UTTE OR H

Fuel Vol. 74 No. 10, pp. 1512-1521, 1995

E I N E”: A :N Copyright 0 1995 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0016-2361(!%)00116-6 0016-2361/95/$10.00+0.00

Natural occurrence of tetramantane

(Cz2Hz8), pentamantane (Cz6HS2) and
hexamantane (Ca0Ha6) in a deep petroleum
reservoir

Rui Lin and Zbigniew A. Wilk

Unocal Corporation, 376 S. Valencia Ave., P.O. Box 76, Brea, CA 92621, USA
(Received 20 December 1993; revised 2 February 1995)

A suite of petroleum polymantanes, including tetramantane, pentamantane and hexamantane, was

discovered in a gas condensate produced from a very deep (- 6800m below the surface) petroleum reservoir
located in the US Gulf Coast. This appears to be the first reported natural occurrence of these compounds.
Three isomers of tetramantane, four isomers of pentamantane and a number of their alkylated compounds
were identified using full-scan GC/MS analysis. Results from selective ion monitoring GC/MS analysis
suggest the presence of hexamantane. The polymantanes are associated with abundant lower
adamantologues, including adamantane, diamantane (congressane), triamantane and their alkyl-
substituted compounds. The genesis of polymantanes in petroleum is not known. It is speculated that
they may have been formed via homologation of the lower adamantologues at high pressure and
temperature in the reservoir. The lower adamantologues are believed to have been formed originally by the
catalytic rearrangement of tricycloalkanes during or after oil generation.

(Keywords petroleum;diamondoid;polymantanes)

Tetramantane (&H&, pentamantane (C26Hs2) and
hexamantane (Cs0H36) are the tetramer, pentamer and
hexamer, respectively, of adamantane (tricyclo[3.3.1. 13’7]
decane) (Ci0H16). Adamantane and its higher homo-
logues belong to a group of hydrocarbons commonly
known as diamond molecules or diamondoids because
their structures resemble that of diamond’-3. The carbon
skeleton of adamantane comprises the smallest repeating
units of the diamond lattice. It is made up of three rigidly
fused cyclohexane rings in an all-chair configuration,
enclosing space in the centre of the molecular structures.
Therefore, adamantane and its higher analogues are
also cage hydrocarbons4. The homologous series of
diamondoid hydrocarbons has the general molecular
formula C4n+6H4n+12? where n is an integer 2 1 (note
that there are non-isomeric polymantanes which do not
obey the above chemical formula)5.
The lower adamantologues, including adamantane,
diamantane and triamantane, each have only one isomer.
Depending on the spatial arrangement of the adamantane
units, higher polymantanes can have numerous isomers
and non-isomeric equivalents. Regular catacondensation
of the adamantane units gives rise to isomeric poly-
mantanes obeying the chemical formula C4n+ 6H4, + ,2. On
the other hand, irregularly cata-condensed and
peri-condensed polymantanes are not isomeric with the
cata-condensed compounds, and they obey different
chemical formulae5. All three possible tetramantanes are
isomeric, designated respectively as iso-, anti- and skew-
tetramantane, according to its similarity to butane
(Figure 1). Anti- and skew-tetramantanes each possess
two quatemary carbon atoms, whereas iso-tetramantane
has three6. There are seven possible pentamantanes, six
being isomeric (C26H32) obeying C4n+6H4n+i2 and one
being non-isomeric (C25H30)5. For hexamantane, there
are 24 possible structures. Among them, 17 are regularly
cata-condensed isomers with the chemical formula C30H36,
six are irregularly cata-condensed isomers with the
chemical fOimUla C2sHs4 and one iS peri-condensed with
the chemical formula C26H305.
Artificial synthesis of tetramantane in laboratory
conditions is tedious. So far, only anti-tetramantane has
been successfully synthesized via double homologation of
alkyl-substituted diamantanes2. Very little published
work is available on pentamantane and hexamantane.
Artificial syntheses of pentamantane and hexamantane
have not been accomplished, and these compounds only
exist theoretically. The structure of a conceptual isomer of
pentamantane (neopentamantane) is shown in Figure 2.
Also shown in Figure 2 is a partial structure of diamond to
demonstrate the structural similarity between the two
materials.
Diamondoid hydrocarbons which contain a mixture of
adamantane, diamantane (congressane), triamantane and
their alkyl-substituted compounds are present in a
number of petroleums3)7. Their concentrations in crude

1512 Fuel 1995 Volume 74 Number 10

 Natural occurrence
IseTetramantane Anti-Tetramantane SkewTetramantane
Figure 1 Carbon skeleton structures of the three isomers of
tetramantane
Neopentamantane Diamond
Figure 2 Carbon skeleton structure of neopentamantane and a partial
structure of diamond to demonstrate similarity
oils are minute, being of the order of several parts per
million’. The natural occurrence of tetramantane,
pentamantane and hexamantane has not been previously
reported.
The generation of oil and gas occurs when organic-rich
sedimentary rocks are exposed to increasingly higher
geothermal stress. Subsequently, oil- and gas-containing
fluids migrate out of the organic-rich rocks and are
trapped in porous or fractured rocks (reservoirs)9?‘0. On
exposure to even higher geothermal temperatures in the
reservoirs, the oil cracks progressively to form lighter
hydrocarbons. Eventually, only gas consisting
predominantly of methane is present in the reservoirs,
along with a carbon residue (pyrobitumen).
Although the occurrence of adamantane in oils was
known as early as 19338, its origin is still debated. It is not
certain whether adamantane is present in biological
systems. By analogy with the laboratory synthesis of
adamantane such as the processes described by Fort’ and
McKervey and Rooney6, Petrov et al.” suggested that
adamantane and alkyl-substituted adamantanes in
petroleum are formed by the catalytic rearrangement of
tricycloalkanes in the presence of Lewis acids.
Tricycloalkanes are widely present in oils. By hydro-
cracking tricycloalkanes isolated from oils, Petrov et al. l1
successfully converted 15-20 wt% to adamantane and its
analogues.
During the diagenesis and catagenesis of sedimentary
rocks, an appreciable amount of organic and inorganic
acids can be present. Temperatures from 100 to 230°C and
pressures greater than 68.9 mPa (10 000 psi) are reached in
geological systems. Under such conditions, rearrangement
of tricycloalkanes to adamantane would be facile’.
All diamondoid hydrocarbons display high thermal
stability and are resistant towards oxidation and
microbial degradation3. As a consequence, the processes
leading to the formation of adamantane and its analogues
can be considered irreversible. During the thermal cracking
of oil, the thermodynamically stable diamondoid
hydrocarbons become increasingly enriched in the residual
oil (or condensate).
Taking advantage of their high stability towards
thermal cracking, oxidation and biodegradation, the
of petroleum polymantanes: R. Lin and 2. A. Wilk
geochemical utility of diamondoids in petroleum explora-
tion and production is potentially very versatile.
Diamondoids may be used to determine the thermal
maturity level of a thermogenic gas and condensate,
which is often difficult using routine geochemical
techniques. The compounds may also be used to assess
the degree of thermal chemical sulfate reduction and
concurrent hydrocarbon oxidation, which are believed to
be the processes leading to the formation and accumula-
tion of sour (H*S-rich) gases12-14. It is believed that the
n-alkanes are relatively more susceptible to oxidation (as
a result of thermochemical sulfate reduction) than
diamondoids. Therefore, the ratio of n-alkanes to
diamondoids is a good indicator of the level of
hydrocarbon oxidation (and concurrent thermochemical
sulfate reduction). Similarly, the ratios can also be used to
determine the extent of oil biodegradation, since micro-
organisms are known to attack preferentially the n-
alkanes but not the diamondoids.
Here we report the first discovery of a suite of
tetramantane, pentamantane and hexamantane com-
pounds in natural occurrence. They are found to be in
association with natural gas in a deep petroleum reservoir
(6800m below the surface). The tetramantane and
pentamantane compounds are identified on the basis of
their mass spectra using full-scan gas chromatography/
mass spectrometry (GC/MS). Selective ion monitoring
(SIM) GC/MS was used to identify tentatively the
presence of hexamantane compounds. Geochemical
processes leading to the formation of tetramantane and
pentamantane in the petroleum reservoir are speculated.
EXPERIMENTAL
Sample
A stock-tank condensate was collected from a well
located in the Mobile Area offshore Alabama and
Mississippi, in the northern Gulf of Mexico, USA. The
well produces mainly natural gas from the Jurassic
sandstone of the Norphlet formation approximately
163 million years of age. Condensate production from
the well is very small, at a rate of approximately
1.68m3 of hydrocarbon liquid per 106m of gas (0.3
barrel per 106ft3). The condensate, light yellow in
colour, has an API gravity of 23 (specific gravity
0.92gmll’) and a viscosity (at 40°C) of 2.62mm2 s-l
(CST).
Instrumentation and conditions
GC was performed using a Hewlett-Packard Model
5890 gas chromatograph equipped with a flame ionization
detector. A 30 m x 0.25 mm i.d. DB-1 capillary column
with a 0.25pm film thickness was used. The injector
temperature was 350°C and the carrier gas was hydrogen.
The initial oven temperature was held at -20°C for 2 min
then increased to 350°C at 8°C mm’,
GC/MS was performed using a VG70/250SE mass
spectrometer equipped with a Hewlett-Packard Model
5890 gas chromatograph. A 30m x 0.25 mmi.d. DB-5
analytical capillary column with a 0.25 pm film thickness
was used. Helium was used as the carrier gas at a flow rate
of 1.1 ml min-’ . The GC/MS interface used was direct.
The injector temperature was 250°C. GC was carried out
using a temperature programme beginning at 35°C held
Fuel 1995 Volume 74 Number 10 1513
Natural occurrence of petroleum polymantanes: R. Lin and 2. A. Wilk

Table 1 Ion monitored and sampling times alkyl-substituted diamantanes (retention time 22.0-
Sampling time Delay time
28.0 min), (3) triamantane and alkyl-substituted triaman-
Channel m/r (ms) (ms) tanes (retention time 28.0-32.0min) and (4) tetra-
mantanes and alkyl-substituted tetramantanes (retention
1 239.1800 55 10 time 32.0-35.0min). Since a similar suite of lower
2 240.1878 55 10
3 (lock mass) 280.9824 45 10 adamantologues (adamantane, diamantane and triaman-
4 (check channel) 280.9824 45 10 tane) has been reported previously3, they will not be
5 291.2113 55 10 discussed in further detail here; we shall focus our
6 292.2191 55 10 discussion in this paper on the first discovery of
7 343.2426 55 10
8 344.2504 55 10
tetramantane, pentamantane and hexamantane.
The concentrations of pentamantane and hexamantane
compounds in the sample are so low that they are not
visible in the gas chromatogram (Figure 3). Nor could the
for 1 min, increased at 4°C min-’ to a maximum of 3 10°C pentamantane and hexamantane compounds be detected
and held there for 2 min. All mass spectra were acquired by observing the total ion chromatogram (TIC) from a
using 70 eV. full-scan GC/MS analysis. For this reason, distillation
Full-scan mass spectra were obtained at a resolution of was performed on the condensate sample to remove the
1000. The masses scanned were from m/z 50 to 500 in 1.Os relatively low-boiling non-diamondoid components and
with a 0.28s interscan time. SIM experiments were the lower adamantologues, and to concentrate tetra-
performed in the voltage-scanning mode. A resolution mantane, pentamantane and hexamantane compounds in
of 5000 was used for all SIM experiments. Low-boiling the residual fraction. After the distillation, the 343”C+
perfluorokerosene (PEK) was leaked into the ion source residual fraction was recovered and analysed using
continuously during SIM acquisition to allow for the use GC/MS. Ideally, separation of individual components
of a lock mass. The ions monitored and sampling times by preparative GC followed by infrared and NMR
are given in Table 1. spectroscopic characterizations is preferred. Given the
complexity of the components in the chromatogram
(Figure 3) (i.e. similarities of boiling points), the isolation
RESULTS AND DISCUSSION
of individual components is not practical. However, we
are continuing to pursue this approach, although
General discussion preliminary GC/IR results indicate that structural
Figure 3 is a partial gas chromatogram of the identifications are difficult to extract using this technique
condensate sample. In addition to the relatively low- owing to insufficient chromatographic resolution.
boiling non-diamondoid components, four clusters of peaks Figure 4 shows the TIC chromatogram obtained
are observed in the sample at a retention time longer than from the full-scan GC/MS analysis of the residual
14.8 min. Almost all peaks in the clusters are found to be distillation (343”C+) fraction. It is dominated by a
members of the diamondoid family. The four clusters cluster of peaks at between 22 and 32min representing
represent (1) adamantane and alkyl-substituted adaman- triamantane and alkyltriamantanes. A second cluster of
tanes (retention time 14.8-22.0 min), (2) diamantane and peaks between 32 and 40min is due to tetramantane

180

150

Adamantanes

I Diamantanes

60

Triamantanes

Tetramantanes

Time (minutes)

Figure 3 Gas chromatogram of the diamondoid-rich condensate sample showing clusters of peaks representing adamantanes, diamantanes,
triamantanes and tetramantanes

1514 Fuel 1995 Volume 74 Number 10

 Natural occurrence of petroleum polymantanes: R. Lin and Z. A. Wilk

100 r- -

60

!I i Triamantanes

Diamantanes

20 Tetramantanes

Pentamantanes

0
I .,I+ I I
1 30 15:oo 20:oo 25:oo 30:oo 35:oo 40:oo 45:oo 5r :oo
Time (minutes)

Figure 4 TIC chromatogram from the full-scan CC/MS analysis of the high-temperature distillation fraction (343”C+)

(a)

80 -

I I I I I I I I I

31 :oo 32:00 33:oo 34:oo 35:oo 36:00 37:oo 38:00 39:oo 40:oo 41 .oo
Time (minutes)

Figure 5 (a) m/z 292 mass chromatogram showing three prominent peaks representing the three isomers of tetramantane. (b) Partial TIC
chromatogram showing the tetramantane region

and alkyltetramantanes. Only a few peaks of penta- hexamantane (m/z 396) compounds was monitored. In
mantane and alkylated pentamantanes are observed from addition, the fragment ion of alkylated pentamantanes at
the TIC chromatogram after 40min (Figure 4). No m/z 395 was also monitored. All SIM analyses were
hexamantane is visible in the TIC chromatogram. performed at a resolving power of 5000 to minimize the
However, a closer look at the GC/MS SIM chromato- effect of any isobaric chemical interferences that may be
grams corresponding to the expected hexamantane present in the sample. In the case of hexamantane having
molecular weight do indeed indicate the presence of a molecular ion at m/z 396.2817, a SIM experiment
such compounds. For this reason, a SIM GC/MS analysis performed at a resolving power of 5000 will exclude ions
was performed on the same residual fraction of the from detection that are less than m/z 396.2024 or those
distillation, during which the molecular ion of that are higher than m/z 396.3610. SIM analysis also

Fuel 1995 Volume 74 Number 10 1515

Natural occurrence of petroleum polymantanes: R. Lin and Z. A. Wilk

100
serves to increase the sensitivity for the compounds
selected.
I=
Petroleum tetramantanes 90-
I 09
I
The lower adamantologues (adamantane, diamantane
and triamantane) all display extremely high molecular
stability3. Even under harsh electron impact conditions,
the mass spectra of the diamondoid compounds exhibit r
relatively little fragmentation. Therefore, the molecular .+T
s
S
ions are also the base peaks in the mass spectra of the 40-

unsubstituted diamondoid hydrocarbons. It is therefore

expected that the mass spectra of the three isomers of
unsubstituted tetramantane would also show a lack of 20 -
fragmentation. For this reason, we selectively scanned the
molecular ion at m/z 292 of the three isomers of
tetramantane, the SIM chromatogram of which is
shown in Figure 5a. Three prominent peaks are present 90 90 ml 120 140 190 190 2w 223 240
Ma
290 290 200 220 940 290 390

in the m/z 292 mass chromatogram, which may represent

the three isomers of the unsubstituted tetramantane.
In order to support the interpretation of the tetra-
mantane structure, the mass spectra of the three
corresponding peaks in the full-scan TIC trace were
analysed. Figure 5b shows a partial TIC chromatogram
displaying the tetramantane region with the main peaks
labelled A-K (for simplicity, the adamantane, diaman- 90

tane and triamantane regions are not displayed). The

mass spectra of peaks C, D (shown in Figure 6a and b) and
H, which correspond to the three prominent peaks in the SW
m/z 292 SIM chromatogram (Figure 5a), indeed suggest 5
.a
the presence of tetramantane structures. These mass :
spectra will be discussed in further detail below. In f 40

addition to the three unsubstituted tetramantanes, there

are alkyl-substituted tetramantanes present, as suggested
by their mass spectra. An example (peak B) is displayed in 20

Figure 6~2,showing a methyltetramantane structure.

The mass spectrum of peak C has a base peak at
m/z 292 (the molecular ion of tetramantane), whereas 0

all the fragment ions are very small (Figure 6a). The 90 90 Km 120 140 194 (90 200 220
M
240 290 290 300 220 340 290 380

molecular ion at m/z 292 and the relative lack of

fragmentation are consistent with the mass spectra of
the other adamantologues and further support the
interpretation of an unsubstituted tetramantane struc-
I-
ture for peak C. Although the lack of fragmentation is -1 !91
also characteristic of polycyclic aromatic hydrocarbons (c)
(PAHs), it is important to note that this molecular ion
does not correspond to any known unsubstituted PAHs
of the same mass commonly found in petroleum. This
is also true for the other polymantanes. The absence of
a significant abundance of multiply charged ions (e.g. M/2
species) further indicates that they are not PAHs.
Additional experiments including NMR and liquid
chromatography (LC) were performed to support 306
that these compounds are not PAHs. Specifically,
13C NMR data showed that over 95% of the distillate
fraction is composed of non-aromatic hydrocarbons.
Additionally, LC was used to separate the saturate
fraction from any possible aromatics. The saturate
fraction was then analysed by GC/MS, and the same
suite of compounds discussed in this paper was identified.
Indeed, the chromatogram of this fraction obtained by
GC/MS is identical with that for the distillate prior to LC
separation. This confirms that these compounds are not Figure 6 Mass spectra of (a) one of the three isomers of tetramantane
(peak C; note the lack of fragmentation in the mass spectrum), (b) a
aromatic. Peak C is then interpreted as one of the three second isomer of tetramantane co-eluting with a Cl- and a C2-alkyl-
isomers of unsubstituted tetramantane. Unfortunately, substituted tetramantane (peak D) and (c) a methyltetramantane
the relative retention order of the three isomers of (peak B)

1516 Fuel 1995 Volume 74 Number 10

 Natural occurrence of petroleum polymantanes: R. Lin and Z. A. Wilk

tetramantane is not known. It cannot be determined with
certainty whether peak C is iso- or anti- or skew-
tetramantane.
It is evident from the mass spectrum of peak D
(Figure 6b) that there was co-elution of more than one
tetramantane compound. The presence or co-elution of at
least three different tetramantane compounds can be
inferred on the basis of the mass spectrum. Five main ions
are present in the spectrum, including m/z 291, 292, 305,
306 and 320. The m/z 292, 306 and 320 peaks are likely
the respective molecular ions of (1) a second isomer of the
unsubstituted tetramantane, (2) a methyl-substituted
tetramantane and (3) a C2-alkyl-substituted tetra-
mantane. The m/z 291 and 305 peaks represent the
logical fragments of the methyl- and C2-alkyl substituted
tetramantanes and therefore support their identifications.
The peaks at m/z 29 1 and 305 can be easily understood as
resulting from the loss of alkyl groups from an alkyl-
substituted tetramantane. The peak at m/z 291 can arise
from either the loss of a methyl group from a
methyltetramantane or the loss of an ethyl group from
an ethyltetramantane, with contributions possible from
both, given the complexity of the chromatogram. The
peak at m/z 305 must be due solely to the loss of a methyl
group from a CZ-alkyl-substituted tetramantane as no
molecular ions for Cs-alkyl-substituted tetramantanes are
observed in this mass spectrum.
Similarly, the mass spectrum of peak H also shows
co-elution of more than one tetramantane compound. On
the basis of the mass spectrum observed, it is believed that
there are four tetramantane compounds co-eluting under
peak H. The base peak at m/z 292, for example, is
probably due to the third isomer of the unsubstituted
tetramantanes. Other peaks observed at m/z 306,320 and
334 are interpreted as arising from Ci-, CZ- and Cs-alkyl-
substituted tetramantanes, respectively. The peaks at m/z
291, 305 and 3 19 are the logical fragment ions of the
alkyl-substituted tetramantanes.
A summary of the tentative assignments of peaks in the
partial TIC chromatogram labelled A-K (Figure 5b) is
listed in Table 2. In addition to the three peaks (C, D and
H) discussed above, all the other labelled peaks show
fragmentation patterns indicative of the alkyl-substituted
tetramantane structures. For example, Figure 6c displays
the mass spectrum of peak B, which has a molecular ion at
m/z 306 and a base fragment peak at m/z 29 1. Since little
fragmentation is observed for the unsubstituted base
tetramantane structure owing to its high stability, it is
evident from the mass spectrum that peak B is a methyl-
substituted tetramantane. The strong base peak (i.e.
fragment ion at m/z 291) corresponds to the loss of a
methyl group from the methyltetramantane.
The presence of the tetramantane components observed
above raises the question of whether they could have been
formed during the relatively high-temperature distillation
process (343°C). However, we do not believe that this is
probable because the same suite of tetramantane com-
pounds are also found in the unprocessed condensate
sample.
Petroleum pentamantanes
Figure 7 shows a mass chromatogram at m/z 344 which
is characteristic of pentamantanes. Five distinct peaks
having good signal-to-noise ratios are observed. The full-
scan data confirm that these are indeed pentamantanes.
The five peaks which are labelled L-P in the mass
chromatogram (Figure 7) have mass spectra that are
consistent with the pentamantane and methylpenta-
mantane structures. The mass spectrum for peak L is
shown in Figure 8a, suggesting that the peak is a
methylpentamantane which has a molecular ion at m/z
358. Loss of the methyl group accounts for the base peak
at m/z 343. This mass spectrum is very consistent with
others described previously for diamondoids in that few
fragments are observed, indicating a high degree of
stability in the compound.
Peak M, the mass spectrum of which is shown in
Figure 8b, is clearly one of the isomers of unsubstituted
pentamantane. The molecular ion at m/z 344 is also the
base peak. In addition, little fragmentation is observed in
the mass spectrum, which is typical of unsubstituted
diamondoid compounds. Like the tetramantanes described
above, the elution of a methylpentamantane (peak L) is
observed prior to the unsubstituted pentamantane. The

Table 2 Tentative peak assignments of tetramantane and alky-substituted tetramantanes

Peak label Tentative assignment Molecular ion (m/z) Base peak (m/z)

A Cl-tetramantane 320 305

B Ct-tetramantane 306 291
C Tetramantane 292 292
D Tetramantane 292 292
Ct-tetramantane 306 291
C1-tetramantane 320 3051291”
E Cz-tetramantane 320 305
Cs-tetramantane 334 3 1s/305*
F Cz-tetramantane 320 291
Cs-tetramantane 334 3051291”
H Tetramantane 292 292
Cl-tetramantane 306 291
I Cz-tetramantane 320 305
C3-tetramantane 334 3 19/305O
J Ct-tetramantane 306 291
Cz-tetramantane 320 305/291
C3-tetramantane 334 319/305/291’
K Ct-tetramantane 306 291
Qtetramantane 320 305/291”
Cs-tetramantane 334 319/305/291a
’ Base peak cannot be determined with certainty owing to co-elution of more than one compound

Fuel 1995 Volume 74 Number 10 1517

Natural occurrence of petroleum polymantanes: R. Lin and 2. A. Wilk

vl

52:oo 5,
Time (minutes)

Figure 7 m/z 344 mass chromatogram showing the presence of pentamantanes

1 (a)
Sm
E
358
.a
I
=

!
40-

20-

360380

loo

(cl (d)
so- 80

Srn Sm
5 B

I 40- -1 40

20- 20

Figure 8 Mass spectra of (a) a methylpentamantane (peak L), (b) an isomer of unsubstituted pentamantane (peak M), (c)a second isomer of
unsubstituted pentamantane (peak N) and (d) an unsubstituted pentamantane and a methylpentamantane

1518 Fuel 1995 Volume 74 Number 10

 Natural occurrence of petroleum polymantanes: R. Lin and 2. A. Wilk

Table 3 Tentative peak assignments of pentamantane and methylpentamantanes

Peak label Tentative assignment Molecular ion (m/z) Base peak (m/z)

L Methylpentamantane 358 343

M Pentamantane 344 344
N Pentamantane 344 344
0 Pentamantane 344 344
Methylpentamantane 358 343
P Pentamantane 344 344

80

=-. 60
5
E
S 40

20

0
52:00 54:oo 56:OO 58:OO l:oo:oo

lime (minutes)

Figure 9 Expanded mass chromatogram of (a) M/Z 396 and (b) m/z 395 indicating the presence of hexamantane and substituted hexamantanes

peak labelled N is also an unsubstituted pentamantane
showing a base peak at m/z 344 (Figure 8~) with no
significant fragmentation. Note that the intensities of the
fragment ions in the mass spectra of the two unsubstituted
pentamantanes (Figure 8b and c) are different; this is
presumably due to their dissimilar spatial configurations of
the basic adamantane cages.
Peak 0 is actually due to co-elution of at least two
pentamantanes, based on its mass spectrum (Figure 8d).
The mass spectrum shows masses consistent with the
presence of an unsubstituted pentamantane and a
methylpentamantane. The molecular ion at m/z 358 and
a peak at m/z 343 (resulting from the loss of a methyl
group) are easily observed to arise from a methyl-
pentamantane. Also, the mass fragment at m/z 344 is
readily observable and is indicative of yet another
unsubstituted pentamantane. The mass spectrum of
peak P, showing a base peak at m/z 344, indicates the
presence of the fourth unsubstituted pentamantane. A
summary of peak assignments for the pentamantane and
substituted pentamantanes is listed in Table 3.
Petroleum hexamantanes
As mentioned earlier, the concentrations of hexa-
mantane compounds are very low and they could only
be detected using SIM CC/MS analysis of the
343°C + distillation fraction. For this reason, no full-
scan mass spectra of the hexamantanes are available. An
attempt was made to detect them using SIM at a resolving
power of 5000 to enhance both selectivity and sensitivity.
The high-resolution SIM data combined with retention
time data allow a strong case to be made for the presence
of these compounds. Currently no hexamantane standard
is available to make the identification completely
unambiguous, and therefore the assignments of the
hexamantane compounds to be discussed below are
made on the basis of the SIM mass chromatograms and
the relative retention times observed.
In the SIM analyses, the masses chosen for monitoring
correspond to ions expected for hexamantane and
alkylhexamantanes, and include m/z 396 and 395,
respectively. Figure 9a and b show the partial mass
chromatograms of the ions at m/z 396 and 395 showing
the hexamantane and alkylhexamantane region, respec-
tively. It is observed that seven of the peaks (shaded) in
the m/z 396 mass chromatogram (Figure 9~) are more
intense than the corresponding peaks (also shaded) in the
m/z 395 mass chromatogram (Figure 9b). These peaks are
inferred to represent seven possible isomers of unsub-
stituted hexamantane. This is reasonable considering that
there are 24 possible isomeric structures for unsubstituted
hexamantane5. The unshaded peaks, which are relatively
stronger in the m/z 395 trace (although the absolute
intensities are very weak owing to low concentrations),
probably arise from the alkyl-substituted hexamantane
structures.

Fuel 1995 Volume 74 Number 10 1519

Natural occurrence of petroleum polymantanes: R. Lin and Z. A. Wilk

R’=H
g$bFib anti
(Triamantane) (Ethyl-dimethyltriamantane) (Anti-tetramantane)

Figure 11 Homologation of triamantane into tetramantane

R* = R3 = C, unit

R* = H
+ /
R1 = R3 = C, unit
R3
,p’ R3 = H
R’ = R* = C, unit
f!?\
069
skew
Figure 10 Schematic diagram showing the synthesis of tetramantane
via double homologation of alkyl-substituted diamantanes (after Burns
et aI.* )
Speculation on the origin of tetramantane,pentamantane
and hexamantane
It has been suggested that the lower adamantologues
including adamantane and diamantane can be formed
via the catalytic rearrangement of tricycloalkanes" .
Tricycloalkanes are present in most oils and are readily
available as precursors for the rearrangement to form
adamantane. However, for the higher adamantologues,
the process of rearrangement becomes a problem
because it is difficult to find large (>22 carbons)
polycyclic hydrocarbons with chemical formula
Cdn+6Hdn+i2. Moreover, polymantanes are not known
to be present in living systems. In other words, it is
unlikely that the polymantane structures, including
tetramantane, pentamantane and hexamantane, could
have been inherited from sedimentary organic matter
(deposited remains of biological materials) during oil
generation.
Burns et aL2 developed a method to synthesize
polymantanes in laboratory conditions. They proposed
that it is possible to make a higher member of the
diamondoid family by adding two new rings with four
carbon atoms (single homologation) or a second higher
member by adding four new rings utilizing eight carbon
atoms (double homologation). Using this approach, the
authors successfully synthesized anti-tetramantane. A boiling points, are also present in nature.
schematic diagram of the synthesis of tetramantane
via the double homologation of alkyl-substituted
diamantanes is illustrated in Figure 10.
We propose a similar mechanism for the formation of
tetramantane, pentamantane and hexamantane via
homologation in the petroleum reservoir. As briefly
mentioned earlier, the gas condensate sample contains
abundant adamantanes, diamantanes and triamantanes
in addition to the tetramantane, pentamantane and
hexamantane. Most peaks of the lower adamantologues
(Figure 3) possess Ct-Cs alkyl and naphthenic (alicyclic)
substitutions. The formation of a higher member of the
diamondoid molecules can be accomplished by the
addition of one adamantane structure using the Cd alkyl
and naphthenic substitutions.
Figure II illustrates the process of homologation by
using the existing alkyl and naphthenic substitutions from
triamantane to tetramantane. The dashed lines suggest
the formation of an additional adamantane structure to
the triamantane structure. In the gas condensate sample,
significant quantities of Cd-substituted diamantanes and
triamantanes are present. Under the extreme high
pressure (over 137.9 mPa or 20 000 psi) and temperature
(over 200°C) conditions, it is speculated that the C4
substitutions can make an additional adamantane
structure to the diamondoid compounds, as suggested in
Figure II. As a result, a higher member of the diamondoid
molecule is formed.
The diamondoid molecules are in association with
abundant methane molecules, which can form alkyl
substitutions on the diamondoid structures. While direct
reactions between methane and diamondoid molecules
may be difficult, the presence of clays in the reservoir may
have provided the acid sites necessary to convert
polymantanes catalytically into polymantyl cations.
Subsequently, the cations can become alkyl substituted
by reactions with methane molecules. Some of the alkyl
substitutions may then undergo transformation to
naphthenic substitutions. The resulting alkyl- and
naphthenic-substituted diamondoid molecules can then
be converted into higher members of the diamondoid
family, tetramantane, pentamantane and hexamantane,
via the homologation process described above (Figure 11).
CONCLUSIONS
Polymantanes, including tetramantane, pentamantane
and hexamantane, are present in natural occurrence,
extending the diamondoid family from adamantane to
hexamantane. This study confirms the theoretical predic-
tions made by chemists’ that higher polymantane
structures are possible and that there are numerous
isomers of polymantanes. It is suspected that higher
analogues of polymantanes, although difficult to detect
owing to their low concentrations, large sizes and high
It is hoped that this study and others3’l1 on diamondoids
will create more opportunities for the geochemical
applications of these compounds in petroleum exploration
and exploitation, especially in determining the levels of (1)
thermogenic gas/condensate maturity, (2) thermochemical
sulfate reduction relating to the accumulation of sour
(H2S-rich) gases, and (3) biodegradation and oxidation of
reservoired hydrocarbons.
ACKNOWLEDGEMENTS
The authors thank Mr Al E. Freiberg and Mr Steven W.
Sperry, both of Unocal Corporation, for the collection of
the gas condensate sample. They also acknowledge Mr
Gregory P. Ouellette for the preparation of the

1520 Fuel 1995 Volume 74 Number 10

 Natural occurrence of petroleum polymantanes: R. Lin and Z. A. Wilk

diamondoid-rich condensate and Mr Richard L. Sloggy
for obtaining some of the analytical results. They thank
Drs John R. Fox and Gary C. Graham and the Unocal
management for their approval to publish this work. They
are grateful that Dr Joseph A. Curiale constructively
reviewed and therefore improved this paper.
REFERENCES
1 Fort, R. C. ‘Adamantane: The Chemistry of Diamond
Molecules’, Marcel Dekker, New York, 1976
2 Bums, W., McKervey, M. A., Mitchell, T. R. B. and Rooney, J. J.
J. Am. Chem. Sot. 1978,100,906
3 Wingert, W. S. Fuel 1991, 71, 37
4 Schleyer, P. W. R. in ‘Cage Hydrocarbons’ (Ed. G. A. Olah),
Wiley, New York, 1991, p. 1
Balaban, A. T. and Schleyer, P. v. R. Tetrahedron 1978, 34,
3599
McKervey, M. A. and Rooney, J. J. in ‘Cage Hydrocarbons’ (Ed.
G. A. Olah), Wiley, New York, 1991, p. 39
Hala, V. S. and Landa, S. Erdiil Kohle Erdgm Petrochemie 1966,
19, 727
Fort, R. C. and Schleyer, P. v. R. Chem. Rev. 1964,&l, 277
Hunt, J. M. ‘Petroleum Geochemistry and Geology’, Freeman,
New York, 1979
Tissot, B. P. and Welte, D. H. ‘Petroleum Formation and
Occurrence’, Springer, New York, 1984
Petrov, A. A., Arefjev, 0. A. and Yakubson, Z. V. in ‘Advances
in Organic Geochemistry’ (Eds B. P. Tissot and F. Bienner),
Editions Technip, Paris, 1974, p. 517
12 Orr, W. L. AAPG Bull. 1974,58,2295
13 Krouse, H. R., Viau, C. A., Elius, L. S., Ueda, A. and Halas, S.
Nature (London) 1988,333,415
14 Wade, W. J., Hanor, J. S. and Sassen, R. Trans. GulfCoast Assoc.
Geol. Sot. 1989, 39, 309

Fuel 1995 Volume 74 Number 10 1521