Escolar Documentos
Profissional Documentos
Cultura Documentos
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
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
0264-8172/88/030205-19 $03.00
1988 Butterworth & Co. (Publishers) Ltd
Marine and Petroleum Geology, 1988, Vol 5, August
205
q8o
Cassipore
Foz Do Amazonas
~
""
0 o --
Par~/'M aranhao
~
Ceara
Potiguar
BRAZIL
Sergipe/Alagoas
.i
Bahia Su{
Espirito Santo
Campos
Santos
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
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
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
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
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).
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
208
N
000
~
< 50 p p m
50-200 ppm
200-300 ppm
300-800 ppm
800-2500 ppm
Depositional
environment
characterization:
114. R. M e l l o
et al.
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
Low
Medium
High
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
isotopic data
o f o i l s f r o m Brazilian o f f s h o r e basins
209
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)
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
!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
211
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)
Group IVoils
These oils are found only in Cassipor6 and Maranhfio
basins in the extreme northern part of the continental
212
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
,
Figure
for
213
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)
215
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
7
8
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
217
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.
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.
References
Abdullah, W. H., Gjelberg, J., Jones, J. M., Murchison, D. G. and
Telnaes, N. (1988) Early carboniferous coal depositional
environment in Spitsbergen, In: Advances in Organic
Geochemistry (Eds. L. Mattavelli and L. Novelli) Pergamon
Press, Oxford, (in press)
Albaiges, J. (1980) Identification and geochemical significance
of long chain acyclic isoprenoid hydrocarbons in crude oils,
In: Advances in Organic Geochemistry (Eds. A. G. Douglas
and J. R. Maxwell) Pergamon Press, Oxford, p. 19-28
Albaiges, J., Algaba, J., Clavell, E. and Grimalt, J. (1986)
Petroleum geochemistry of the Tarragona Basin (Spanish
Mediterranean off-shore), In: Advances in Organic
Geochemistry (Eds. D. Leythaeuser and J. Rullk6tter)
Pergamon Journals, Oxford, p. 441-450
Aquino Neto, F. R., Restle, A. and Connan, F. (1982) Novel
tricyclic terpanes (C19, C2o) in sediments and petroleums
Tett. Letts. 2027
Aquino Neto, F. R., Trendel, J. M., Restle, A., Connan, J. and
Albrecht, P. A. (1983) Occurrence and formation of tricyclic
and tetracyclic terpanes in sediments and petroleums, In:
Advances in Organic Geochemistry (Eds. M. Bjoroy et aL)
Wiley, Chichester, p. 659-667
Asmus, H. E. (1975) Controle estrutural da deposi(;&o mesoz6ica
nas bacias da Margem Continental Brasileira Rev. Bras.
Geoc. 5, 160-175
Bertani, R. T. and Carozzi, A. V. (1985) Lagoa Feia Formation
(Lower Cretaceous) Campos Basin offshore Brazil: Rift valley
stage carbonate reservoirs I & I1. J. Petrol. Geol. 8, 37-58,
199-220
Boon, J. J., Hines, H., Burlingame, A. L., Klok, J., Rijpstra, W. I.
C., de Leeuw, J. W., Edmunds, K. E. and Eglinton, G. (1983)
Organic geochemical studies of Solar Lake laminated
cyanobacterial mats, In: Advances in Organic Geochemistry
(Eds. M. Bjoroy et al.) Wiley, Chichester, p. 207-227
Brassell, S. C. and Eglinton, G. (1986) Molecular geochemical
indicators in sediments, In: Organic Marine Geochemistry
(Ed. M. Sohn) American Chemical Society, Washington, D.C.,
p. 10-32
Geology,
1988, V o l 5, A u g u s t
219
220
Geology,
1988, V o l 5, A u g u s t
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-
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, V o l 5, A u g u s t
221
192021222324252627282%
303132-
222
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)
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, 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
223