Paleoreconstruction by biological markers*

WOLFGANG K. SEIFEKTand J. MICHAEL MOLDOWAN

Chevron 011 Field Research Company. P.O. Box 1637. Richmond. CA 93x02. L1.S.A.

Abstract--During diagenesis and conversion of the original lipid fraction of biological systems to pet-
roleum hydrocarbons. the following four basic events needed for paleoreconstruction may be monitored
by biological markers: (1) sourcing. (2) maturation. (3) migration and (4) biodegradation.
Actual cases of applying biological markers to petroleum exploration problems m different parts of
the world are demonstrated, Cretaceous- and Phosphoria-sourced oils in the Wyoming Thrust Belt can
be distinguished from one another by high quality source fingerprinting of bromarker terpanes using gas
chromatography mass spectrometry. Identification of recently discovered biological markers. head-to-
head isoprenoids. allows source differentiation between some oils from Sumatra.
The degree of crude oil maturation in basins from California. Alaska. Russia. Wyoming and Louisrana
can be assessed by specific biomarker ratios (70S/ZOR sterane epimers).
Field evidence from such interpretation is augmented by laboratory pyrolysis of the rock.
Extensive migration is documented by biomarkers in several oils.
Biological marker results are consistent with the geological setting and add a dimension in asststmg
the petroleum explorationist toward paleoreconstrustion.

INTRODUCTION geochemistry to petroleum exploration using GCMS

has been reported recently (SEIFERT. 1980).
THE DIAGENESISof petroleum is presently understood
In Prudhoe Bay, Alaska, biological marker tech-
as a complex process of conversion of the original niques produced strong evidence for the cosource
lipid fraction of biological systems to hydrocarbons
concept (SEIFERTer trl., 1980): i.e. several sources from
and to a lesser extent to polar compounds of varying
different stratigraphic locations were thought to con-
degree of thermodynamic stability during sedimenta- tribute to most of the commercial deposits.
tion and maturation. Expulsion of mobile liquid reac-
The four key parameters which benefit from bio-
tion products from the sediment at elevated tempera-
logical marker data input are: (I) source. (31 matur-
ture and pressure (due to increased depths of burial)
ation, (3) migration. and (4) biodegradation. In fact, in
and subsequent migration from the source rock into
many instances. of all combined organic geochemical
porous reservoir rocks is thought to lead to the ac-
analyses, such as carbon isotopes. microscopic exam-
cumulation of reservoired petroleum. Consequently.
ination, H/C ratios, organic carbon contents. etc.. the
compounds of similar structures are found in bitumen
interpretation of biological marker data is often the
extracted from sediments and in petroleum; and,
crucial factor governing the final conclusions made
therefore, discussions of chemical composition of
(SEIFERTrt &.. 1980).
bitumen in sediments and petroleum from a natural
It is the intent of this presentation to exemplify the
products point of view belong together. Of the com-
first three parameters described above using biolopi-
pounds structurally elucidated by petroleum organic
cal markers with cases of Chevron’s current research.
chemists, those resembling the structures occurring in
chosen from different parts of the world. For a treat-
the living organisms are the most intriguing. They
ment of case (4) biodegradation. the reader is referred
have been called petroleum biological markers and
to SEIFERT and MOLIN~AN. 1979. and references
include such classes as porphyrins (BAKER and
therein.
PALMI:R. 1978), carboxyhc acids (SEIFERT. 1975) iso-
prenoids (PATIENCEef trl.. 1978). terpanes (VAN DORS-
RESULTS AND DISWSSION
SELAER t’r (II., 1977). steranes (SEIFERT and MOL.-
DOWAY, 1978, 1979). and certain aromatics (SC‘HAEFLE Sow-cc
et trl., 1978). GCMS m/r 191 fragmentograms of terpanes (%I-
A spectrum of precursor;product relationships
FERT. 1977). coined ‘m/e 191 terpanograms’t, have
highlighting applications of biological marker organic become powerful source fingerprints. particularly
* Presented at the Ninth Annual Convention of the
when used jointly from the bitumen as well as the
Indonesian Petroleum Association (IPA), Jakarta. Indone- kerogen pyrolyzates (SEIFERT. 1978).
sia. May 27-29, 1980.
t The )n:e 191 fragmentograms have been called ‘Hopa-
nograms’ (OURISSON et (11.. 1979). but we prefer the more
general term *m;e 191 terpanograms‘ to include the diter-
panes. tricyclic terpanes. and special structures like gam- Based on mass spectral, gas chromatographic. and
mnccrane and oleanane. carbon isotope data. it was recently suggested (ROSEN-
784 W. K. SEIFERT and .I. M. MOLDOWAN

FELD et al., 1979) that the Pineview oil from the Nug- some subtle differences, including the triplet starting
get Jurassic formation was sourced from Cretaceous with the elution of C2, 17aH-hopane (T,), from the
rather than Phosphoria. Our biological marker tech- other three oils and their source rock. Nevertheless.
niques were applied to this basin. Figures 1 and 2 this oil appears to belong with the Cretaceous group
depict the geographic and stratigraphic locations of (compare Figs 3 and 4).
the samples investigated, including the American In contrast to the terpane fingerprints characteristic
Quasar, Nugget, Jurassic oil (Sample No. 160). The for Cretaceous sources (Fig. 3), we are showing those
top of Fig. 3 shows the m/e 191 terpanagram of a typical for Phosphoria sources in Fig. 4. An outcrop
Mowry Cretaceous source shale in comparison with from a Permian formation in S.W. Montana (No. 282,
the following three oils which we consider to be di- top of Fig. 4) correlates well with the Tensleep
rectly derived from it: (1) the Mowry oil from the Pennsylvanian oil (Type II) from Hamilton Dome
Shell Haight Well in the Powder River Basin (No. (No. 81-3). Other Phosphoria-sourced oils tire the
183), (2) the Dakota oil at Bridger Lake Field at the Thaynes, Triassic, reservoired oil (No. X3-1) from
Southern end of the Moxa Arch (No. 179, see also Bridger Station on the Hogsback Plate (compare
Fig. I), (3) the Bear River oil in the Spring Valley Fig. 2), also the Tensleep Pennsylvanian oil from
Field on the Hogsback Plate (No. 161). The near Beaver Creek (No. 175) and the condensate rn the
identity of the subtle details of the terpane finger- Nugget at Dry Piney (No. 177) Field. In the latter
prints of the source rock and the three oils permits three Type II oils, increases in relative concentrations
the assumption of a genuine source rock/oil corre- for multiplets I-VI, including the tricyclics JSEIFEKI
lation. The fourth oil at Nugget Jurassic from Pine- and MOLDOWAN, 1978; and SEIFERTet d.. 19HO).may
view Field (160) shown at the bottom of Fig. 3. shows signal a migrational effect on those oils.

SAMPLE LOCATIONS

. OILS
* ROCKS

I 7
0

MILES

Fig. I. Overthrust Belt. Utah- Wyoming.

 Paleoreconstruction by biological markers 785

SAMPLE LOCATIONS
IMMATURE 0 OILS

Perm.-
Triassic Jurassic LowerCretaceous UpperCretaceous
Penn.

282 233-l 171 228(111227,231fIV)233fVl

230(Vlla
81-3 160 179 (Ill)
175 269
270 161 l&?(l)
183
Fig. 2. Diagramatic cross section, Thrust Belt. Wyoming. ,‘Roman numerals in parenthesis refer to
designations used in previous paper (SEIFERT and MOLDOWAN. 1980).

Basic differences between Cretaceous- and Phos- Damar (307) the mode at paraffin n-Cl,. which is
phoria-sourced samples can easily be recognized in generally thought to be the insignia of a terrestrial
the Cretaceous doublet II containing trisnorhopane II input to the source, derived from higher plant waxes
(T,) (SEIFERTand MOLDOWAN. 1978), which has turned (ALBRECHT and OURISSON. 1971). However, certain
into a triplet in Phosphoria-sourced oils and in the species of algae contain distributions of aliphatic hy-
multiplet III (Cretaceous) containing trisnorhopane drocarbons with odd carbon predominance often
(T,), which has turned into a doublet in the Phos- centered at C2, (GELPI et al., 1970). This last point is
phoria-type samples. Furthermore, the Phosphoria particularly relevant in view of the specific evidence
oils contain relatively higher concentrations of tricyc- for algal input in several samples (see below),
lit terpanes (quadruplet I) and additional terpanes in Differentiation of Damar (307) from the other oils
the region above CJ3 (VI), which are absent in the is confirmed by the m/e 191 terpanograms in Fig. 7.
Cretaceous-sourced oils. Thus, these results augment The most striking differences are relatively large
and extend to the molecular level the source conclu- homohopane (CJ1) concentrations and a different dis-
sions reached by previous investigators (ROSENFELPet tribution of the black shaded peaks (thought to be
al., 1979). tricyclic terpanes), including the complete absence of
the first four tricyclic terpanes in 307.
The organic geochemical data provided in Table 1
E.uamplr 3; Sumatra
aid in distinguishing the oils according to differences
The crude oils investigated from Sumatra are in their organic source input. These differences allow
shown in their relative geographical positions in groupings of oils according to (source) Types ILIV.
Fig. 5. In order to establish the various source group- Distinguishing parameters for Damar in Table 1 are
ings among these oils, a number of biomarker and pristaneiphytane and group-type paraffin content,
bulk parameters were useful, particularly high mol- allowing its classification by itself as a type I oil. The
ecular weight isoprenoids in addition to terpanes. carbon isotope ratio fails to distinguish this Type I
Some interesting differences are evident from capil- example from the Type III oils. which, however, are
lary gas chromatography of the saturates shown in clearly different by the other parameters.
Fig. 6. The chromatogram of Damar Oil 307 is un- The similarity of the m/e I91 terpanograms in
usual in its appearance with a large pristane peak and Fig. 7 for Duri (303) and Minas (305) leads to a simi-
relatively high concentrations of high molecular lar source hypothesis for these two oils, which are
weight paraffins centered at n-C2,. Chromatograms of designated Type IV. This conclusion is possible in
all other oils examined (except Duri) are quite similar spite of moderate biodegradation in Oil 303. indicated
to Petapahan (306) in Fig. 6. These oils share with by n-paraffin depletion (Fig. 6) and decreased saturate
786 W. K. SEIFERT and J. M. MOLIIOWAN

TERPANES
MOWRV. CRET c,, HOP .- -
9000 ! C,,HOP Phasphorra.Perm
SHELL 44-14 HAIGHT 0utcraD
Shale
S. W. Montana
2X?

MOWRV, CRET
9000' I mr
SHELL 44-14 HAIGHT I

c DAKOTA, CRET 1 OIL

E
BRIOGER LAKE, 15.500
1
PHILLIPS BRIDGEA LAKE UNIT

5
m
cc 011 ihdp!s, Ill.%
3.410-3.455 Ft
RriaqerStation

BEAR RIVER. CRET OIL

SPRING VALLEY, 1000
BIG PINEV M-l I

Ii OIL
NUGGET. JUR.
PINEVIEW. 10.000'
AM OIJASAR 1

Condensate
GE Time Oirsctlon

Fig. 3. Rocky Mountain Overthrust Belt. C_;o~)d CINC-

lation of Mowry Cretaw~us source \halc \\ith Type I ,>11\.

and paraffin-by-group-type contents and saturates

di- + triaromatics ratio (Table 1I_
Within 10 miles of the Duri 1303) deposit. we find
the Pematang Field (302) crude (Fig. 5). The m!c 191
terpanogram (Fig. 7) of the saturates of the Pematang
Crude (302) is different from 303 and 305. having ;I
relatively higher proportion of the tricyclic-type ter- ~1.. 1968). The presence of this structure stgnals a
panes (black shaded peaks), allowing the possibility of specific link between botryococcane-containing crude
a migration explanation to account for the differences oils and the alga Botryococcus hruunii. unless other
(see above, Examplr 1. Type II oils]. organisms containing possible botryococcane precur-
The hypothesis of a source distinction between Oil sors are discovered. The botryococcanc index, besides
302 and the Type IV oils is in the carbon isotope data having botryococcane in the numerator, has CA7 I‘.L,,
and the botryococcane index in Table 1 (MOLDOWAN head-to-head isoprenoids in the denominator. These
and SEIFERT. 1979a). The latter is high for Type IV common head-to-head isoprenoids were recently dis-
and zero for Type II oils. Botryococcane is an un- covered (MOLDOWAN and SEIFERT, 1979b) to OCCUI
usual Cl4 isoprenoid hydrocarbon shown in Fig. 6, widely in crude oils. The origin of this series ol’ isopre-
which has been identified by mass spectral compari- noids in bacterial cell wall hpids has been discussed
son and gas chromatographic coinjection (details (MICHAELISand ALBRECHT.1979: CHAPPE ~‘f(11..1979 :
reported, MOLLXJWANand SEIFERT, 1980) with auth- MOLDOWAN and SEIFERT. tY7Ya,b: nr, ROSA (‘f (I!
entic botryococcane (Cox et tri.. 1973: MAXWELL L’r 1Y77a.b).
 Paleoreconstruction by biological markers 7x7

’ @DAMAR value of + 5.7. intermediate between Type IV (+4.X

307
average) and Type II ( + 7.7 average).
The Pematang oil (302) is joined in Table 1 by the
0 oils from SE. Balam (351) and Hitam (352). which are
loosely grouped as Type II oils by carbon isotope
S.E. BALAM ~~
351 value and geographical location. The oils are subclas-
sified, respectively, as IIa. IIb and Ilc. however. based
on their biological marker characteristics. A striking
difference is seen in the tri, Y I X3 fragmentograms for
isoprenoids in Fig. X for the 351 oil. Members of the
group of shaded peaks found only in that oil typically
SOUTH BEKASAP --%’ o
304 002 have mass spectra which feature three major ion
HITAM 0 o doublets above m/e 224 in a pattern resembling the
352 B0 fragmentation around the quaternary carbon atoms
MINAS
305 in botryococcane (m,e 23X and 239. 294 and 295. 448
Di, and 449; MOLDOWAN and SEIFERT. 1980). although
PETAPAHAN botryococcane itself is absent, For example the
0 306
starred peak has prominent ion doublets at WLJ 738
KASl&NaQ SUR$< x and 239. 280 and 281. 434 and 435. and the doubly
349 350 starred peak has m/e 266 and 267, 308 and 309. and
I I I I I I
434 and 435. A specific algal origin is again sus-
0 10 20 30 SAMPLE LOCATIONS
pected for these isoprenoids. which may have also
MILES INDICATED BY NUMBERS
been derived from botryococcene. Other parameters
Fig. 5. Sumatra. Relative sample location. m Table I distinguishing the SE. Balam oil (351) from
the other Group II oils are its yield and group-type
values and. in particular. its CPI value, which is high-
The diverse bio-origins of botryococcane and the est among all the oils listed. In Fig. 8. the WY 191
head-to-head isoprenoids make the botryococcane terpanogram for 351 is also significantly difl’crent
index another possible source parameter. The last oil from 301 in relative concentrations of tricyclic ter-
in Table 1, So. Bekasap (304) lies in the vicinity of panes,
302 and 303 (Fig. 5) and has a botryococcane index of
intermediate size (Table 1). pointing the way to a
possible mixed source for the So. Bekasap (304) oil.
Supporting this hypothesis. we find a carbon isotope and relative distributions of the other minor peaks,

0 n-PARAFFINS,
EXAMPLES LABELED
n ISOPRENOIDS
DAMAR 1
4500 FT
307

nC27

PETAPAHAN 4
5100 FT
306

\ COINJECTED
BIODEGRADATION 1 BOTRYOCOCCANE iC34

DURI 147
500 FT
303
)

TIME DIRECTION

Fig. 6. Evidence for tenestrial origin and biodegradation. Capillary gas chromatography
788 W. K. SEIFERT and J. M. MOLD~WAN

TERPANES - GCMS

TRICYCLICS

17a(H)-HOPANES
TRISNORHOPANE II
c32

TYPE C 34 DAMAR 1
4500 FT
307
6”7 I

I
;;; PEMATANG 1
4900 FT
al IIb
302
-z

I :
TRICYCLIC

DURI 147
500 FT
303

MNAS 7E-86
2500 FT
305
c
GC TIME DIRECTION

Fig. 7 Sumatra. Differentlatlon of sources of crude oils.

Table I, Sumatra, correlation parameters

Isoprenoids / c 1.j *
Ylelds
GCMS Depth, Bot. Prlstane Sat., Sat. Group Type I 1 p
Type No. Identity Ft Indexb Phytane % m Par. 1 Terp. ! cPI S.3 i>,oo ’
I 307
IIa 302
IIb 351
IIC
III
III 349
III 350
IV Minas 7E-86
1va ;005
II + IV 304

’ Biodegraded.
b
botryococcane
x 100. Based on integration of peaks on the m;r 183 mass fragmentogram for the saturate
CJ7-C40 head-head
fraction urea nonadduct.
’ Di f triaromatics.
Paleoreconstruction by biological markers 789
790 W. K. %I+XT and .I. M. MOLIHWAY

including gammacerane. which elute between the The sterol or stanol-to-steranc conversion 11~s heen
17a(EI)-hopanes, Gammacerane was identified by its studied (GAWSIAN and SMITH. 1979: NISHIMUR~
mass spectrum and by GC’MS coinjection with auth- 1977; DASTILLUN~;and AI.RRHCH-I. 1977: Ci,zsw~~
entic gam~~rane. and E~;LKTON.1975). During diagcnesis. as ;i hlnction
The source differentiation of Hitam (3521 from the of time. temperature, and catalysis. the petrostcranc 11
Pematang oil (302) by biological markers is somewhat is isomerized to its epimer 14~. I?a 20s lli. :GI the
more subtle. In Fig. 8, there are differences in internal one hand, and to the Ring C. D ~~i.~-stcrrcli~or~~t~~.sIt
ratios between tricyclic components labeled 11 and III (148. 178 20R + ZOS),on the other hand. The km&s
(black shaded peaks) and an extra C’,,-terpane of un- of these interconvcrsions arc being studied tc;.&~l:r-
known structure eluting just after ~7~(~~norhopane tions to be published elsewhere). lsonler~~~~ti~~~;II
(Cz9) is present in 332 in unusually high abundance. C-14 to C/D cis was first recognized ah a function of
The ~1,E 183 fragmentogram for the isoprenoids ot maturation by &TRW rr rd.(1976). Evidcncc iitr the
352 in Fig. 8 shows a slighti) greater amount of production of the more extensive list of sterane SW
CJJ---CJg head-to-head isoprenoids relative to 302. eoisomers in petroleum as reported in a cholrstanc
and in Table I the pristane’phytanr’ ratio is signiii- isomerizate (SEIFERTand MOLLXWAN. 19791.~nclu&
cantly different for 357. ing 58, 14/?, 17/J and 5~. 14/f, 17%. has been &tained
Finally. the Type III oils form a rather close geu- by examination of the reportedly 700 million :;~saro!d
graphical group (Fig. 5) comprised of’ Kasikan (344,~ Siva crude oil (Seifert, 1980).
Suram (350) and Petapahan 1306). The consistent During isolation work of individual stcrane\ IYCC
similarities of all parameters in Table 1 for the Type Experimental. page 113, in SEIHXI..kNUMoI.~x~+.~~.
III oils, including carbon isotope data. d&e them as 1979), it was learned that. on alumina. C’.D 4.~ corn--
a common source trio. pound IV (Fig. 9) elutes c~~nsider~~blyfaster than C’ Ii)
ft’tms compound II. The same relationshilt bctwcen
the two compounds II and IV was rccoguiled 10
MATURATION AND MIGRATION
exist in the geosphere in numerous examples. (UXJoi
In a recent paper (SHFERT and MOLDOWA~‘. 1979). a which was reported recently (see ‘Table 4. column h. HI
summary of the occurrence of petroleum stcranes was SlilFERTor al.. 1980). In contrast. the geostcr,rnc 111.
given jointly with the structure proof by the authors Fig. Y, (20s C.‘D fruns) appears 1~) migrate real
of the geosteranes 142. 17% 200s and 14/L 178 slightly faster in the geosphere than its ‘OR cpm~~ If.
20R + 205. The 20R/20S assignments of the 148. 17[{ WC have solved for the two unknowns. maluratioti
pair are to be inverted (MOLUOWAN(JI CI/., 1980: and migration, by plotting the SLY XS (III):% llOR (111
MACKENZIEef ul.. 1980). Figure Y shows precursor, ratio on the ordinate and the 5~. 1411,17/1XR {IV),Sn
product relationships. The present day biological sys- 20R (II) ratio on the abscissa (Fig. 10). The thc~~rctical
tem almost entirely contains the 14%. 17~ 20R con- curve (Fig. 10) was arrived at empirically uimg data
~~uration (NES P? &.. 19771 as depicted in the prrcur- points from bona fide source rocks and li~tle-r~l~grat~d
sor sterol I and its derived petrosterane II (Fig. Yt. oils. as judged from other migration paramcttsrh (cnm”

H
Ii

P
\ H
HO
& Sterol Living Organism

LJ-d LL. i?ulaw

Configuration
Geological
/

iieat
f
Catalysis
il H

H
14a, 17alXlR1 ’ \
Biolcqical Configuration
Ii IV
&
144.
174L?0RI
Configuration
Geological
Fig. I). Kinetic tirst order rekttionship of geosterancs.
 Paieoreconstruction by biological markers 791

- m @ Prudhoe Bay
_ m 0 Ship Shoal
m @ Ove~hrust Belt
- l Miscellaneous

0 Shale Bitumens

5a (20R) (I I)
0.5

- First Order Kinetic conversion

(Maturation)
- -- Geochromatography (Migration)

140, 17fi (20R) (Iv)

5a (20RI ii-ii
Fig. 10. Comparative maturation/migration study of crudes and bitumens using C,, ster;~nes

pare Table 10 in SEIFERT.and MOLDOWAN. 1978, and (I) The biomarker maturation index (BMAl) is the
Table 4 in SEIFER’Fr~ it/., 1980). Potential source rocks linear distance from the origin along the theoretical
which have not yet generated petroleum may also lie curve (solid line, Fig. 10).
on the curve if they are on the correct kinetic path (2) The biomarkcr migration index (BMII) is the
toward petroleum generation. Migrated oils are dis- distance of displacement from this curve along the
placed to the right of the curve. dashed lines, a few examples of which arc shown. The
First order kinetics are temperature dependent and slope of the latter provides the correction arising from
therefore demand variations in the position of the the slight difference in migrational aptitude between
kinetic curve with oil generation temperature differ- compounds 5~ 20s (III) and 5r 20R (II).
ences. Severe variations in the curve are not expected
due to the rather narrow temperature range in the For example. bona fide source rock bitumens
window for peak oil generation (-50-115 C. TISSOT Green River shale. Eocene. 10.400’. Utah (I). and
and WELTE, 1978). The grey area to the right of the Canal shale. Devonian. 16X’, Canada (25) lie on the
kinetic curve (Fig. 10) is an attempt to take into curve. These rocks gave an excellent correlation with
account the temperature window for oil generation, Green River oil (1) (SEIFERT, 1977) and Kee Scarp
but the extent of this grey area is not well defined at limestone oil (23). respectively (Table ?I using all
this writing. other geological and geochemical considerations. A
The significance of utilizing these biomarker ratios line connecting 0 to 1 and 75 to 23 indicates the
lies in the fact that they are source-independent. migrational changes occurring in the stcrane rnrios
because each lipid deposition, regardless of type of (Fig. 10) of these crudes. A slight increase in 5~. 14~.
organic input, starts out with sterane configuration II. 1% (20s) and relatively large increase in 5a. 1411. 17(1
This is in contrast to any other migration- and matur- @OR) compared with 5x, 14~. 17~ (20R) are observed
ation-sensitive biomarker concentrations and ratios in the oils.
reported previously (SEIFERT and MOLWWAN. 1978: Some examples from the Prudhor Bay Field which
SEIE.ER.T ~pf& 1980). all of which are source-sensitive have been described in detail (!%IH:KT 1x1J.. 1980).
and. thus. can only be utilized for a given set of demonstrate the use of the stcranc‘ kinetic pi01
samples in a meaningful way, once a common source (Fig. IO) in source rock evaluation. Kinpak shalt
for all samples to be compared has been established. samples 713 and 110 lying near the curve were shown
We, therefore, are in a position to introduce source- to correlate with Kingsk oil (219). While neither 717
independent maturation and migration parameters to nor 210 would constitute a per/& match for oil 119
organic geochemical correlation studies, defined as via Fig. 10, the average of the two shales looks exccl-
follows: lent. Upper Cretaceous shale 226 was shown to he a
792 W. K. SEIFEKTand J. M. MOLIX~WAN

Table 2. Survey of maturation and migration of crude oils by source independent sterane parameteri
._ -__-_--___,-. _ __...
_--.__.i
,SCMS 1
NO. Fiel<l ,_ Location Pormat.itir~ Age Depth, Ft 3lAI” Maturi!.) j BillI1~’ ;
L0UiSi3El ?I ,‘lliC&Fl .;%I’1 hli 0 . l,‘,lOC . _,i:‘: u
YcKittrick California Carner’or Ci 1 n-r,. 5,655 t.8, I . .-
F’cKittrick California Carne?or !‘i! vlio. h,9RCr I .: ! I. !
.----- -_-.. , -.__-_+__ .___. /- _.__. I/
J.l,
‘8.I.,
Rear River
,:’
Green Hivrr
(1” -7
d,*‘,
Jur. 3.4 ;
i,’

-_-...-_...- ...-... _;-._.___. /

.r. /
Ii.

’ Representative for 8 011s from Ship Shoal. Fig. 10. BMAI range 1.7 2.4. BMII range 0.2 ~i.h.

misfit for correlation with the Prudhoe Bay oils. Its Nugget Jurassic. Thrust Belt. appear cvzn morr
position to the left of the curve indicates that it is on migrated relatively speaking. Returning to the North
an improper sterane kinetic pathway for oil gener- Slope, the Sag River oil (No. 218) had been described
ation. Post-neocomian shale No. 212 was shown to be as a most migrated oil in that particular investigation
immature for oil generation (SEIFERTcf 111..lY80) and based on a number of source-dependent molecular
occupies a position of immaturity on the kinetic curve and bulk migration parameters (compare Table 4 in
(Fig. 10) below any oils found to date. In contrast. SEIFERT et al.. 1980). This is now confirmed by its
deep Post-neocomian shales 2OY and 233 are within biomarker migration index. being the highest of all
the oil generation zone in agreement with the puh- Prudhoe Bay oils on a relative scale. In contrast. the
lished data (SEIFERTet al.. 1980). Kingak oil from the same basin, which ii sole14
Potential source rocks Bear River (228) and Aspen sourced from Kingak shale, shows characteristics d
(227) from the Wyoming Overthrust Belt (see below) little migration (SEIFERT tl’f ul.. 1980). which is also
have been demonstrated to show a lack of thermal confirmed by its low biomarker migration index.
stress for petroleum generation based on incomplete In spite of the encouraging results. on iI relative
hopane epimerization (SEIFEKT and MOLDOWAX. scale. it is not possible to translate the BMII data into
1980). Likewise, their position in F‘ig. 10 to the left of absolute migration distances because, at present. the
the curve is inconsistent with the empirically observed effect of the inorganic matrix is unknown. i.c. when-
sterane petroleum generation kinetics. ever clay was reported in the oil migration Pathway
Table 2 shows a worldwide selection of oils possess- large effects on the BMII parameters were observed.
ing a wide range of maturation indices. The Cambrian With clean sand in the carrier bed the effects observed
oil from Russia and the deep oils from the North were much smaller or zero. Migration through an
Slope and the Overthrust Belt display the highest open fault would leave the absorption/dcsorption
maturation indices, i.e. the largest extent of epimeriza- phenomenon inoperative making an oil appear *i/z
tion of 20R to 20s regular steranes as a result of situ’ by the BMII even though it may h&e moved any
thermal stress. In contrast, in Ihe immature Ship distance.
Shoal Basin, all samples appear near the bottom of Likewise, the rate of epimerlzation of Sa ZUR to 5~
the curve (Fig. lo), likewise the young California oils 20s may be affected differently by clay than b\, carbo-
(Table 2). nate, prohibiting an ubiquitous extrapolation of all
From the position of the above discussed Pineview BMAI’s for the present. However, in one instance. iI
oil from the Thrust Belt iSample No. 160) on the plot maturity sequence of suspected source rocks recently
in Fig. 10, it is agreed with previous investigators reported on the basis of homohopane epimer ratios in
(ROSENFELDet al.. 1979) that we are dealing with an the Overthrust Belt (SEIFERT and M~LDOWA?., 1980)
extensively migrated oil (BMII = 2.5): likewise, Ryck- was confirmed by 5~ 20S/20R sterane ratios (Table 3.
man Creek (No. 269) and Painter Reservoir (No. 2701, compare also Figs 1 and 2 for sample iocati,),,,)
 Paleoreconstruction by biological markers 793

Table 3. Side chain epimerization in steranes and hopanes as maturity indicators.

Sequence of cretaceous” shales

GCMSb
No. Formation Depth, Ft Eitumell Pyrolysate
I ML
182 M0wry go00 1.11 1.1 1.3 A N
228 Bear River 160 0.53 1.4 1.1 T C
120 0.42 1.1 0.9 ‘J H
100 0.19 0.97 0.5 / ? I!
.50 0.09 0.31 n.3. I / a
-50 0.10 0.24 n.a. 1 I >,
i Y i E

* Overthrust Belt, Wyoming.

b Identical to Samples I-VI, see SEIFERTand MOLDOWAN(1980).

Laboratory simulation to document the response of shale pyrolysate points trace out their own kinetic
the above described biomarker ratios to maturation curve which is very different from the petroleum gen-
succeeded by pyrolyzing Green River shale at 26O~C eration curve. This could be anticipated due to the
for various lengths of time. Figure 11 (black peaks) special artificial history of these samples. But it also
depicts the higher contents of 5a 20s (III) and 5%. 148, points the way to anomalies due to very special cir-
178 (ZOR) geosteranes relative to biosterane 5a 20R cumstances in nature.
(II) in the longest term pyrolyzate as compared to ihe For practical purposes. we always measure the
short term experiments. Other changes in compo- components 5r ZOR, 5c( 20s. and 5% 14p, 178 2OR at
sition of the steranes evident by comparison of the CL9 in the m/e 217 mass fragmentograms because they
two m/e 217 fragmentograms in Fig. 11 reflect the are not masked by coelution of other steranes, which
relative increase in geosteranes of all sterochemistries is largely the case with the steranes of lower carbon
compared to steranes of biological configuration. The numbers (see Fip. I in SEIFERT and M~LWWAX.
appropriate ratios plotted in Fig. 10 for Green River 1979).

5a
20s

0 0.29 0.05
- .-A 10 0.29 0.05
28 0.33 0.05
171 0.44 0.07
-* 242 0.59 0.14
5a
348 0.59 0.10
20s
(III) 348 0.62 0.12

5a
20R
(Ii)

GC TIME DIRECTION

Fig. 11. Pyrolysis of Green River shaie at 260 ‘C. Effect of steranes used in maturation parameters.
7Y4 W. K. SEIFER~ and .I. M. MOLWWAS

,1c,krlo~it,dy~mr,lr,s~ ~The authors thank Dr R. W. JONES for MOLDOWAN J. M. and SmfmT W. k. (19801 I-IP-~d~‘rcov~i.j
sample selection and geological counseling in the Over- of botryococcane in petroleum .I (‘lzt,m .%<a~ ( ‘XL,lli
thrust Belt. Dr L. W. <LFVI.; for the same Tn Sumatra. Dr Commun. 912-914.
S. R. SILLERMANfor the ovrolvsis samnles and Dr E. J. MOLWWAX J. M.. SIZIFERTW. K.. Iihi.t\ ‘VI. .[ ru~it I).~I-K-
GALLEC;OSfor assistance iiih dCMS in’strumentation. An
authentic sample of botryococcene was obtained courtesy
of Drs J. TAYLOR and J. R. MAXWELI.. Technical assistance
was by Messrs P. NWOT?~Y. R. G. PRINCE,R. W. HALL and
Ms. M. M. PENA. Appreciation for permission to publish to NFS W. R., VARU~ .T. E. and KKI \I II 1\;. j 1’1 ;?I i iw as.
the management of Chevron Oil Field Research Cornpan). eochemistry of sterols at C-70 and 11s hiosynthctti mlplr-
La Habra. California. cations. J. .dm. C’hem SOL..99, 260 26I.
NISHIMURA M. (1977) The geochemical sigmtic,mcL, in car1.1
sedimentation of geolipids obtained by ~apo~uii~~.iirr~1.>1
lacuslrine sediments. C;e0chim ( ~~.~nttr~+im !:!ii 4%.
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