Extended ketones of the tricyclic terpane series in a Tasmanian

tasmanite bitumen
D. A. AZEVEDO
1
, F. R. AQUINO NETO
1
and B. R. T. SIMONEIT
2
1
Instituto de Qu mica, Centro de Tecnologia, Bloco A, Sala 607, Universidade Federal do Rio de
Janeiro, Ilha do Funda o, Rio de Janeiro, 21949-900, Brazil and
2
Petroleum and Environmental
Geochemistry Group, College of Oceanic and Atmospheric Sciences, Oregon State University,
Corvallis, OR 97331, U.S.A.
(Received 12 May 1997; returned to author for revision 18 August 1997; accepted 18 August 1997)
AbstractThe following novel ketones of the extended tricyclic terpane series (cleistanthane skeleton)
were identied in the ketone fraction of a Permian tasmanite bitumen from Tasmania, Australia by
HRGCMSC and HRGCMSMSCSRM:C
20
; the C
23
13,14-stereoisomers bb,ab,ba,aa; the
C
28
and C
33
diastereomers R/S ba and R/S aa; and higher homologs in lower relative abundance.
These tricyclic terpane ketones may be derived from oxidation of the side chain of a tricyclooctaiso-
prene. The proposed biological precursor for these series is tricyclooctaprenol (C
40
), derived from cycli-
zation of octaprenol in the tasmanites algae. # 1998 Elsevier Science Ltd. All rights reserved
Key wordstricyclic terpane ketones, tasmanite, molecular markers, tandem mass spectrometry
INTRODUCTION
Tasmanian tasmanite is of particular interest
because its bitumen is composed mainly of com-
pounds with the same tricyclic terpenoid (cleis-
tanthane) skeleton in all fractions analysed so far.
The saturated plus monounsaturated hydrocarbon
fraction is comprised primarily of the ubiquitous
extended tricyclic terpane series (Simoneit et al.,
1990; Aquino Neto et al., 1992; Revill et al., 1994)
and two less abundant series of D
9(11)
- and D
13(14)
-
tricyclic terpenes (Azevedo et al., 1995). The aro-
matic hydrocarbon fraction is characterized by
series of extended ring-C monoaromatic and minor
ring-B,C diaromatic tricyclic terpenoids (Azevedo et
al., 1990; 1992). The acid fraction contains a series
of extended saturated and monoaromatic tricyclic
terpenoid carboxylic acids (Azevedo et al., 1994).
Initially, the proposed biological percursor of the
tricyclic terpane series was tricyclohexaprenol, C
30
,
derived from cyclization of hexaprenol (Aquino
Neto et al., 1982; Ourisson et al., 1982). In this tas-
manite sample the tricyclic terpenoid series extends
to C
40
, which suggests a tricyclooctaprenol precur-
sor (Azevedo et al., 1995). Mapping the transform-
ation of these tricyclic terpenoids in sediments
could lead to a better denition of their biological
precursors and geological fate, thus aiding in the
search for the source organisms.
With this in mind, we report the identication of
a specic distribution of a series of extended tri-
cyclic terpanones in the ketone fraction of the bitu-
men from a Tasmanian tasmanite. To our
knowledge no data have been published on these
compounds in bitumen; however, some of these
ketones have been reported to be chemical oxi-
dation products of the kerogen from this tasmanite
(Simoneit et al., 1996).
EXPERIMENTAL
The sample preparation and extraction pro-
cedures were given elsewhere (Azevedo et al., 1992;
Simoneit et al., 1990). The ketone fraction was iso-
lated by thin-layer chromatography (TLC) on silica
gel using dichloromethane as eluent and cholestan-
2-one/lupan-3-one/cleistanthan-7-one as elution
standards. The band corresponding to the ketones
was scraped o the TLC plate after visualization
under UV-light (254 nm) and exposure to iodine
vapor.
The ketone fraction was analyzed by computer-
ized high resolution gas chromatographymass
spectrometry (HRGCMSC) on a Hewlett-
Packard 5987A quadrupole instrument, using linear
scanning (50500 Da, 1.87 s/decade), electron
impact ionization (70 eV), with a SE-54 capillary
column (25 m0.30 mm, d
f
=0.25 mm), helium as
the carrier gas, and temperature programming from
80 to 3008C at 88C min
1
.
The HRGCMSMSC (the combination of
high resolution gas chromatography with tandem
mass spectrometry) analyses were performed with a
Hewlett-Packard 5890 gas chromatograph con-
Org. Geochem. Vol. 28, No. 5, pp. 289295, 1998
# 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
0146-6380/98 $19.00 +0.00 PII: S0146-6380(97)00129-0
289
nected to a TSQ-70 (Finnigan MAT) mass spec-
trometer operated at 70 eV (CENPES/
PETROBRA

S). The system was used in the selected

reaction monitoring (SRM), the product scan
(daughter scan), and the precursor (parent) ion scan
modes. Transitions were from molecular ions m/z
(262 + 14n, n =0.19) to base peak (m/z 191).
Argon was used as the collision gas and the col-
lision oset voltage was 10 eV. The gas chromato-
graph was equipped with a fused silica capillary
column (30 m0.32 mm i.d.) coated with DB1701
(0.25 mm lm thickness). Operating conditions of
the GC oven were: 708C (1 min); 258C min
1
to
1508C; 1.58C min
1
to 2608C, and 2.08C min
1
to
3008C (isothermal for 10 min).
RESULTS AND DISCUSSION
The tricyclic terpane ketones are characterized by
their m/z 191 fragmentogram (Azevedo et al., 1996),
and are constituted mainly of the C
20
and C
23
pseu-
dohomologs (Fig. 1), but also show maxima at C
28
Fig. 1. (A) Total ion current (TIC) trace of the ketone fraction from Tasmanian tasmanite bitumen; (B)
m/z 191 fragmentation, key ion characteristic for tricyclic terpane ketone series.
D. A. Azevedo et al. 290
and C
33
. These ketones could be formed by oxi-
dation of the double bonds in the presumed precur-
sor, as illustrated in Fig. 2. This would explain the
essential absence of the C
21
C
22
, C
24
C
27
and C
29

C
32
tricyclic terpane ketones because the precursor
does not have a double bond at a suitable location
for their formation.
The mass spectra of two C
23
isomers of the tri-
cyclic terpane ketones series are shown in Fig. 3.
They are almost identical to the mass spectra of the
tricyclic terpane hydrocarbons, but the ketones with
the same molecular weight have higher relative
retention times in gas chromatographic analysis
(Fig. 4). The mass spectra consist mainly of M
.
+
and fragments (M0CH
3
)
+
, m/z 191 (base peak)
and m/z 261 or 259 (loss of the side chain at C-14).
No loss of H
2
O (M-18) as observed for n-methyl
ketones is found in these mass spectra. The m/z 191
Fig. 2. Proposed origin of the tricyclic terpane ketones.
Novel ketones in tasmanite bitumen 291
and 261 (or m/z 259) ions indicate that the ketone
group is not on the ABC rings. It is proposed that
mass spectrum (A) is for the 13b(H),14a(H)-C
23
tri-
cyclic terpane ketone and mass spectrum (B) is for
the 13a(H),14a(H) isomer (Fig. 3). This is based on
the stereoisomeric distribution and elution order in
gas chromatographic analysis as compared to the
results reported by Chicarelli et al. (1988).
The results of the analysis by HRGCMS
MSCSRM are shown in Fig. 4. The tricyclic
terpane ketone series is composed mainly of the C
20
member, the bb-, ab-, ba- and aa-C
23
stereomers,
the C-22 R/S ba- and R/S aa-C
28
and C
33
diastereo-
mers, with C
21
C
22
, C
24
C
27
, C
29
C
32
and higher
homologues in trace relative abundances. The
elution order of the C
23
tricyclic terpanones is the
Fig. 3. (A) Mass spectrum of a C
23
-tricyclic terpane ketone (proposed to be the 13b(H),14a(H)-confor-
mation; (B) mass spectrum of a C
23
-tricyclic terpane ketone (proposed to be the 13a(H),14a(H)-confor-
mation).
D. A. Azevedo et al. 292
same as reported by Chicarelli et al. (1988) for the
tricyclic terpanes.
The collision activated dissociation (CAD) mass
spectra, acquired in the product mode, of the C
20
,
C
23
and C
28
tricyclic terpane ketones are shown in
Fig. 5. Mainly the M
.
+, (M0CH
3
)
+
and the base
peak (m/z 191) are observed in these mass spectra,
except for the 13b(H),14b(H)- and 13a(H),14a(H)-
C
23
tricyclic terpane ketones, which like the aa-C
23
electron-impact mass spectrum [Fig. 3(b)], also
show an intense ion at m/z 259. This ion may be
the result of a McLaerty-type rearrangement
(Todd, 1991; McLaerty and Turec ek, 1993), as-
sociated with a methyl group loss. It is still unclear
why not all C
23
isomers show this fragmentation
(mass spectra B and D vs. C in Fig. 5).
CONCLUSIONS
Ketones of the extended tricyclic terpane series
were identied by HRGCMSC and HRGC
MSMSCSRM in the ketone fraction of a
Permian tasmanite bitumen from Tasmania,
Australia. They consist of the tricyclic C
20
terpane
ketone, the C
23
stereoisomers with the 13,14-bb, ab,
ba and aa congurations, the C
28
and C
33
diastereo-
Fig. 4. HRGCMSMSCSRM for the transitions m/z (262 + 14n, n = 019) to m/z 191: (A)
saturated tricyclic terpane series (standard); (B) tricyclic terpane ketone series.
Novel ketones in tasmanite bitumen 293
F
i
g
.
5
.
C
o
l
l
i
s
i
o
n
a
c
t
i
v
a
t
e
d
d
i
s
s
o
c
i
a
t
i
o
n
(
C
A
D
)
s
p
e
c
t
r
a
(
o

s
e
t

1
0
e
V
)
a
c
q
u
i
r
e
d
i
n
t
h
e
p
r
o
d
u
c
t
m
o
d
e
o
f
t
r
i
c
y
c
l
i
c
t
e
r
p
a
n
e
k
e
t
o
n
e
s
:
(
A
)
C
2
0
;
(
B
)
b
b
-
C
2
3
;
(
C
)
b
a
-
C
2
3
;
(
D
)
a
a
-
C
2
3
;
(
E
)
b
a
-
C
2
8
;
(
F
)
a
a
C
2
8
.
D. A. Azevedo et al. 294
mers with the C-22 R/S ba- and R/S aa congur-
ations with other trace homologues, and are charac-
terized by the m/z 191 fragmentogram. Their mass
spectra are identical to those of the tricyclic terpane
hydrocarbons, but they have longer relative reten-
tion times in gas chromatographic analysis.
Collision activated dissociation (CAD) mass spectra
were acquired in the product mode to conrm the
C
20
, C
23
and C
28
tricyclic terpane ketones. The
important m/z 259 ion in the CAD mass spectra of
the bb- and aa-C
23
tricyclic terpanones may be the
result of a McLaerty-type rearrangement. The pro-
posed biological precursor of these ketone series is
a tricyclooctaprenolC
40
, derived from cyclization
of octaprenol in the tasmanites algae.
Associate EditorP. Farrimond
AcknowledgementsWe would like to thank Dr M. R.
Mello and Dr S. M. B. De Grande for HRGCMS
MSCSRM analysis in DIVEX/CENPES/
PETROBRA

S; CNPq and PETROBRA

S S.A. for a scho-

larship to D. A. Azevedo; Prof. H. Budzikiewicz, Dr T.
Peakman, Dr P. Farrimond and an anonymous reviewer
for their helpful comments and reviews.
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