Org. Geochem. Vol. 18, No. 6, pp. 791- 803, 1992 0146-6380/92 $ 5 . 0 0 + 0 .

0 0
Printed in Great Britain. All rights reserved Copyright 1992 Pergamon Press Ltd
Organic geochemistry of geographically unrelated tasmanites*
F. R. AQUINO N~TO, I J. TRIGOIS, 2 D. A. AZEVEDO, ~ R. RODRIGUES 2 and B. R. T. SIMO~Srr 3
J Instituto de Qulmica da UFRJ, Ilha do Fundfio, CT, Bloco A, Sala 607, 21945, Rio de Janeiro, Brazil,
2Cenpes / Di vex/ Segeq/ PETROBRAS, Ilha do Fund.~o, Quadra 7, 21910, Rio de Janeiro, Brazil and
3petroleum Research Group, College of Oceanography, Oregon State University, Corvallis, OR 97331,
U.S.A.
(Recei ved 13 January 1992; accepted in revised f o r m 19 June 1992)
Abstract--The biomarker analysis of three tasmanite rock samples from Tasmania, Alaska and Brazil
showed an unusually high tricyclic terpane concentration relative to hopanes and steranes. A possible
product-precursor relationship is advanced, associating Tasmanaceae algae with these tricyclic terpanes.
These results support the search of possible precursor molecules in present day organisms which may be
taxonomically related to these algae.
Key words- - t ri cycl i c terpanes, biomarkers, algae
INTRODUCTION
Sediments containing t a s ma n i t e s - t y p e microorganisms
are very common in the geological record. Usually
these organisms occur dispersed with other organic
remains which complicates the study of their compos-
ition. Certain modern organisms have been postulated
as descendants of these unicellular fossil organisms,
thought to be algae by some authors (Burlingame
e t al . , 1969; Tappan, 1980 and references therein).
Wall (1962) proposed a possible close affinity between
Tasmanian t a s ma n i t e s and present day Pa c h y s p h a e r a
p e l a g i c a Ostenfeld (1899) and other species of
Pachysphaera. Wall (1962) suggested that t a s ma n i t e s
could be classified in the class Chlorophyceae.
Combaz (1966, 1967) reached similar conclusions
while analyzing Saharan samples. Simoneit and
Burlingame (1973) suggested that these organisms
could be spores of green algae, and Sargeant (1989)
also suggested that these unicellular organisms could
be green algae (i.e. zoosporongia of Prasinophycean
algae). A detailed classification of Brazilian Tasman-
aceae has been put forward by Sommer and Bockel
(1967).
Massive concentrations of these organisms in geo-
logical sediments are rare, the best known example
being the Tasmanian tasmanite (for a comprehensive
review of t a s ma n i t e s s ee Cane, 1974 and Muir and
Sargeant, 1971). Other occurrences, such as the
Alaskan (Tourtelot e t al . , 1967) and Saharan
(Combaz, 1966) tasmanites, have also been reported.
Recently, we have found some t a s ma n i t e . r i c h
sediments in the Amazonia area of Brazil.
The molecular composition of these materials has
been studied by several authors. Hydrocarbon analysis
*Presented at the 14th International Meet i ng on Organic
Geochemistry, Paris, France, 18-22 September 1989.
showed a normal alkane distribution in Alaskan
samples and a peculiar distribution for Tasmanian
samples, with an abundance of a Ci9 alkyi-substituted
tricyclic alkane (Cane, 1974). Carboxylic acid analysis
from extracts and kerogen oxidations showed the
presence of normal acids as well as keto, aromatic,
mono and dicarboxylic acids, including tricyclic carb-
oxylic acids (Burlingame e t aL, 1969; Simoneit and
Burlingame, 1973). The aromatic acids were related
to phenanthrenes. Pyrolysis and hydrogenation of
Tasmanian tasmanite alginite yielded alkyl-substituted
cyclohexanes and a series of tricyclic and tetracyclic
alkanes with unknown structures (Philp e t al . ,
1981). A probable triterpane-like A,B-ring structure
was proposed for the tricyclic series based on mass
spectrometric data.
We have found that Tasmanian tasmanite hydro-
carbons consist mainly of several C~9 and C20 tricyclic
terpanes (Grimalt e t al . , 1988; Simoneit e t aL, 1990)
together with structures related to the now ubiquitous,
extended tricyclic triterpane series (Aquino Neto e t al . ,
1982, 1983; Heissler e t al . , 1984; Chicarelli e t al . ,
1988). The aromatic fraction is composed primarily
of ring-C aromatic tricyclic terpanes (Azevedo e t al . ,
1992; Simoneit e t al . , 1990).
The purpose of the present work is to verify whether
this unique lipid composition is a characteristic of
these fossil organisms, irrespective of geological
occurrence. I f this is shown to be the case, then, for
the first time, a direct connection between tricyclic
terpanes and a precursor organism will have been
established.
EXPERI MENTAL
After washing with dichloromethane, the samples
were powdered in an agate mort ar and extracted at
least four times with dichloromethane/methanol (9: I)
791
792 F.R. AQUINO NF.TO et al.
in an ultrasonic bath. The solvent was removed from
the extracts by rotary evaporation and the resulting
bitumens were fractionated with hexane on silica gel
60 TLC plates (20 x 20 era, 0.25 ram). Visualization
under u.v. light (254nm) allowed the isolation of
saturated hydrocarbons, aromatic hydrocarbons,
and resins plus asphaltenes. The saturate fractions
of the Alaskan and Brazilian samples were further
fractionated by urea adduction. The hydrocarbon
fractions were analyzed by high resolution gas
chromatography (HRGC) on a SE-54 capillary
column (35 m x 0.30 mm, d r - 0.35 #m) using hydro-
gen as carrier and temperature programming from
50 to 280C at 3C/rain. The same chromatographic
conditions were used for HRGC-mass spectrometry
(MS) analysis on a Hewlett-Packard-5987A quadru-
pole instrument, using linear scanning (50-500 dalton,
1.87 s/decade) and electron impact ionization (70 eV).
Multiple ion detection (MID) analyses were also
performed when the concentration of key compound
families was low. The biomarkers were identified by
comparison of the mass spectra and GC retention
index with those of standards and previously published
data (Anders and Robinson, 1971; Aquino Neto
e t al . , 1982, 1983; Moldowan e t al . , 1983; Rodrigues
e t al . , 1987; Zumberge, 1983).
Stable carbon isotope analyses were carried out
on demineralized whole rock and bitumens, using a
continuous oxygen flow combustion line. The evolved
CO2 was analyzed with a Finnigan Delta E mass
spectrometer and the results expressed in 613C (%0)
values relative to PDB standard.
For vitrinite reflectance, Ro, measurements the
crushed rock was prepared as a scatter mount in a
polyethylene mold. A cold setting methyl methaerylate
("Metset") resin and hardener were mixed (50:1),
poured into the molds, and allowed to set (about 1 h).
After sample polishing Ro values were measured in a
Zeiss Standard Universal reflected light microscope
fitted with a photomultiplier. The illumination was
provided by a stabilized 12 V high-intensity tungsten
filament lamp, filtered to ensure incidence of mono-
chromatic green light (546 nm). The oil objective
lens used (magnification 40) had a reflective index of
1.518 (n) at 23C. The polished blocks used for
vitrinite reflectance measurements were also used for
the observation of the fluorescence of the macerals
under ultraviolet light.
Kerogen isolation was carried out by breaking
the rock into 3-5 mm particles and washing under
ultrasonic agitation for about 1 min with methanol to
remove the excess soluble organic matter. Carbonates
were removed with HCI (20%) and demineralization
was performed with HF (40%). The neutral, washed
residue was ultrasonicated with 2ml of ZnBr2
solution (2.0 g/era 3) and centrifuged for 10min at
1700 rpm. After washing, the supernatant kerogen
concentrate was dried in a vacuum oven at 30C.
GEOGRAPHI CAL DI STRI BUTI ON
OF THE SAMPLES STUDI ED
The samples were purposely selected from widely
different geographical and age settings.
The Tasmanian tasmanite (Upper Permian) sample
was collected by T. C. Hoering and B. R. T. Simoneit
in an abandoned shale mine on the Mersey River,
3 miles south of Latrobe, Tasmania, Australia
(latitude 4117'S, longitude 14628'E and elevation
~35m) .
The Alaskan tasmanite (Triassic) sample was
obtained at 6 8 3 7 " 3 0 " N and 15822'30"W (U.S.
Geological Survey field number 65 ADL 8) by H. A.
Tourtelot.
The Brazilian tasmanite (Upper Devonian) core
samples are from the Amazon Basin, from strata
situated between 1072 and 1075.5m of a well
designated 2-UM-1-AM (220'47"S, 5842'57"W).
Tabl e 1. Gener al feat ures and anal yt i cal results for the t asmani t e sampl es
Sampl e l ocat i on
Feat ur e Tas mani a Al as ka Brazil
Geol ogi cal age Per mi an Lat e Jurassi c/ Devoni an
Ear l y Cret aceous
Range of tasmanites sizes ( #m) 472-690 290-523 290-559
Tasmanttes i ndi vi dual s/ ram of sediment* appr ox. 25 appr ox. 80 appr ox. 10
Est i mat ed mat ur at i on level ( R, , %) t 0. 3-0. 4 0. 5- 0. 6 0. 5-0. 6
% Al gi ni t e of amor phous or gani c mat t er ~ 80 ~ 100 ~ 25
Ot her recogni zabl e or gani c remai ns none none 10- 20%
acr i t ar chs
Tot al or gani c car bon ( %) 20. 16 28. 69 9.73
Ext r act yield (g/ g TOC) 138 - - - -
Bi t umen fract i ons ( %)
Sat ur at e 19.8 2.6 - -
Ar omat i c 15.2 12.8 - -
N, S a nd O c ompounds 49. 4 28.2 - -
Asphal t enes 15.6 56.4 - -
6 ~3C of demi neral i zed whol e r ock (Y~, vs PDB) - 13.86 - 14.41 - 30. 74
(%,, vs PDB)
613C of the or gani c ext r act (%., vs PDB) - 11.37 - 2 7 . 2 0 - 2 8 . 8 0
(gh, vs PDB)
*Measur ed perpendi cul arl y t o t he deposi t i onal pl ane, see Pl at e I.
1"In the absence of vitrinite and spores, onl y or gani c mat t er col or at i on and algal fluorescence col ors were
used t o i nfer the mat ur at i on levels.
793
Organic geochemistry of geographically unrelated tasmanites 795
RESULTS AND DISCUSSION
Description of the samples
Table 1 shows some typical data for the
tasmanites analyzed. Microscopic observation of the
samples shows the dense packing of the cells in
the Alaskan and Tasmanian samples, while the
individual cells are more isolated in the Brazilian
sample (Plate 1). During kerogen preparations, the
aggregation of the cells resulted in their extensive
breakage, yielding mostly fragments in the samples
from Alaska and Tasmania. On the other hand,
well-preserved whole cells were obtained in the
kerogen concentrate from the Brazilian tasmanite.
The tasmanites present in the Brazilian tasmanite
can also be assigned as tasmanites punctatus. Other
recognizable organisms in this sample are acritarchs
(Table 1).
A
Normal alkanes
Pregnane
+ Alkyl-cyclohexanes
o Isoprenoids
co Alkyl-methyl-cyclohexanes
Tricyclic terpanes
B
4 2 '
4 2 *
a t J 4 M " 4 |
$2 M | 4 4
. , t l l i ' k g L I . ' : ' .
, I . lL~b..i . b~ l A i b l i F - r " q l ~ h _ -
t R ( m i n )
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Monoaromatic tricycli terpanes
A1kyl-phenanthrenes
2 '
2 ' I '
$1 a t $
H i / I S 2 ' 4 I I
h e
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Fig. 1. HRGC traces of the hydrocarbons from Tasmanian tasmanite. A--Saturate fraction; B---aromatic
fraction (for peak identification see Appendix and for conditions see experimental).
796 F. R. AQUINO NETO et al.
B i o ma r k e r s
The molecular composition of the saturates and
aromat i c fractions can be discerned in the GC and
GC- MS dat a shown in Figs 1-6. The numbers and
symbols referring to peaks in the gas chromat ograms
and mass fragmentograms are related to the com-
pound structures given in the Appendix. Several
series of compounds are present, but they do not
occur in every sample in the same relative amount s
(cf. Table 2).
Nor mal alkanes, alkylcyclohexanes, alkylphen-
anthrenes and tricyclic terpanes are the only series
present in all three tasmanites. What is rather unusual
is the high abundance of the tricyclic terpanes over
hopanes and steranes in the three samples. I n effect,
the Tasmani an sample is constituted of only tricyclics
(Fig. 4). The Alaskan sample has a tricyclic to hopane
ratio of l : l and the Brazilian sample about 3:1
(Figs 5 and 6).
The presence of simple biomarker distributions
in geological samples is usually associated with
immature sediments. I n more mature samples,
hydrocarbon generation usually dilutes this initial
biologically related fingerprint, shifting the pattern to
a more typical petroleum-like distribution.
A 5,
87
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B
Normal alkanes
~ Pregnane, methyl-pregnane
+ Alkyl-cyclohexanes
Isoprenoids.
CO Alkyl-methyl-cyclohexanes
D
m m 40
m +& 71
I ~ I I I I
3 0 5 0 6 0 7 0 8 0
t R ( r a i n )
17
Alkyl-phenanthrenes
o Alkyl-chrysenes
IQ
r ~
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Fig. 2. HRGC traces for the hydrocarbons from Alaskan tasmanite. A--Saturate fraction; B---aromatic
fraction (for peak identification see Appendix and for conditions see Experimental).
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Organic geochemistry of geographically unrelated tasmanites
Table 2. Relative molecular composition of the saturate and aromatic
fractions of the three tasmanites studied, based on the total ion current traces
(TIC) o r m/z 191 and 217 mass fragmentograms
Relative occurrence based on the TIC
Compound classes Tasmania Alaska Brazil
Tricyclic terpanes* + + + + + + + + +
Hopanes* - - + + + Tr.
Steranes C27--Cff[" Tr. Tr. Tr.
Alkylcyclohexanes + + + + + +
Methylalkylcyclohexanes + - - + +
Normal alkanes + + + + + + + +
Acyclic isoprenoids - - + + + + + + +
Ring-C monoarom, tricyclics + + + + - - - -
Alkylbcnzenes
C~-alkylbenzenes + + - - + + +
C2-alkylbenzenes + + - - __
C3-alkylbenzenes - - __ +
Alkyltetralins + + - - + +
Alkylnaphthalenes + + + + +
Alkylphenanthrenes + + + + + + + + + +
Alkyldibenzothiophenes - - - - + +
Alkylchrysenes - - + + + +
Alkylpyrenes - - - - Tr.
Perylene - - + - -
Tr. = traces.
* = Based on m/z 191.
~" = Based on m/z 217.
799
I n t he case of Ta s ma n i a n t a s ma ni t e , t he co-
oc c ur r e nc e of a b u n d a n t t asmani t es a n d a b u n d a n t
t r i cycl i c t e r pa ne s suggest s a pr e c ur s or ( o r g a n i s m) -
p r o d u c t ( bi oma r ke r ) r e l a t i ons hi p (see al so Si mone i t
et al., 1986, 1990, 1992). The o t h e r t wo s ampl es ar e
mo r e ma t ur e , s howi ng a c ompl e x p a t t e r n e ve n af t er
r e mova l o f t he n - a l k a n e s by ur e a a dduc t i on. Ho w-
ever, t he unus ua l l y hi gh t ri cycl i c t o h o p a n e r at i o a n d
t he essent i al a bs e nc e o f s t er anes , r ei nf or ces t he pr o-
pos ed t asmani t es-t ri cycl i cs c onne c t i on. The unus ua l
a b u n d a n c e o f al kyl cycl ohexanes a n d al kyl benzenes i n
t hes e s e di me nt s suggest s t h a t t hes e c o mp o u n d s coul d
al so be char act er i s t i c p r o d u c t s of t hes e or ga ni s ms .
The e s t i ma t e d vi t r i ni t e r ef l ect ance val ues gi ven i n
Ta bl e 1 f or t he Ta s ma n i a n t a s ma n i t e r ei nf or ce t he
evi dence t h a t t hi s s a mpl e is mo r e i mma t u r e t h a n t he
ot he r t wo. The i s ot opi c val ues f or t he Ta s ma n i a n
t a s ma ni t e ( Ta bl e 1) ar e not cl ose t o t hos e f or t ypi cal
r ecent ma r i n e al gae a n d t hey devi at e si gni f i cant l y
f r o m t he n o r m o f Pe r mi a n ma r i n e or ga ni c ma t t e r .
Thi s ma y i ndi cat e bi os ynt hes i s of t hes e t asmani t es
u n d e r b l o o m c ondi t i ons ( Si mone i t et al., 1992). The
t3C d a t a f or t he Al a s k a n a n d Br azi l i an s ampl es ar e
mo r e negat i ve, a n d ar e t hus s i mi l ar t o t hos e nor ma l l y
f o u n d i n b i t u me n f r om ma t u r e ma r i n e shal es wi t h
al gal affi ni t i es ( Degens , 1969).
CONCLUSIONS
Tr i cycl i c t e r pa ne s ar e t he p r i ma r y b i o ma r k e r s i n
Ta s ma n i a n t a s ma ni t e .
Al a s k a n a n d Br azi l i an t a s ma ni t e s al so ha ve
r el at i vel y hi gh a mo u n t s o f t ri cycl i c t er panes .
A r e l a t i ons hi p be t we e n t asmani t es a n d t ri cycl i c
t e r pa ne s is p r o p o s e d a n d a ppe a r s t o cor r el at e wi t h
t he c o mp o s i t i o n a l de s c r i pt i ons of t he ma c e r a l s i n
t hes e s edi ment s .
A s ear ch f or t ri cycl i c t e r pa ne pr e c ur s or s s houl d
be pur s ue d i n pr e s e nt da y mi c r oor ga ni s ms r el at ed t o
tasmanites.
Acknowledgements--We t hank FI NEP and CNPq for
financial support, PETROBRAS for permission to publish
this work, and M. A. McCaffrey, R. N. Leif and T.
Aboul-Kassim for their comment s which greatly improved
the manuscript.
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Appendix opposite
Organic geochemistry of geographically unrelated tasmanites
A P P E N DI X
Structures of Biomarkers Identified
1. C18H26 2. CtgH2s 3. C20H30
5. C23H36
6. C24H3s
4. C22H34
7. C27H ~
11. C~oHso
/ ~ 13. C33H ~
801
Continued overleaf
802 F.R. AQUINO NEro et al.
15. C14Hlo 16. C15H12 17. C16H14 18. C17H16
19. C18Hls 20. C18H12 21. C19H14 22. C2oH16
23. C23H34 24. C18H22 25. C12H8S 26. Cl3Hio S
27. C14H12S
31. C14It2o
28. ChilI6
32. C13H14
33. C15HIs
42. C20H36 43. C21H38 44. C23H42
29. C13H18 30. C12H12
40. C20H36 41. C19H34
45. C~t t ~
Organic geochemistry of geographically unrelated tasmanites 803
46. C25H46
49. C22H38 50. C24H42
~ R
57. CIaH38 R = C3H 7
5S. C19H40 C4H9
59. C20I"I42 CsHI1
47. C~t 4a
48. C21H36
51. C13H28 R = H
52. C14H30 CH 3
53. C15H32 C2H5
54. C16H34 C3H 7
55. Cv/H36 C4H 9
56. C18H38 CsHll
61. C17H34 CH 3
62. C18H36 C2H 5
~
R
64. C17H~ CH 3
65. Cl sH~ C2H5
66. Cl~'13s C3H7
6% c~4o c4 ~
68. C21H42 CsHII
69. C22H44 C6H13
70. C23H46 CTHI5
71. C24H4a CsHt7