Documente Academic
Documente Profesional
Documente Cultură
Organic Geochemistry
journal homepage: www.elsevier.com/locate/orggeochem
Petrobras Research & Development Center, Cidade Universitria, Rio de Janeiro, RJ 21941-598, Brazil
Stanford University, School of Earth Sciences, Department of Geological & Environmental Sciences, Stanford, CA 94305-2115, USA
c
Department of Cellular and Molecular Biochemistry, University of Kentucky, Lexington, KY 40536, USA
d
Warsaw University of Technology, Faculty of Chemistry, ul. Noakowskiego 3, 00-664 Warszawa, Poland
b
a r t i c l e
i n f o
Article history:
Received 26 June 2010
Received in revised form 30 January 2011
Accepted 18 February 2011
Available online 23 February 2011
a b s t r a c t
Certain biomarkers in petroleum provide information on of the geologic age of its source rock and these
can also be used to track the evolution, radiation and relationships between taxa and as proxies for paleoenvironmental reconstruction. Triaromatic 23,24-dimethylcholesteroids (TA-DMC), which undoubtedly
derive from 23,24-dimethylcholesterols in dinoagellates, haptophytes and diatoms, provide a useful
parameter to distinguish Paleozoic from Mesozoic and younger oil and rock extracts at higher specicity
than previously proposed biomarkers. In this report, we present a study of the relative abundance of a
novel series of TA-DMC in source rock extracts and crude oil from different global localities and ages.
Based on their taxon specicity for important primary producers, such biogeochemicals also have implications for paleoenvironmental studies, including paleoclimate and global change, such as radiations following the PermianTriassic boundary mass extinction.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
A growing number of studies have shown the utility of steroids
as indicators of geologic age (Moldowan et al., 1985, 1996, 2001;
Summons et al., 1992; McCaffrey et al., 1994; Holba et al., 1998),
which is particularly useful to constrain the age for petroleum that
has not been rigorously correlated to a source rock.
Steranes correlated to specic organisms (termed taxon specic, Moldowan and Jacobson, 2000) are often found in crude oil
where their presence sometimes allows a geological age to be inferred (Moldowan, 2000). For example, Holba et al. (1998) reported
that 24-norcholestanes (1, see Fig. 1 and Table 1 for numbered
structures) are more prominent in some oil samples derived from
Jurassic, Cretaceous and Tertiary source rocks than oil from
older ones, which is consistent with a possible origination from
diatoms. 24-n-Propylcholesterols are present in members of an
order (Sarcinochrysidales) of chrysophyte algae and the related
hydrocarbons (2) are specic indicators of marine input from
Precambrian to present (Moldowan et al., 1985, 1990). 24-isoPropylcholesterols are present in Demospongiae (McCaffrey et al.,
1994; Love et al., 2009) and the derived taxon specic 24-isopropylcholestanes (3) are particularly abundant in some Ediacaran
to Ordovician oil and extracts (Peters et al., 2005). Dinosteranes
(4, 4a,23,24-trimethylcholestanes) and the structurally related
410
8,
9,
10,
11,
X=H
X = CH3
X = C2H5
X = n-C3H7
order to investigate the distribution of triaromatic 4,23,24-trimethylcholesteroids (5, TA-dinosteroids) through geologic time.
2.1. Samples
2.2. Analytical procedures
Two sets of samples were selected for this study in order to test
the correlation of TA-DMC to dinoagellate, haptophyte and diatom evolution and investigate the application of TA-DMC as an
age related biomarker; one set of 102 organic matter rich marine
source rocks from Proterozoic to Cretaceous core, sidewall core
and outcrop samples (Table 3) and another set of 186 oil samples
generated from marine and non-marine Proterozoic to Tertiary
source rocks (Table 4). A similar set of organic rich marine source
rocks was previously studied by Moldowan et al. (1996, 2001) in
Name
Carbon
number
Triaromatic 23,24dimethylcholesteroid
Triaromatic 23,24dimethylcholesteroid
Triaromatic 23,24dimethylcholesteroid
Triaromatic 23,24dimethylcholesteroid
Triaromatic 23,24dimethylcholesteroid
Triaromatic 23,24dimethylcholesteroid
Triaromatic cholesteroid 20S
Triaromatic cholesteroid 20R
Triaromatic 24-methylcholesteroid
20S
Triaromatic 24-ethylcholesteroid 20S
Triaromatic 24-methylcholesteroid
20R
Triaromatic 24-ethylcholesteroid 20S
Triaromatic 24-n-propylcholesteroid
20Sc
Triaromatic 24-n-propylcholesteroid
20Sc
Triaromatic 24-n-propylcholesteroid
20R
28
28
28
28
28
28
26
26
27
8
8
9
28
27
10
9
28
29
10
11
29
11
29
11
b
c
d
e
f
g
h
i
j
k
l
m
n
o
Structureb
411
mode (ions m/z 231, 245 and 253). GC was carried out on a capillary column (60 m 0.25 mm i.d.) coated with DB-1 (100% methyl
silicone, 0.25 lm lm thickness). GC condition: initial temperature
of 55 C for 2 min, followed by heating at 20 C/min to 150 C and
then a second heating ramp at 1.5 C/min to 320 C for 20 min. The
six isomers of TA-DMC were identied by co-elution with authentic standards (Fig. 2) using two types of capillary columns, DB-1
and DB-5.
All the aromatic hydrocarbon fractions, including those from organic matter rich rocks and oil samples, were analyzed under the
same analytical conditions. In addition, some aromatic hydrocarbon fractions were analyzed by metastable reaction monitoring
GCMS (MRM-GCMS) in order to conrm the presence or absence
of TA-DMC compounds with higher specicity. Although a hybrid
mass spectrometer (Autospec-Q, EBE-qQ system, Micromass) was
used the analyses were carried out by metastable reaction monitoring mode using the eld-free region (FFR-1) of the instrument.
412
Table 2
Occurrence of 23,24-dimethylcholesteroids in organisms and sediments.
23,24-Dimethylcholesteroids
Dinoagellate
Other algae
Other organisms
Sediments
5,22-dien-3b-ol
5,23-dien-3b-ol
5a,7,22-dien-3b-ol
(28) Asteroidea
7,22-dien-3b-ol
5a,22-en-3b-ol
5-en-3b-ol
(1) Gonyaulax
polygramma
(8) Prorocentrum sp.
(41) Gymnodinium simplex
5a,3b-ol
(47) mollusc
5a,3a-ol
4,22-dien-3-one
5,22-dien-3b-sulphate
5,17(20)-dien-3b-ol
5,17(20)-diene-3b,25-diol
5f,22-en-3b-ol
(1) Volkman et al. (1984). (2) Withers (1987). (3) Nichols et al. (1983). (4) Kokke et al. (1981). (5) Kokke et al. (1982). (6) Withers et al. (1982). (7) Nichols et al. (1984). (8)
Volkman et al. (1999). (9) Jones et al. (1983). (10) Robinson et al. (1987). (11) Zielinski et al. (1983). (12) Volkman et al. (1980). (13) Volkman et al. (1981b). (14) Volkman et al.
(1993). (15) Volkman et al. (1981a). (16) Rampen et al. (2009). (17) Kobayashi et al. (1989). (18) Kanazawa et al. (1974). (19) Kanazawa et al. (1977). (20) Kelecom et al.
(1980). (21) Itoh et al. (1983). (22) Barnathan et al. (1992). (23) Barnathan et al. (2003). (24) Kalinovskaya et al. (1983). (25) Ando et al. (1979). (26) Kerr and Baker (1991).
(27) Kerr and Southgate (unpublished results). (28) Sato et al. (1980). (29) Kobayashi et al. (1979). (30) Kobayashi (1994). (31) Wardroper et al. (1978). (32) Cranwell (1982).
(33) Shaw and Johns (1985). (34) Shaw and Johns (1986). (35) Wilson et al. (2001). (36) Lee et al. (1980). (37) Volkman (1986). (38) Vron et al. (1998). (39) Bohlin et al.
(1981). (40) de Leeuw et al. (1983). (41) Goad and Withers (1982). (42) Fernandes et al. (1999). (43) Marlowe et al. (1984). (44) Mansour et al. (1999). (45) Leblond and
Chapman (2002). (46) Wakeham (1995). (47) Murphy et al. (2002). (48) Barrett et al. (1995).
a
Possibly input from coelenterates.
b
Kobayashi et al. (1979) reported that the identication of 23,24-dimethylcholesta-5,22-dien-3b-ol is incorrect. They proposed based on PMR spectral properties that the
compound is in fact sarcosterol (23,24-dimethylcholest-5,17(20)-dien-3b-ol).
c
Unpublished results.
d
Trace.
e
Summer season only.
f
As minor component.
viscous and was heated for 3.5 h at 5354 C. The solution was
cooled and the phases were separated. The aqueous layer was
413
414
Table 3
Identication of organic rich marine source rocks and measurements of triaromatic steroid ratios.
Sample
ID
Country-Region
A565
A564
A468
A466
S2
A476
C9
333
S3
C151
S1
C152
A316
(Australia)
(Australia)
AZ (USA)
AZ (USA)
Middle East
Middle East
MO (USA)
ND (USA)
Middle East
E. Siberia (Russia)
Middle East
E. Siberia (Russia)
E. Siberia (Russia)
McArthur
McArthur
Colorado Plateau
Colorado Plateau
Central Arabia
Central Arabia
?
Williston
Central Arabia
Yudoma-Olenek
Central Arabia
Yudoma-Olenek
Yudoma-Olenek
Velkerri
McMinn
Kwagunt, Chuar
Kwagunt, Chuar
Huqf
Huqf
Bonneterce
?
Huqf
Kuonamka
Huqf
Kuonamka
Kuonamka
181.3 m
64.0 m
Surface
Surface
>1000 m
4447 m
2337 ft.
?
>1000 m
C156
A221
E. Siberia (Russia)
(Australia)
?
Georgina
?
Inca
Surface
107.6 m
M. Pro.
M. Pro.
E. L. Pro.
E. L. Pro.
L. L. Pro.
L. Pro.
Cam.
Cam.
E. Cam.
E. Cam.
E. Cam.
E. Cam.
E. M.
Cam.
M. Cam.
M. Cam.
A220
A197
A198
A200
A199
315
A569
A568
A436
A382
A229
A333
A030
A330
(Australia)
(Sweden)
(Sweden)
(Sweden)
(Sweden)
(Russia)
(Australia)
(Australia)
(Australia)
Middle East
(Australia)
IA (USA)
IA (USA)
NV (USA)
Georgina
?
?
?
?
?
Amadeus
Amadeus
Amadeus
Central Arabia
Canning
?
Currant Bush
Alum Shale
Alum Shale
Alum Shale
Alum Shale
Dictyonema
Horn Valley
Horn Valley
Horn Valley
Hanadir
Goldwyer
Glenwood
Decorah-Guttenberg
Vinini
22.18 m
44.88 m
24.21 m
22 m
9m
<1000 m
227.9 m
217.5 m
216.5 m
14.829 ft.
936 m
752.1 ft.
953.3 ft.
8 ft.
M. Cam.
M. Cam.
L. Cam.
E. Ord.
E. Ord.
E. Ord.
E. Ord.
E. Ord.
E. Ord.
M. Ord.
Ord.
Ord.
Ord.
Ord.
A437
A900
C25
A242
A291
A289
A332
A241
IA (USA)
(Jordan)
NV (USA)
(Libya)
(Algeria)
(Algeria)
IA (USA)
(Libya)
St. Peter
?
Vinini Cr
761 ft.
2576 m
Surface
?
3214 m
2083 m
461.6 ft.
?
Ord.
Ord.
M. L. Ord.
L. Ord.
L. Ord.
L. Ord.
L. Ord.
E. Sil.
A383
A288
A449
Middle East
(Algeria)
(Bolivia)
A448
(Bolivia)
A447
A376
A239
Basin
Formation
Depth
>2000 m
Surface
Surface?
Period
Age
Ectasian-Tonian
Ectasian-Tonian
Cryogenian
Cryogenian
L.V
Ediacaran
?
L. TempletonFlorian
Florian-Undillian
Tremadocian
Tremadocian
?
Floian
Floian
Floian
?
Dapingian
Sandbian
Sandbian
Sandbian
Sandbian
Sandbian
Biomarker ratiosa
TADMC
TAdinosteroids
0.000
n/a
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
n/a
0.000
0.069
0.000
0.699
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.028
n/a
0.000
L
0.000
0.000
0.000
0.000
0.000
0.000
0.055
0.000
0.000
0.000
n/a
n/a
0.000
L
0.000
0.000
0.000
0.000
0.000
0.000
0.363
0.000
0.000
0.000
n/a
0.000
0.000
0.000
0.050
0.000
0.000
n/a
0.000
0.000
0.000
0.000
0.313
0.188
0.000
n/a
0.280
0.000
n/a
0.000
0.189
n/a
0.000
0.000
0.000
0.000
n/a
0.000
0.000
n/a
0.000
Qusaiba
Oued Ali
?
13,505 ft.
?
2191.5 m
E. Sil.
Sil.
L. Sil.
2188.9 m
L. Sil.
(Bolivia)
Middle East
(Russia)
Central Arabia
Ghadames
South Sub-Andean
FTB
South Sub-Andean
FTB
Chaco
Central Arabia
Timan-Pechora
Atuguis
Jauf
?
E. Dev.
E. Dev.
E. Dev.
A237
(Russia)
Timan-Pechora
E. Dev.
Emsian
0.000
0.000
A446
A605
C73-d93
A606
A604
A602
A949
A940
A445
A227
654
A948
(Bolivia)
(Bolivia)
(Bolivia)
(Bolivia)
(Bolivia)
(Bolivia)
(Bolivia)
(Bolivia)
(Bolivia)
(USA)
ND (USA)
Manchester (UK)
?
Sub-Andean
?
Sub-Andean
Sub-Andean
Sub-Andean
?
?
?
?
Williston
?
Tita
?
?
?
?
?
?
?
?
Woodford Shale
Bakken (Upper Member)
?
?
14,379 ft.
4028
4034 m
3700
3708 m
?
?
?
?
?
?
?
?
?
8943 ft.
10,002 ft.
Surface
Sandbian
Sandbian
Sandbian
Katian-Hirnantian
RuddanianTelychian
?
?
GorstianLudfordian
GorstianLudfordian
?
?
Emsian
Dev.
M. Dev.
L. Dev.
L. Dev.
L. Dev.
L. Dev.
L. Dev.
L. Dev.
L. Dev.
Car-Dev.
E. Car.
E. Car.
?
L. Givetian
?
Frasnian
Frasnian
Frasnian
?
?
?
0.000
0.000
n/a
0.000
0.000
0.000
0.000
0.000
0.000
0.000
n/a
n/a
0.000
0.002
n/a
0.200
0.000
0.000
0.000
0.000
0.000
0.000
n/a
n/a
A226
A225
A190
OK (USA)
UT (USA)
TX (USA)
Anadarko
Paradox
Palo Duso
Big Lime
Hermosa
Motley Co TX
0.000
0.000
0.000
0.000
0.000
0.000
A391
C73-d3
Middle East
(Bolivia)
Central Arabia
?
Unayzah
Bolivia
0.000
n/a
0.000
n/a
Rhazziane
?
Maquoketa Shale
Cryenacian Platform
4022.2 ft.
2782 ft.
5461
5471 ft.
6196 ft.
?
M. Car.
M. Car.
M.-L. Car.
Per-Car.
Per.
Tournaisian
SerpukhovianBashk.
Moscovian
Moscovian
Pennsylvanian
415
Country-Region
Basin
A603
(Bolivia)
Sub-Andean
E. Per.
A601
(Bolivia)
Sub-Andean
E. Per.
A559P
(Brazil)
E. Per.
A367
(Brazil)
Parana
Irati
E. Per.
A337
MT (USA)
Rocky Mountain
Peak
408.5 ft.
A342
MT (USA)
Rocky Mountain
Peak
A336
MT (USA)
Rocky Mountain
A335
MT (USA)
Rocky Mountain
C124
C125
A576
A416
A415
A414
C123
393
898
280
208
Svalbard (Norway)
Svalbard (Norway)
Alaska (USA)
WY (USA)
WY (USA)
WY (USA)
Svalbard (Norway)
(Switzerland)
(Syria)
ID (USA)
Alaska (USA)
Phosphoria (Mead
Member)
Phosphoria (Mead
Member)
Phosphoria (Mead
Member)
Phosphoria (Mead
Member)
Sticky Keep
Sticky Keep
207
797
A793
Depth
Period
Age
Biomarker ratiosa
TADMC
TAdinosteroids
0.000
0.000
0.000
0.000
n/a
n/a
n/a
n/a
E. Per.
SakmarianArtinskian
SakmarianArtinskian
ArtinskianKungurian
ArtinskianKungurian
Kungurian
0.000
0.000
431.5 ft.
E. Per.
Kungurian
n/a
n/a
Peak
207 ft.
E. Per.
Guadalupian
0.000
0.000
Peak
205 ft.
L. Per.
Guadalupian
0.000
0.000
?
?
Surface
34.1 ft.
32.1 ft.
30.9 ft.
?
327332 ft.
675825 m
1941 ft.
8891
8903 ft.
8825
8830 ft.
Surface
?
E.
E.
E.
E.
E.
E.
n/a
n/a
0.608
0.237
0.000
0.000
n/a
0.901
n/a
0.523
0.355
Tri.
Tri.
Tri.
Tri.
Tri.
Tri.
M. Tri.
Tri.
Tri.
Tri.
Anisian-Landinian
?
?
?
n/a
n/a
0.071
0.000
0.000
0.000
n/a
0.232
n/a
0.000
0.040
Tri.
0.126
0.548
L. Tri.
M. Jur.
Norian
E.-M. Callovian
0.113
n/a
0.663
n/a
L. Jur.
L. Jur.
?
?
0.064
0.059
0.475
0.472
L. Jur.
L. Jur.
M. Jur.
M. Jur.
M. Jur.
?
?
Bathonian
E.-M. Callovian
0.024
0.050
0.006
0.218
n/a
0.416
0.461
0.182
0.795
n/a
Oxfordian
L. Oxfordian
Oxford.-E. Kimm.
L. Oxford.-Kimm.
E. Kimmeridgian
0.087
0.090
n/a
0.057
0.037
0.584
0.475
n/a
0.517
0.441
North Slope
Dinwoody
Dinwoody
Dinwoody
Botneheia
Meride Shale
?
Thaynes Limestone
Shublik
Alaska (USA)
North Slope
Shublik
(Italy)
(Papua New
Guinea)
Alaska (USA)
Alaska (USA)
Central Apennines
South Papuan FTB
Dolmia Pricipale
Koi-Lange
North Slope
North Slope
Kigak Shale
Kigak Shale
Barrow Dampier
Barrow Dampier
North Sea
Celtic Sea
South Papuan
Dingo Clayston
Dingo Clayston
Cullaidh
Koi-Lange
Central Arabia
Central Arabia
North Sea
Central Arabia
South Papuan FTB
Tuwaiq Mountain
Hanifa
Kimmeridge Clay
Hanifa
Imburu
6815 ft.
6540 ft.
5320 ft.
1009 ft.
Surface
L.
L.
L.
L.
L.
North Sea
South Papuan FTB
Kimmeridge Clay
Imburu
53,201 ft.
9380 ft.
L. Jur.
L. Jur.
Kimmeridgian
L. Kimmeridgian
n/a
0.043
n/a
0.372
Imburu
Surface
L. Jur.
E. Tithonian
0.051
0.507
West Siberia
South Papuan FTB
Bezhenov
Leru
2773 m
7880 ft.
L. Jur.
E. Cret.
Tithonian
L. Berriasian
0.130
0.053
0.608
0.496
A503
(Australia)
(Australia)
(UK)
(Scotland)
(Papua New
Guinea)
Middle East
Middle East
(UK)
Middle East
(Papua New
Guinea)
(UK)
(Papua New
Guinea
(Papua New
Guinea)
(Russia)
(Papua New
Guinea)
(Argentina)
Neuquen
Vaca Muerta
Surface
E. Cret.
0.062
0.411
312
209
A619
(Australia)
Alaska (USA)
(Colombia)
Barrow Dampier
North Slope
Upper Magdalena
Muderong Shale
?
Paja
1291 m
11,568 ft.
Surface
E. Cret.
E. Cret.
E. Cret.
0.097
0.095
0.067
0.782
0.516
0.615
A631P
A627P
A617
A629P
A616
A539P
A630P
A533
A600
(Italy)
(Ecuador)
(Colombia)
(Australia)
(Colombia)
(Angola)
(Italy)
(Angola)
(Bolivia)
?
Napo
Similti
Toolebuc
Similti
Vermelha
?
Vermelha
?
Surface
295 m
Surface
?
Surface
9500 ft.
Surface
7088 ft.
Surface
E. Cret.
E. Cret.
E. Cret.
E. Cret.
L.-E. Cret.
L. Cret.
L. Cret.
L. Cret.
L. Cret.
Berriasian-L.
Valang.
Hauterivian
Barremian-Albian
L. Berriasian-L.
Haut.
Aptian
Aptian
L. M. Albian
L. Albian
E. Cenomanian
E. Cenomanian
Cenomanian
L. Cenomanian
CenomanianTuronian
0.019
0.060
0.097
0.065
0.107
0.058
0.023
0.067
0.098
0.250
0.595
0.570
0.451
0.442
0.347
0.304
0.472
0.197
213
210
313
314
997
993
A793
413
412
A789P
410
A790
A788P
A799
A791
A142
A798
?
?
?
Formation
9390 ft.
8399
8405 ft.
2835 ft.
2545 ft.
6888 ft.
Jur.
Jur.
Jur.
Jur.
Jur.
Induan-Olenekian
Induan-Olenekian
Induan-Olenekian
416
Table 3 (continued)
Sample
ID
Country-Region
Basin
C34
A554P
A411
A547P
226
A552
A545
583
A623
A543
A613
A608P
A537
A386
CO (USA)
(Angola)
(Ecuador)
(Angola)
Alaska (USA)
(Angola)
(Angola)
WY (USA)
CA (USA)
Cabinda (Angola)
(Colombia)
(Colombia)
(Angola)
(Trinidad)
?
Lower Congo
Oriente
Lower Congo
North Slope
Lower Congo
Lower Congo
A385
(Trinidad)
Formation
Depth
Period
San Joaquin
Lower Congo
Upper Magdalena
Upper Magdalena
Lower Congo
Onshore Trinidad
Vermelha
Napo
Vermelha
Seebee Shale
Vermelha
Vermelha
Hilliard (Upper Member)
?
Vermelha
La Luna
La Luna
Labe
Naparima Hill
?
8233 ft.
144 m
6100 ft.
11,161 ft.
7536 ft.
5366 ft.
7080 ft.
14,112 ft.
4545 ft.
Surface
Surface
9952 ft.
Surface
L.
L.
L.
L.
L.
L.
L.
L.
L.
L.
L.
L.
L.
L.
Cret.
Cret.
Cret.
Cret.
Cret.
Cret.
Cret.
Cret.
Cret.
Cret.
Cret.
Cret.
Cret.
Cret.
Onshore Trinidad
Naparima Hill
Surface
L. Cret.
Age
L. Turonian
Turonian
Turonian
Coniacian
?
Santonian
Santonian
Santonian
Campanian
Campanian
L. Campanian
L. Campanian
L. Campanian
L. CampanianMaast.
Maastrichtian
Biomarker ratiosa
TADMC
TAdinosteroids
n/a
0.096
n/a
0.053
0.077
0.057
0.061
0.000
0.051
0.048
0.260
0.083
0.079
n/a
n/a
0.424
n/a
0.354
0.482
0.449
0.549
0.000
0.434
0.461
0.830
0.536
0.528
n/a
n/a
n/a
417
Country-Region
Stan 434
Stan 435
Caspian T171
Caspian T023
Caspian T173
Caspian T286
Caspian T299
Tengiz 177
Tengiz 291
Stan 616
Stan 7
B-1
B-2
WT-2
WT-7
Stan 840
ZZ005404
NG000066?
NG000068?
NG000079
ID004313
ID004315
Stan 693
Stan 3
Stan 1-3
Stan A90
Stan 307
Stan 305
Stan 302
Stan C256
Stan 21
B-22
B-23
B-3
B-4
B-5
B-6
B-7
B-8
B-9
B-10
B-11
B-12
B-13
B-14
B-15
B-16
B-17
B-18
B-19
B-20
B-21
B-24
B-25
B-26
B-27
B-28
B-29
B-30
B-31
B-32
B-33
B-34
B-35
B-36
B-37
B-38
B-39
AE001788
Stan 181
Stan 846
Stan C255
Stan A89
Tarragona (Spain)
Tarragona (Spain)
So. Caspian (Azerbaidjan)
So. Caspian (Azerbaidjan)
So. Caspian (Azerbaidjan)
So. Caspian (Turkmen)
So. Caspian (Turkmen)
So. Caspian (Azerbaidjan)
So. Caspian (Turkmen)
Pt. Arguello (USA)
San Joaquin (USA)
(Brazil)
(Brazil)
(Vietnam)
(Vietnam)
Lower Magdalena (Colombia)
W. Natuna Sea (Indonesia)
Niger Delta (Nigeria)
Niger Delta (Nigeria)
Niger Delta (Nigeria)
W. Natuna Sea (Indonesia)
W. Natuna Sea (Indonesia)
Pearl River Mouth (China)
San Joaquin (USA)
UT (USA)
Niger Delta (Nigeria)
(Central Sumatra)
(Central Sumatra)
(Central Sumatra)
N.E. Trinidad (Trinidad)
GOM LA (USA)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
(Brazil)
Middle East (Dubai)
WY (USA)
San Jacinto (Colombia)
San Joaquin (USA)
Niger Delta (Nigeria)
Tertiary
Tertiary
Tertiary
Tertiary
Tertiary
Tertiary
Tertiary
Tertiary
Tertiary
Tertiary
Tertiary
Tertiary
Tertiary
Tertiaryb
Tertiary b
Tertiary b
Tertiary
Tertiary
Tertiary
Tertiary
Tertiary b
Tertiary b
Tertiary b
Tertiary
Tertiary b
Tertiary
Tertiary b
Tertiary b
Tertiary b
Tertiary b
Tertiary
Late Cretaceous
Late Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Early Cretaceous
Cretaceous
Cretaceous
Cretaceous
Cretaceous
Cretaceous
Biomarker ratiosa
TA-DMC
TA-dinosteroids
0.088
0.043
0.106
0.108
0.126
0.104
0.104
0.120
0.097
0.122
0.120
0.050
0.071
0.041
0.056
0.081
0.057
0.050
0.209
0.081
0.069
0.095
0.048
0.076
0.033
0.074
0.021
0.062
0.058
0.050
0.057
0.039
0.070
0.222
0.204
0.211
0.226
0.234
0.243
0.245
0.172
0.199
0.177
0.122
0.081
0.140
0.147
0.076
0.095
0.082
0.113
0.095
0.068
0.079
0.060
0.043
0.032
0.042
0.025
0.027
0.046
0.034
0.049
0.048
0.045
0.030
0.026
0.061
0.099
0.074
0.135
0.084
0.091
0.598
0.689
0.583
0.633
0.758
0.672
0.623
0.735
0.645
0.726
0.697
0.591
0.554
0.713
0.764
0.458
0.664
0.708
0.786
0.683
0.558
0.758
0.793
0.528
0.460
0.509
0.412
0.765
0.644
0.246
0.476
0.270
0.724
0.966
0.962
0.944
0.952
0.952
0.953
0.955
0.934
0.933
0.944
0.863
0.830
0.900
0.924
0.825
0.766
0.611
0.749
0.680
0.844
0.862
0.780
0.756
0.678
0.698
0.650
0.476
0.750
0.622
0.546
0.765
0.767
0.642
0.636
0.787
0.736
0.557
0.774
0.587
0.624
(continued on next page)
418
Table 4 (continued)
Sample ID
Country-Region
Stan 895
Stan 861
Stan A402
Stan 896
Stan 917
Stan 889
Stan A28
Stan 179
Stan 161
Stan 599
Stan 601
Stan 494
Stan A192
TE-A-1
SWZB-301B
Kuwait
Stan C7
Stan 9
Stan 975
NO001158
NO001144
SK-3
Stan 93
Stan A2
Stan B199
Stan 219
Stan A27
Stan C144B
SK-21
TH96-08
TH96-05
BT2 Cooper
A-1
A-2
A-3
A-4
A-5
A-7
A-8
A-9
A-10
A-11
A-12
A-13
A-14
A-15
A-16
A-17
A-18
A-19
A-20
A-22
A-23
A-24
A-26
A-27
A-28
A-30
A-31
A-32
A-34
A-35
A-40
Stan 563
Stan 559
Stan 19
Stan 218
Tengiz 18
Tengiz 12
Tengiz 21
Caspian T018
Caspian T019
Caspian T021
Caspian T195
(Jordan)
Maracaibo (Venezuela)
Oriente (Ecuador)
(Jordan)
(Angola)
(Angola)
(Oman)
Rocky Mtn FTB (USA)
Rocky Mtn FTB (USA)
(Sudan)
(Sudan)
GOM FL (USA)
Magallanes-Austral (Chile)
(Mongolia)
(Mongolia)
Central Arabia (Kuwait)
(New Zealand)
(Canada)
North Sea (UK)
North Sea (Norway)
North Sea (Norway)
Barrow-Dampier (Australia)
Barrow-Dampier (Australia)
South Papuan FTB (PNG)
Sureste (Mexico)
North Slope (USA)
(Oman)
Onshore Gulf Coast AL (USA)
Vulcan Graben (Australia)
Turpan (China)
Turpan (China)
Cooper (Australia)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
(Argentina)
Central Adriatic (Italy)
Southern Adriatic (Albania)
(Canada)
North Slope (USA)
Manghyshlak (Kazakhstan)
Pricaspian (Russia)
Manghyshlak (Kazakhstan)
Manghyshlak (Kazakhstan)
Manghyshlak (Kazakhstan)
Manghyshlak (Kazakhstan)
Pricaspian (Kazakhstan)
Cretaceous
Cretaceous
Cretaceous
Cretaceous
Cretaceous b
Cretaceous b
Cretaceous
Cretaceous
Cretaceous
Cretaceous b
Cretaceous b
Cretaceous
Cretaceous
Cretaceous b
Cretaceous b
Cretaceous
Cretaceous
Cretaceous
Late Jurassic (Oxfordian-Tithonian)
Late Jurassic (Oxfordian-Tithonian)
Late Jurassic (Oxfordian-Tithonian)
Late Jurassic (Tithonian)
Late Jurassic (Tithonian)
Late Jurassic (Oxfordian-Tithonian)
Late Jurassic (Oxfordian)
Late Jurassic (Oxfordian-Kimm.)
Late Jurassic (Oxfordian-Kimm.)
Late Jurassic (Oxfordian-Kimm.)
Middle Jurassic
Early Middle Jurassic b
Early Middle Jurassic b
Jurassic b
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Jurassic
Triassic/Jurassic
Triassic/Jurassic
Triassic/Jurassic
Triassic/Jurassic
Triassic/Jurassicc
Triassic/Jurassic b
Triassic/Jurassic c
Triassic/Jurassic c
Triassic/Jurassic c
Triassic/Jurassic c
DevonianPermian
Biomarker ratiosa
TA-DMC
TA-dinosteroids
0.183
0.159
0.099
0.076
0.103
0.178
0.083
0.109
0.101
0.073
0.080
0.044
0.034
0.015
0.034
0.040
0.123
0.074
0.136
0.085
0.090
0.025
0.030
0.079
0.054
0.049
0.036
0.069
0.015
0.010
0.000
0.028
0.098
0.108
0.133
0.140
0.095
0.131
0.136
0.070
0.101
0.098
0.104
0.107
0.051
0.082
0.055
0.092
0.101
0.094
0.090
0.072
0.088
0.108
0.090
0.101
0.092
0.037
0.058
0.026
0.030
0.028
0.096
0.022
0.039
0.107
0.044
0.014
0.000
0.000
0.007
0.044
0.000
0.000
0.752
0.845
0.749
0.605
0.845
0.918
0.745
0.694
0.715
0.807
0.802
0.543
0.359
0.418
0.716
0.532
0.656
0.563
0.753
0.658
0.665
0.462
0.353
0.833
0.681
0.543
0.453
0.734
0.156
0.240
0.154
0.370
0.652
0.684
0.812
0.815
0.695
0.801
0.808
0.615
0.608
0.639
0.681
0.686
0.509
0.634
0.496
0.652
0.690
0.664
0.667
0.583
0.696
0.689
0.639
0.626
0.627
0.421
0.522
0.336
0.363
0.335
0.640
0.600
0.418
0.696
0.470
0.197
0.000
0.000
0.089
0.403
0.000
0.109
419
Country-Region
Caspian T201
Caspian T202
Caspian T206
Caspian T214
Caspian T224
Caspian T225
Caspian T228
Caspian T357
TH96-10
BT4 Cooper
Stan 359
Stan C215
Stan 644
Stan C115
Stan 28
Stan 23
Stan A115
Tengiz 181
Tengiz 15
Tengiz 1
Tengiz 197
Tengiz 353
Tengiz 199
Tengiz 206
Tengiz 203
Stan A179
Hawtah-1
980930-09
Stan A136
Stan A138
Stan A137
Stan 259-1
T466
T335
T338
T528
Stan C216
Stan A24
N530
Pricaspian (Russia)
Pricaspian (Russia)
Pricaspian (Kazakhstan)
Pricaspian (Kazakhstan)
Pricaspian (Kazakhstan)
Pricaspian (Kazakhstan)
Pricaspian (Kazakhstan)
Pricaspian (Kazakhstan)
(China)
Cooper (Australia)
Rocky Mtn FTB-WY (USA)
East Middlands (UK)
Moncton (Canada)
Madre de Dios (Bolivia)
(Canada)
(Canada)
Timan-Pechora (Russia)
Pricaspian (Kazakhstan)
Pricaspian (Russia)
Pricaspian (Kazakhstan)
Pricaspian (Kazakhstan)
Pricaspian (Kazakhstan)
Pricaspian (Kazakhstan)
Pricaspian (Russia)
Pri-Caspian (Russia)
NW Arabian (Turkey)
Central Arabia (Saudi Arabia)
Tarim (China)
Timan-Pechora (Russia)
Timan-Pechora (Russia)
Timan-Pechora (Russia)
Urals (Russia)
East Siberia (Russia)
East Siberia (Russia)
East Siberia (Russia)
East Siberia (Russia)
(Oman)
(Oman)
Moscow (Russia)
DevonianPermian
DevonianPermian
DevonianPermian
DevonianPermian
DevonianPermian
DevonianPermian
DevonianPermian
DevonianPermian
Paleozoic b
Paleozoic b
Paleozoic
Paleozoic
Paleozoic b
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Paleozoic
Biomarker ratiosa
TA-DMC
TA-dinosteroids
0.000
0.000
0.000
0.000
0.057
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.023
0.000
0.000
0.000
0.000
0.000
0.000
0.022
0.000
0.000
0.000
0.000
0.023
0.000
0.014
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.095
0.039
0.006
0.464
0.000
0.000
0.144
0.069
0.551
0.164
0.266
0.263
0.280
0.078
0.103
0.113
0.051
0.182
0.302
0.284
0.079
0.091
0.000
0.000
0.336
0.153
0.368
0.000
0.096
0.000
0.000
0.303
0.500
0.000
0.211
0.000
0.000
0.139
Talyzina, 1998), while the TA-DMC appear to relate almost exclusively to post-Permian species.
4. Conclusions
Triaromatic 23,24-dimethylcholesteroids (TA-DMC) occur in all
analyzed marine Jurassic and Cretaceous and about one half of the
Triassic rock samples. The TA-DMC also occur in oil samples (marine and non-marine) derived from source rocks of that age range
where triaromatic steroids of any type are present. Proterozoic
Paleozoic samples record rare occurrences of TA-DMC, which are
limited thus far to several Ordovician rock and oil samples from
North Africa.
The distribution of TA-DMC in the analyzed samples (a set of almost 300 samples ranging from Proterozoic to Tertiary) has led to
the conclusion that these biomarkers can be used together with
triaromatic dinosteroids (TA-dinosteroids) to distinguish Proterozoic to Triassic from Jurassic and younger oil and rock samples.
Both of these triaromatic steroid types appear to be taxon specic
for dinoagellates and possibly haptophytes based on the fossil
record. During the Triassic, the initial radiation and probable a lack
of a signicant contribution of the related taxa correspond to
sporadic TA-DMC occurrence. TA-DMC compounds are abundant
420
Fig. 2. Mass chromatograms showing the distribution and identication of triaromatic 23,24-dimethylcholesteroids (chromatographic peaks af) among other triaromatic
steroids (peaks go) by GCMS monitoring the ion m/z 231 in (A) Upper Cretaceous source rock from the Upper Magdalena Basin, Colombia, sample A613 and (B) Proterozoic
source rock from Central Arabia Basin, Middle East, sample S2; and by MRM-GCMS monitoring the transition m/z 372 ? 231 in (C) sample A613, and (D) the authentic
standard (Table 1).
in source rock extracts and oil samples from Cretaceous rift basin
lacustrine environments of the Brazilian margin. This suggests
421
a
HO
H
2
13
13
PhO C(S )O
H
4
15
15
H
3
14
14
CH 2 I
CH 2 O H
20
e,f
H
7
18
18
CH 2
d
H
6
17
17
H
5
16
16
23
20
CO 2 CH 3
CH 2 O H
h
H
8
19
19
24
e,h
H
9
20
20
H
1B
12B
12B
Fig. 3. Synthesis of (20f,23f,24f)-23,24-dimethyl-5a-cholestane 12B. (a) PhOC(S)Cl, Py, CH2Cl2; (b) (n-Bu)3SnH, AIBN, C6H6; (c) Ph3P@CH2, KOt-Am, benzene; (d) BH3 THF;
NaOH, H2O2; (e) Et3N, MsCl, CH2Cl2; (f) NaI, acetone; (g) LDA, (CH3)2CHCH(CH3)CH2CO2CH3; (h) LiAlH4, THF.
1.00
TA-Dinosteroid Ratio
0.80
0.60
Proterozoic
Cambrian
Ordovician
0.40
Silurian
Devonian
Carboniferous
Permian
0.20
Triassic
Jurassic
Cretaceous
0.00
0.00
0.10
0.20
0.30
TA-DMC Ratio
Fig. 4. Cross plot of TA-DMC versus TA-dinosteroids for rock samples. Triaromatic 23,24-dimethylcholesteroids are, with few exceptions, restricted to Mesozoic and younger
rock extracts. Triassic source rocks are split 3:4 between TA-DMC absence and occurrence, while only two of 57 Paleozoic source rocks show these compounds. This contrasts
with a much wider occurrence of triaromatic dinosteroids in Paleozoic rocks. The TA-DMC ratio is calculated based on the compounds identied as peaks b and j (b/(b + j),
Fig. 2). The TA-dinosteroid ratio is the sum of eight stereoisomeric (at C-20, C-23 and C-24) TA-dinosteroids (5, Fig. 1) divided by the summation of compounds 5 plus TA-24ethylcholesteroid (20S, peak j, Fig. 2).
Acknowledgements
The authors thank the Center for Structural Biology Chemistry
Core Facility, the NIH National Center for Research Resources
422
Fig. 5. Frequency of occurrence of TA-DMC in the rock samples. (a) Dinoagellate cyst genera (adapted from MacRae et al., 1996, by Moldowan et al., 2001) and (b) acritarch
genera (adapted from Strother, 1996, by Moldowan et al., 2001) compared with (c) frequency of occurrence of TA-DMC in rock samples by percentage from a given period.
1.00
TA-Dinosteroid Ratio
0.80
0.60
0.40
Tertiary
Cretaceous
Jurassic
0.20
Jurassic/ Triassic
Paleozoic
Cretaceous (Brazil)
0.00
0.00
0.20
0.10
0.30
TA-DMC Ratio
Fig. 6. Cross plot of TA-DMC versus TA-dinosteroids for oil samples. Using the same parameters as Fig. 4, triaromatic 23,24-dimethylcholesteroids distinguish Mesozoic and
Paleozoic oils sampled from many basins. The Cretaceous oil families of Brazil are indicated individually. Oil samples generated from the Brazilian Cretaceous lacustrine
source rocks show high TA-DMC ratios.
comments, and Frederick J. Fago of Stanford University for assistance in preparing the pyrolyzate.
Associate EditorJohn Volkman
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