). The data in
Tables 2 - 4 show clearly that no single geochemical
property is sufficient to suitably characterize and assess
a specific environment of deposition for the source
rocks that gave rise to the oils. However, consideration
of the various properties in a multiparameter approach,
does provide diagnostic criteria for differentiation and
assessment of specific depositional environments.
depositional environments.
As observed in Tables 2 and 3, the association of a
high wax content, a dominance of high molecular
weight n-alkanes, low sulphur and V/Ni values, light 6
13C values, high pristane/phytane ratios, an absence of
C30 steranes and a paucity of the other steranes
discriminates the lacustrine freshwater environment
(group I). The oils from a lacustrine saline water
environment (group II) show a similar set of
characteristics diagnostic of non-marine oils, but differ
in respect of elemental, isotopic and molecular features
arising from enhanced salinity, for example, higher
values of sulphur and V/Ni ratios, heavier 6 13C values,
and the presence of the C25 regular isoprenoid,
[3-carotane, low molecular weight steranes (C21-22),
28,30-bisnorhopane and abundant tricyclic terpanes up
to C35.
The distinction between the non-marine oils (groups
I and II) and those related to a dominant input of
marine organic matter (groups III, IV), is based on a
variety of parameters (Tables 2-4). The most useful are
the high wax content and the abundance of high
molecular weight n-alkanes in the non-marine oils and
the presence of C30 steranes, and the abundance of
steranes,
28-30
bisnorhopane
and
25,28,30trisnorhopane in the marine oils. Distinction between
the marine evaporitic (group III) and marine carbonate
(group IV) oils is made using compounds such as
gammacerane, 13-carotane, low molecular weight
steranes and tricyclic terpanes. In the evaporitic oils
gammacerane and [3-carotane occur in very high
abundance. In the carbonate oils, there is a high
relative abundance of tricyclic terpanes up to C35 and of
C21 and C22 steranes. Several features shared by these
two environments distinguish them from all the others,
namely a dominance of phytane over pristane linked
with an even over odd n-alkane preference, high
sulphur contents, high sterane concentrations, low
relative abundance of diasteranes, a tendency for a
dominance of C35 hopanes over their C34 homologues,
and high amounts of long chain regular C25 and C30
(squalane) isoprenoids. The marine deltaic oils (group
V) can be differentiated from all the other groups of
oils using diagnostic markers for specific higher plant

contributions, namely 18c~(H)-oleanane and high


relative abundance of the C24 tetracyclic terpane. They
also show some of the features of the carbonate-derived
oils, such as low pristane/phytane ratios, even/odd
n-alkane dominance, high V/Ni ratios, dominance of
C35 hopanes over their C34 counterparts, and high
relative abundances of low molecular weight steranes.
These features demonstrate the value of biological
markers
in the
assessment
of depositional
environments using oils. From the results of this work
we propose, as an extension of previous studies
(Waples et al., 1974; Hall and Douglas, 1983; Brassell
and Eglinton, 1986), that pristane/phytane ratios,
even/odd n-alkane preference and abundances of
specific
acyclic
isoprenoids
(2,6,10,14,18pentamethyleicosane and squalane), [3-carotane and
gammacerane may be considered useful salinity
indicators related to the water column in the
depositional environment of source rocks.

Acknowledgements
The authors would like to thank the Geochemistry
section of Petrobr~is research centre for all the
elemental and bulk analyses, Birger Dahl and Mr L. W.
Mohriak for helpful comments, and Mrs A. P. Gowar
and Miss L. Dyas for advice during analytical work.
The authors are also grateful to Nils Telnaes for the
metastable g.c.-m.s, results and NERC for g.c.-m.s.
facilities (GR3/2951 and GR3/3758) and to Petrobrds
for permission to publish.

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Appendix I

Compound assignment
Pr- 2,6,10,14-tetramethylpentadecane (pristane)
Ph- 2,6,10,14-tetramethylhexadecane (phytane)
iC25 2,6,10,14,18-pentamethyleicosane (regular),
and/or 2,6,10,15,19-pentamethyleicosane
(irregular)
iC3o squalane
[3--Carotane
1- 1313(H),17ot(H)-diapregnane (C20
2- 5offH),14[3(H),17oc(H)-pregnane (C21) +
(13~(H),17~(H)-diapregnane (C20?)
3- 5o(H),1415(H),1713(H)- +
5o(H),14o~(H),17ot(H)-pregnane (C21)
4- 4o~-methyl-5ot(H),14[3(H),17[3(H)- +
4o~-methyl-5ot(H),14o~(H),17offH)-pregnane (C22)
5- 5o~(H),1413(H),1713(H) - +
5offH),14oc(H),17offH)-homopregnane (C22) +

131~(H),170~(H)-bishomodiapregnane (C23)
67891011121314151618-

1313(H),17oc(H)-diacholestane, 20S diasterane


1313(H),17oc(H)-diacholestane, 20R diasterane
5ec(H),14o~(H),17oc(H),20S cholestane
5offH),1413(H),1713(H),20R + 20S cholestanes
5o~(H),14ot(H),17oc(H),20Rcholestane
5oc(H),14oc(H),17o~(H),20S24-methylcholestane
5o~(H),1413(H),1713(H),20R + 20S
24-methylcholestanes
5~(H),14oc(H),17oc(H),20R24-methylcholestane
5o~(H),14oc(H),17o~(H),20S24-ethylcholestane
5ec(H),1415(H),1713(H),20R + 20S
24-ethylcholestanes
5offH),14oc(H),17offH),20R24-ethylcholestane
C2o tricyclic terpane

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Depositional environment characterization: 114.R. Me/Io et al.

192021222324252627282%
303132-

C2~ tricyclic terpane


C23 tricyclic terpane
C24tricyclicterpane
C25tricyclicterpane
C26tricyclic terpanes
C24 tetracyclic terpane
C2stricyclicterpanes
C29 tricyclic terpanes
C26tetracyclic terpane
C2v 18o~(H)-trisnorneohopane(Ts)
C~otricyclicterpanes
C27 17o~(H)-trisnorhopane(Tm)
C3~ tricyclicterpanes
17o~(H),18o~(H),21 [3(H)-28,30-bisnorhopane
(C2~)

222

Marine and Petroleum Geology, 1988, Vol 5, August

333435363738394041424344-

C29 17o~(H),21[3(H)-norhopane
C29 1713(H),21o~(H)-norhopane
C3o 17o~(H),2113(H)-hopane
C33tricyclicterpanes
C3~ 17[3(H),21o~(H)-hopane
(734tricyclicterpanes
C.~l 17o~(H),21f3(H)-homohopane(22S + 22R)
C3o gammacerane
Ca2 17o~(H),2113(H)-bishomohopane(22S + 22R)
C35 tricyclic terpanes
C33 17o~(H),21[3(H)-trishomohopane (22S + 22R)
C34 17c~(H),2113(H)-tetrakishomohopane (22S +
22R)
45- C3~ 17o~(H),21[3(H)-pentakishomohopane (22S +
22R)

Depositional environment characterization: M. R. Mello et al.

APPENDIX 2

C23 n- ALKANE

PRISTANE
i-C25

(REGULAR)

PHYTANE
l

i-C25

(IRREGULAR)

i-C3o
SQUALANE

- CAROTANE

PREGNANES AND
METHYLPREGNANES DIASTERANES ococo~STERANES
HOMOPREGNANES
R
R

R:H,Me,Et

R=H,Me
TRICYCLIC
TERPANES

4-METHYL
STERANES

TETRACYCLIC
TERPANES
R1

R: H,CH3,C2Hs, i-C 3H7 _


i

25, 28, :30


TRISNORHOPANE

R:H, Me,Et

18 ec (H)
17ec (H)
TRISNORNEOHOPANE
TRISNORHOPANE

R2

R1 : H, R2:CH3
RI=R2 = CH3

28, :30
BISNORHOPANE

o~ 19 HOPANES

R: H,CH3~.C6H13

HOP-13 (18)-ENE

oC p ~ STERANES

GAMMACERANE

18O~(H) OLEANANE

I~o~ HOPANES

R = H ,CH3....C6H13

8,14 - SECOHOPANES

R= H,CzH5, i-C3H7

Marine and Petroleum Geology, 1988, Vol 5, August

223