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Organic Geochemistry 42 (2011) 409424

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Organic Geochemistry
journal homepage: www.elsevier.com/locate/orggeochem

New triaromatic steroids distinguish Paleozoic from Mesozoic oil


Silvana M. Barbanti a,, J. Michael Moldowan b, David S. Watt c, E. Kolaczkowska d
a

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

Corresponding author at: Integrated Petroleum Expertise Company Ltda., Rio de


Janeiro, RJ 22280-030, Brazil. Tel.: +55 21 3622 9500; fax: +55 21 3622 9513.
E-mail address: silvana.barbanti@ipexco.com.br (S.M. Barbanti).
0146-6380/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.orggeochem.2011.02.007

triaromatic 4,23,24-trimethylcholestanes (5, TA-dinosteroids) can


be used to distinguish Mesozoic from older petroleum (Moldowan
et al., 1996, 2001). Their precursor dinosterols have been widely
reported in dinoagellates (Withers, 1987), the fossil cysts of
which show a history ranging from Triassic to present. The early
origin of dinoagellates has been discussed (e.g., Fensome et al.,
1996) with some additional biogeochemical evidence from acritarch geochemical studies (Moldowan and Talyzina, 1998; Talyzina
et al., 2000). The biochemically related 23,24-dimethylcholesterols
have been found in dinoagellates, diatoms and haptophytes
(Withers, 1987; Volkman et al., 1981a, 1993) (Table 2). Dinoagellate and haptophyte remains (cysts and coccoliths, respectively)
have similar paleontological records, Triassic to present. 23,24Dimethylcholesteroids (6) might be expected to show a similar
distribution to the dinosteroids because they also occur in
dinoagellates. However, the structure of the 23,24-dimethylcholesteroids suggest chemistry with additional biosynthetic steps
compared to that of dinosteroids, i.e., the loss of a 4-methyl group.
As such, one could speculate that the occurrence of 23,24-dimethylcholesteroids might be expected to be skewed toward younger
sediments. This possible age related tendency is supported by the
nding of 23,24-dimethylcholesterols in numerous diatom species
(Rampen et al., 2009), which radiate in the Jurassic, whereas
4,23,24-trimethylcholesterols have only one known low level
occurrence in diatoms (Volkman et al., 1993).
This report presents a study of the relative abundance of a novel
series of triaromatic 23,24-dimethylcholesteroids (7, TA-DMC) in
source rock extracts and oil samples from different global localities
and ages.

410

S.M. Barbanti et al. / Organic Geochemistry 42 (2011) 409424

8,
9,
10,
11,

X=H
X = CH3
X = C2H5
X = n-C3H7

Fig. 1. Structures of the steroid hydrocarbons cited in text and gures.

2. Materials and methods

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

Aromatic hydrocarbon fractions were prepared from extracts of


rock samples using high performance liquid chromatography
(HPLC) as described by Moldowan et al. (1996) and Peters et al.
(2005) and from oil samples using medium pressure liquid chromatography (n-hexane as solvent). Gas chromatographymass
spectrometry (GCMS) analyses of aromatic hydrocarbon fractions
were carried out using an HP 6890 gas chromatograph interfaced
to an HP 5973 MSD system using the selective ion monitoring

S.M. Barbanti et al. / Organic Geochemistry 42 (2011) 409424


Table 1
Identication of compounds shown in Fig. 1.
Peaka

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

diastereomers 17 was used to synthesize 12B. For the preparation


of either 12A or 12B, the chemistry from this point forward was the
same and therefore only the synthesis of 12B will be described in
detail. The alcohols 17 were converted to the corresponding
iodides 18 in a standard reaction and the alkylation of 18 with
racemic methyl 3,4-dimethylpentanoate (Stoilov et al., 1993)
secured the steroidal ester 19. A standard sequence involving
reduction of the ester to the alcohol 20, mesylation and further
reduction of the mesylate afforded the target sterane, (20f,
23f,24f)-23,24-dimethyl-5a-cholestane 12B.
2.3.2. Synthesis of C29 cholestanes
2.3.2.1. 3b-Hydroxy-5a-pregnan-20-one phenyl thiocarbonate
(14). See Barton and McCombie (1975) and Robins et al. (1983).
A solution of 8.97 g (28.2 mmol) of 5a-pregnan-3b-ol-20-one
(13) and 7.29 g (42.2 mmol, 5.85 ml) of phenyl chlorothioformate
in 9.1 ml of anhydrous pyridine and 165 ml of anhydrous CH2Cl2
afforded 10.2 g (80%) of 14 as pale yellow plates: mp 189
190 C; IR (CHCl3) 1690 (C@O), 1590 (C@O), 1485, 1290, 1190,
1015 cm1; 1H NMR (CDCl3) d 0.61 (s, 3, C-18 CH3), 0.87 (s, 3, C19 CH3), 2.12 (s, 3, C-21 CH3), 5.105.30 (m, 1, CHOC(S)OPh),
7.087.5 (m, 5, ArH); 13C NMR (CDCl3) d 11.9, 13.2, 20.9, 22.5,
24.2, 26.4, 28.3, 31.3, 31.7, 32.8, 35.2, 35.3, 36.4, 38.8, 44.1, 44.4,
53.9, 56.5, 63.7, 84.2, 122.2, 126.6, 129.6, 153.5, 194.8, 210.1.
Anal. Calcd. for C28H38SO3: C, 73.96; H, 8.42; S, 7.05. Found: C,
74.04; H, 8.42; S, 7.12.

Peak labels used in Fig. 2.


Structures are presented in Fig. 1.
The C29 20S compound is split into a doublet (peaks m and n) consisting of 24S
and 24R epimers (Peters et al., 2005).
b

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.

2.3. Preparation of the standard


2.3.1. Synthesis of (20S,23f,24f)- and (20f,23f,24f)-23,24-dimethyl5a-cholestane
The synthesis of (20S,23f,24f)-23,24-dimethyl-5a-cholestane
12A and (20f,23f,24f)-23,24-dimethyl-5a-cholestane 12B utilized
3b-hydroxy-5a-pregnan-20-one 13 as a starting material and employed an ester-alkylation sequence (Stoilov et al., 1992, 1993,
1994; Shetty et al., 1994) to construct the side chain. As shown
in Fig. 3, the starting material 13 was deoxygenated at C-3 using
a tri-n-butyltin hydride reduction of the corresponding xanthate
14 (Barton and McCombie, 1975; Robins et al., 1983). A Wittig
reaction of 15 and hydroborationoxidation of the resulting alkene
16 provided the alcohols 17 as a mixture of C-20 diastereomers
that were separable by chromatography. The C-20S diastereomer
of 17 was used to synthesize the target 12A and the mixture of

2.3.2.2. 5a-Pregnan-20-one (15). A solution of 27 g (92.8 mmol) of


(n-Bu)3SnH in 200 ml of anhydrous benzene was added dropwise
over 5 h to a reuxing solution of 12.8 (28.1 mmol) of 14 and
0.46 g (2.81 mmol) of 2,20 -azobisisobutyronitrile (AIBN) in 735 ml
of anhydrous benzene. The mixture was reuxed an additional
6 h and cooled. The solution was washed successively with 1 M
HCl solution, water, 5% NaOH solution, brine and dried over anhydrous MgSO4. The crude yellow oil was chromatographed on silica
gel with 1:3 EtOAc: hexane, and the product was recrystallized
from EtOH to give 6.13 g (72%) of 15: mp 134135 C. See Janot
et al. (1960): mp 136 C.
2.3.2.3. 20-Methylene-5a-pregnane (16). To a stirred suspension of
7.9 g (22.3 mmol) of methyltriphenylphosphonium bromide (dried
over P2O5) in 10 ml of anhydrous benzene under a N2 atmosphere
were added 13.4 ml (22.3 mmol) of 1.66 M potassium tert-amylate
in benzene. The yellow mixture was reuxed for 1 h, and 1.0 g
(3.3 mmol) of 15 in 17 ml of anhydrous benzene was added. The
orange mixture was reuxed for 4.5 h and stirred for 12 h at
25 C. The mixture was poured into water and extracted with
Et2O. The combined organic layers were washed successively with
10% HCl solution, saturated NaHCO3 solution and brine and dried
over anhydrous MgSO4. The crude product was chromatographed
twice on silica gel using hexane to give 0.70 g (70%) of 16: mp
129131 C; IR (CHCl3) 1640 cm1; 1H NMR (CDCl3) d 0.55 (s, 3,
C-18 CH3), 0.78 (s, 3, C-19 CH3), 1.75 (s, 3, C-21 CH3), 4.684.72
and 4.824.86 (m, 2, C-22 vinylic H); 13C NMR (CDCl3) d 12.0,
12.7, 20.7, 22.0, 24.0, 24.5, 25.2, 26.7, 28.9, 32.0, 35.7, 36.1, 38.6,
38.8, 43.2, 47.0, 54.8, 56.3, 57.3, 110.6, 146.1 (21 lines).
Anal. Calcd. for C22H36: C, 87.93; H, 12.07. Found: C, 87.85; H,
12.02.
2.3.2.4. (20R) and (20S)-20-Hydroxymethyl-5a-pregnane (17). To a
suspension of 1.83 g (6.1 mmol) of 16 in 6.1 ml of anhydrous THF
at 0 C under a N2 atmosphere were added 2.43 ml (2.43 mmol)
of 1 M borane-THF solution via a syringe over a 10 min period.
The ice bath was removed and the clear solution was stirred at
25 C for 1 h. The mixture was again cooled to 0 C and the excess
borane was destroyed with 100 ll of H2O. To this solution were

412

S.M. Barbanti et al. / Organic Geochemistry 42 (2011) 409424

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

(1) Gonyaulax polygramma


(2, 4, 6, 20, 39)
Zooxanthellae

(3) marine alga FCRG 51


(12) diatom Biddulphia sinensis

(31) diatomaceous oozea


(13, 32, 33, 34, 35, 36, 37,
40, 42, 46)

(5, 45) Pyrocystis lunula

(13, 14) diatom

(7, 8) Prorocentrum sp.

(15, 43) Prymnesiophyceae


(Haptophyceae)
(16) various cultured diatoms

(18) soft coral


(19) soft coral coelenterates:
alcyonarians Sinularia polydactyla,
Sarcophyta elegansb
(4, 20) soft coral, gorgonians,
coelenterates
(21) sponge Axinella cannabina

(41) Gymnodinium simplex

(48) diatom Fragilaria pinnata

(44, 45) Symbiodinium


micro-adriaticum
(45) Coolia sp.,
Prorocentrum sp.,
Scrippsiella sp.,
Alexandrium andersoni

(22, 23) sponge Cinachyra alloclada,


Cinachyra kuekenthali
(24) holothurian Stichopus japonicus
Selenka
(25, 26, 47) mollusc
(27) mollusc Tridacna gigasc

5,23-dien-3b-ol

(19) soft coral Sarcophyta elegans

5a,7,22-dien-3b-ol

(28) Asteroidea

7,22-dien-3b-ol

(8) Prorocentrum sp.

5a,22-en-3b-ol

(1) Gonyaulax polygramma

(3) marine alga FCRG 51

(4, 39) Zooxanthellae


(5, 45) Pyrocystis lunula
(7) Prorocentrum cordatum
(8, 45) Prorocentrum sp.
(9) Thoracosphaera heimii
(10) Ceratium furcoides,
freshwater
(44) Gymnodinium
sanguineum and
Fragilidium sp.
(45) Coolia sp.

(16) diatom Ditylum brightwellii

5-en-3b-ol

(1) Gonyaulax
polygramma
(8) Prorocentrum sp.
(41) Gymnodinium simplex

5a,3b-ol

(1) Gonyaulax polygramma


(11) Zooxanthellae
Orbulina universa
(6) Zooxanthellae
(8) Prorocentrum sp.

(24) holothurian Stichopus japonicus


Selenka

(13, 32d, 33, 35e, 36, 37, 40,


46)

(16) diatom Haslea ostrearia

(47) mollusc

(13, 34, 35, 36, 37, 40, 46)

(38) diatom Haslea ostrearia

(11) bryozoan Bugula neritinac,f

(33, 36, 37, 40)

5a,3a-ol
4,22-dien-3-one

(11) sponge Stelletta conulosa


(5) Pyrocystis lunula

5,22-dien-3b-sulphate
5,17(20)-dien-3b-ol

(17) haptophyte Hymenomonas sp.


(45) Alexandrium andersoni

5,17(20)-diene-3b,25-diol
5f,22-en-3b-ol

(29) soft coral Sarcophytum glaucum


(30) soft coral Sinularia mayi

(41) Gymnodinium simplex

(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.

added 4.1 ml (12.2 mmol) of 3 M NaOH solution followed by 4.1 ml


(12.2 mmol) of a 30% H2O2 solution. The mixture was initially

viscous and was heated for 3.5 h at 5354 C. The solution was
cooled and the phases were separated. The aqueous layer was

S.M. Barbanti et al. / Organic Geochemistry 42 (2011) 409424

extracted with Et2O. The combined organic layers were washed


with brine and dried over anhydrous MgSO4. The product was
chromatographed on silica gel using 1:5 EtOAc: hexane to give
1.43 g (74%) of 17 as a mixture of 20R and 20S diastereomers:
mp 158160 C; IR (CHCl3) 3615 cm1; 1H NMR (CDCl3) d 0.67 (s,
3, C-18 CH3), 0.78 (s, 3, C-19 CH3), 0.95 and 1.03 (two d, 3,
J = 6.6 Hz, C-21R and C-21S CH3), 3.303.80 (m, 2, CH2OH).
The 20R and 20S-isomers were separated by MPLC (medium
pressure liquid chromatography) on silica gel using 1:5 EtOAc:
hexane. The isomers had the following spectral and physical data:
The 20S-isomer: mp 129.5131 C; IR (CHCl3) 3615, 30002810,
1435, 1370 cm1; 1H NMR (CDCl3) d 0.67 (s, 3, C-18 CH3), 0.78 (s, 3,
C-19 CH3), 0.95 (d, 3, J = 6.6 Hz, C-21 CH3), 3.403.80 (m, 2,
CH2OH); 13C NMR (CDCl3) d 12.0, 12.2, 16.5, 20.5, 22.0, 23.8, 26.6,
27.6, 28.9, 32.0, 35.3, 36.1, 37.8, 38.5, 39.4, 42.2, 46.9, 52.4, 54.6,
56.4, 66.8 (21 lines); mass spectrum m/z (rel. intensity) 318 (55),
303 (36), 218 (44), 217 (100), 149 (43), 109 (34), 95 (37), 81
(39), 67 (35), 55 (41), 41 (33); exact mass calcd. for 318: found
318.2924.
Anal. Calcd. for C22H36O: C, 82.95; H, 12.02. Found: C, 82.72; H,
12.00.
The 20R-isomer: mp 161164 C; IR (CHCl3) 3615 cm1; 1H
NMR (CDCl3) d 0.67 (s, 3, C-18 CH3), 0.78 (s, 3, C-19 CH3), 1.03 (d,
3, J = 6.6 Hz, C-21 CH3), 3.303.68 (m, 2, CH2OH); 13C NMR (CDCl3)
d 11.9, 12.0, 16.5, 20.5, 22.0, 24.1, 26.6, 27.5, 28.9, 32.0, 35.4, 36.1,
38.5, 38.6, 39.8, 42.5, 46.9, 52.4, 54.6, 56.3, 68.0 (21 lines); mass
spectrum m/z (rel. intensity) 318 (30), 303 (29), 218 (45), 217
(100), 149 (52), 109 (42), 95 (35), 81 (34), 67 (28), 55 (33), 41
(23); exact mass calcd. for 318: found 318.2925.
2.3.2.5. (20f)-20-Iodomethyl-5a-pregnane (18). See Crossland and
Servis (1970). A solution of 517 mg (1.62 mmol) of (20f)-17 dissolved in 22 ml of anhydrous CH2Cl2, 247 mg (2.44 mmol, 340 ll,
1.5 equiv) of Et3N and 204 mg (1.79 mmol, 138 ll, 1.1 equiv) of
CH3SO2Cl afforded, after stirring at 5 C for 45 min and employing
a standard isolation procedure, the crude mesylate as a mixture of
C-20 diastereomers that was used directly in the next reaction: mp
109.5113 C; 1H NMR (CDCl3) d 0.67 (s, 3, C-18 CH3), 0.78 (s, 3, C19 CH3), 0.99 and 1.08 (two d, 3, J = 6.6 Hz, C-21 CH3), 3.00 (s, 3,
CH2OSO2CH3), 3.914.41 (m, 2, C-22, CH2OSO2CH3).
See Partridge et al. (1974). A solution of 630 mg (1.59 mmol) of
crude mesylate and 2.38 g (15.9 mmol) of NaI in 31.5 ml of acetone
at the reux temperature for 8 h afforded, after chromatography on
silica gel using 1:3 EtOAc-hexane, 507 mg (75%) of 18: mp 95
103 C; IR (CHCl3) 1460, 1445, 1380, 1190, 960 cm1; 1H NMR
(CDCl3) d 0.66 and 0.70 (two s, 3, C-18 CH3), 0.77 (s, 3, C-19 CH3),
0.95 and 1.01 (two d, 3, J = 6 Hz, C-21 CH3), 3.113.53 (m, 2, CH2I).
Anal. Calcd. for C22H37I: C, 61.67; H, 8.70. Found: C, 61.77; H,
8.74.
2.3.2.6. Methyl (20f,23f,24f)-24-methyl-5a-cholestane-23-carboxylate (19). To a solution of 2.7 g (26.7 mmol) of diisopropylamine in
5.5 ml of anhydrous THF at 20 C were added 5.34 ml
(13.4 mmol) of 2.5 M n-BuLi in hexane. The solution was stirred
at 20 C for 20 min and cooled to 78 C. To this solution were
added 1.92 g (13.4 mmol) of racemic methyl 3,4-dimethylpentanoate in 2.4 ml of THF over a 15 min period. The mixture was stirred
at 78 C for 40 min, and 572 mg (1.33 mmol) of 18 in 7.2 ml of
THF and 2 ml of ((CH3)2N)3PO were added dropwise. The mixture
was stirred at 78 C for 7 h, allowed to warm to 25 C, and stirred
for an additional 12 h. The mixture was diluted with Et2O and
poured into cold H2O. The aqueous layer was extracted with
Et2O. The combined organic extracts were washed successively
with saturated NH4Cl solution and brine and dried over anhydrous
MgSO4. The crude product was chromatographed on silica gel
using a gradient of hexane and 1:20 EtOAc: hexane. A second

413

chromatography on silica gel using 1:50 EtOAc: hexane afforded


445 mg (75%) of 19: IR (CHCl3) 1730 (C@O) cm1; 1H NMR (CDCl3)
d 0.580.94 (m, 21, CH3 signals at 0.61, 0.63, 0.72, 0.77, 0.79, 0.83,
0.85, 0.88, 0.92), 3.64 and 3.66 (two s, 3, OCH3).
2.3.2.7. (20f,23f,24f)-23-(Hydroxymethyl)-24-methyl-5a-cholestane
(20). To a suspension of 120 mg (3.16 mmol) of LiAlH4 in 1 ml of
anhydrous THF at 0 C under a N2 atmosphere were added
445 mg (1.0 mmol) of crude 19 in 5 ml of THF over a 15 min period.
The mixture was stirred at 25 C for 3 h. The mixture was cooled to
0 C and diluted with Et2O. To this solution were added 120 ll of
water followed by 360 ll of 15% NaOH solution and nally an additional 360 ll of water. The supernatant was decanted and the
remaining white precipitate was triturated with of Et2O. The combined organic extracts were washed with brine and dried over
anhydrous MgSO4. The crude product was chromatographed on silica gel using 1:10 EtOAc: hexane to afford 295 mg (71%) of 20 as a
mixture of C-20, C-23, and C-24 diastereomers: 1H NMR (CDCl3) d
0.620.68 (m, 3, C-18 CH3), 0.740.96 (9 peaks, C-19 and side chain
CH3 at 0.77, 0.81, 0.83, 0.85, 0.86, 0.88, 0.90, 0.92, 0.94), 3.253.75
(m, 2, CH2OH).
2.3.2.8.
(20f,23f,24f)-23,24-Dimethyl-5a-cholestane
(12B). See
Crossland and Servis (1970). A solution of 295 mg (0.71 mmol) of
20 in 4.8 ml of anhydrous CH2Cl2, 108 mg (1.06 mmol, 1.5 equiv)
of Et3N and 89.3 (0.78 mmol, 1.1 equiv) of CH3SO2Cl afforded a
crude mesylate: 1H NMR (CDCl3) d 0.65 and 0.66 (two s, 3, C-18
CH3), 0.720.98 (C-19 and side chain CH3 at 0.75, 0.77, 0.80, 0.83,
0.86, 0.89, 0.91, 0.93, 0.94), 3.00 (s, 3, CH2SO2CH3), 3.754.30 (m,
2, CH2OSO2CH3). This mesylate was used directly in the next
reaction.
To a stirred suspension of 75.3 mg (1.98 mmol) of LiAlH4 in 3 ml
of anhydrous THF under an N2 atmosphere were added 329 mg
(0.66 mmol) of crude mesylate in 6 ml of anhydrous THF. The mixture was reuxed for 5 h. The solution was cooled to 0 C and diluted with 5 ml of Et2O. To this solution were added 75 ll of
water followed by 215 ll of 15% NaOH solution and nally
215 ll of water. The organic layer was separated and the white
precipitate was triturated with Et2O. The combined organic layers
were washed with brine and dried over anhydrous MgSO4. The
crude product was chromatographed on silica gel using hexane
to afford 218 mg (82%) of 12B: IR (CHCl3) 30002730, 1445,
1465, 1380, 1100 cm1; 1H NMR (CDCl3) d 0.620.94 (m, 21, CH3
signals at 0.64, 0.65, 0.66, 0.70, 0.74, 0.77, 0.79, 0.80, 0.83, 0.85,
0.86, 0.89, 0.90, 0.94). GCMS data conrmed that all eight isomers
were C29H52 compounds.
Anal. Calcd. for C29H52: C, 86.92; H, 13.08. Found: C, 86.94; H,
13.02.
2.3.3. Preparation of triaromatic 23,24-dimethylcholesteroid standard
Synthetic 23,24-dimethylcholestane (12B) was treated with 5%
Pd/C catalyst in a sealed, evacuated glass tube at 268 C for 72 h
according to the published procedure (Seifert et al., 1983). The
pyrolysate was recovered and separated into saturated and aromatic hydrocarbon fractions using HPLC. The yield of aromatic steroids was about 73% by GCMS. The produced TA-DMC standard
gave a pattern of six peaks (eight stereoisomeric compounds with
two co-elutions, Fig. 2D).
3. Results and discussion
3.1. Triaromatic 23,24-Dimethylcholesteroids (TA-DMC)
The conversion of 23,24-dimethylsterols to triaromatic steroid
hydrocarbons proceeds with the migration (i.e., C-13b ? C-17b)

414

S.M. Barbanti et al. / Organic Geochemistry 42 (2011) 409424

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

Basin & Range


Province
?
?
Cryenacian Platform
Ghadames
Illizi

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

S.M. Barbanti et al. / Organic Geochemistry 42 (2011) 409424


Table 3 (continued)
Sample
ID

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

South Papuan FTB

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)

South Alps FTB


Oriente
Upper Magdalena
Eromanga
Upper Magdalena
Lower Congo
South Alps FTB
Lower Congo
Sub-Andean Basin

?
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

Southern Alps FTB


Northwest Arabian

9390 ft.
8399
8405 ft.
2835 ft.
2545 ft.
6888 ft.

Jur.
Jur.
Jur.
Jur.
Jur.

Induan-Olenekian
Induan-Olenekian
Induan-Olenekian

(continued on next page)

416

S.M. Barbanti et al. / Organic Geochemistry 42 (2011) 409424

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

TA-DMC ratio: TA-DMC/(TA-DMC + C28 TA-steroid 20S).


TA-dinosteroid ratio: TA-dinosteroids/(TA-dinosteroids + C28 TA-steroid 20S).
n/a = measurement not taken.
L = low biomarker concentrations.
a
Refer to Fig. 1 and text for compound structures and names.

of an angular methyl group but the constitution of the side chain


remains unaltered (Ludwig et al., 1981). TA-DMC analysis of a
Campanian source rock (sample A613, Table 3) from the Upper
Magdalena Basin, Colombia, and an authentic TA-DMC standard
are illustrated (Fig. 2A, C and D). GCMS (m/z 231) and MRMGCMS (transition m/z 372 ? 231) analyses of both sample and
standard were carried out by using similar analytical conditions.
TA-DMC occur as a series of six peaks (Fig. 2, peaks af) related
to stereoisomerization at C-20, C-23 and C-24. Eight S and R stereoisomers are expected and therefore two of the peaks are most
likely co-elutions. The GCMS trace (m/z 231) of a Proterozoic
source rock from Central Arabia Basin, Middle East (sample S2, Table 3), is also illustrated (Fig. 2B).
In contrast with their saturated counterparts (23,24-dimethylcholestanes), TA-DMC are reliably identied by GCMS in the aromatic hydrocarbon fractions of most extracts and oil samples using
the mass spectral base peak m/z 231. The predominant C29 steranes, 24-ethylcholestanes, completely mask the 23,24-dimethylcholestanes in most samples, where they are present, when
analyzed using m/z 217 or metastable transition of the molecular
ion m/z 400 to the diagnostic ion m/z 217 by MRM-GCMS.
A new ratio is proposed in order to monitor the distribution of
TA-DMC. This normalized TA-DMC Ratio refers to the second isomer of TA-DMC relative to 20S triaromatic 24-ethylcholesteroid
(peaks b/(b + j), Fig. 2). This particular TA-DMC (peak b) was chosen
for the ratio because it elutes in a part of the m/z 231 mass chromatogram relatively free of interference (Fig. 2A).
3.2. Organic rich rocks
Normalized ratios of TA-DMC/TA-C28 20S plotted against
TA-dinosteroids/TA-C28 20S for the set of organic rich marine source
rocks (Table 3) exhibit values ranging from 0.006 up to 0.260 for all
extracts of the Jurassic and Cretaceous rock samples, while TA-DMC
were not detected in any except two Paleozoic (Ordovician) rocks
(Fig. 4). The presence of TA-DMC in those two samples from
Ordovician (A382, Middle East, Central Arabia basin and A242,
Libya) was conrmed by MRM-GCMS analysis.
In contrast, the percentage of Paleozoic samples that reveal
TA-dinosteroids is higher (30%) compared to those that show
TA-DMC (4%). However, almost all Jurassic and younger marine
rock samples in the present data set contain TA-DMC and TA-

dinosteroids with the exception of few samples that are severely


depleted in all TA-steroids due to a low steroid source component
overall or advanced maturity. TA-DMC were undetected in 50% of
the Triassic samples and TA-dinosteroids in 25% of them (Fig. 5).
Two Triassic core samples (Wyoming, USA, Dinwoody Fm. and Idaho, USA, Thaynes Fm.) exhibit high TA-dinosteroid ratios, 0.237 and
0.523, respectively, but lack TA-DMC. The contrast in the frequency
of TA-DMC occurrence between Proterozoic to Triassic and Jurassic
and younger rocks parallels the earliest appearance of dinoagellates and haptophytes in the Triassic, with strong radiation of species and, presumably, an increase in the prevalence and relative
abundance of their biomass in the Jurassic and Cretaceous and
continuing throughout the Tertiary.
3.3. Oil samples
The oil samples originated from Proterozoic to Tertiary source
rocks yield a result similar to that of the rock samples (Fig. 6 and
Table 4). A few Paleozoic samples contain TA-DMC. The presence
of TA-DMC in Paleozoic oil samples may be related to a pre-Mesozoic
chemical record of dinoagellates or closely related forms
(Moldowan et al., 2001), or haptophytes or diatoms. Therefore,
TA-DMC demonstrate good potential for application as age related
biomarkers and they can be analyzed together with TA-dinosteroids.
Besides their application as age related biomarkers, TA-DMC
also are potential indicators to distinguish source rock depositional
environments (Fig. 6). The oil samples from different depositional
environments record systematic variations in the relative abundance of TA-DMC compounds. The Cretaceous oil samples from
Brazil emanate from the synrift section, where source rocks were
deposited in restricted lacustrine environments at various salinities. They show the highest TA-DMC and TA-dinosteroid ratios in
the data set. The related source rocks of these lacustrine oil samples from Brazil have abundant dinoagellate cysts (Arai et al.,
2000), methylsterane/sterane ratios greater than 1.0 and abundant
TA-dinosteroids and their saturated dinosterane counterparts
(Mello et al., 1988a,b, 1989). These results favor the interpretation
that the algal population in these rift lake environments was
dominated by dinoagellates or that dinoagellate blooms occurred frequently.
Although the likely sterol precursors for both TA-DMC and
TA-dinosteroids occur in dinoagellates, diatoms and haptophytes,

417

S.M. Barbanti et al. / Organic Geochemistry 42 (2011) 409424


Table 4
Identication of oil samples and measurements of triaromatic steroid ratios.
Sample ID

Country-Region

Source rock age

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

S.M. Barbanti et al. / Organic Geochemistry 42 (2011) 409424

Table 4 (continued)
Sample ID

Country-Region

Source rock age

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

S.M. Barbanti et al. / Organic Geochemistry 42 (2011) 409424


Table 4 (continued)
Sample ID

Country-Region

Source rock age

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

TA-DMC ratio: TA-DMC/(TA-DMC + C28 TA-steroid 20S).


TA-dinosteroid ratio: TA-dinosteroids/(TA-dinosteroids + C28 TA-steroid 20S).
a
Refer to Fig. 1 and text for compound structures and names.
b
Refer to non-marine.
c
Refer to possible non-marine.

the paleontological records of these compounds are different. On


the one hand, Moldowan et al. (1996) demonstrated the earlier
occurrences of triaromatic dinosteroids in some extracts from Proterozoic to Devonian rocks, with the frequency of occurrence ranging from 960% per geologic time period. On the other hand, the
frequency of occurrence of the triaromatic 23,24-dimethyl steroids
in Paleozoic rocks is very low exhibiting a frequency of 10% and
only in some Ordovician samples. Therefore, the occurrence of
TA-DMC is more specic to the Mesozoic Era as can be viewed
by comparing the frequency of their occurrence against geologic
time (Fig. 5).
The chemical record of TA-DMC parallels that of dinoagellate
cysts (Fig. 5), which rst appear with certainty in the Triassic
and are abundant in the Jurassic and Cretaceous. Haptophytes
are responsible for coccolith fossils, which increase in occurrence
in the Triassic and are abundant throughout the later Mesozoic.
The TA-DMC could be related to any, or possibly all three taxa,
but may represent a modied chemical evolutionary adaptation
(i.e., the loss of a methyl group at C-4 from the sterol precursor).
TA-dinosteroids occur relatively more frequently in the Proterozoic
and Paleozoic, particularly during periods of high acritarch diversity (Ediacaran to Devonian) (Moldowan et al., 1996, 2001). Thus,
they may indicate dinoagellate ancestors (e.g., Moldowan and

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

S.M. Barbanti et al. / Organic Geochemistry 42 (2011) 409424

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

depositional environments dominated by algae and dinoagellate


blooms, in accordance with the available paleontological data.

421

S.M. Barbanti et al. / Organic Geochemistry 42 (2011) 409424

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

(NCRR) and the Molecular Organic Geochemistry Industrial


Afliates (MOGIA) of Stanford University for providing the funding.
The authors would also like to thank Dr. Jrgen Rullktter and Dr.
Roger E. Summons for their reviews of the manuscript and helpful

422

S.M. Barbanti et al. / Organic Geochemistry 42 (2011) 409424

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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