Organic Geochemistry 42 (2011) 566571

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

A novel method for isolation of diamondoids from crude oils for

compound-specic isotope analysis
Ling Huang a, Shuichang Zhang a,, Huitong Wang a, Xiaofang Fu b, Wenlong Zhang a, Yirui Xu a, Caiyun Wei a
a
Key Laboratory of Petroleum Geochemistry of PetroChina, Research Institute of Petroleum Exploration and Development (RIPED), PetroChina,
20 Xueyuan Road, Haidian District, Beijing 100083, China
b
College of Urban and Environmental Sciences, Peking University, Beijing 100871, China

a r t i c l e

i n f o

Article history:
Received 12 November 2010
Received in revised form 28 January 2011
Accepted 25 February 2011
Available online 4 March 2011

a b s t r a c t
A novel, effective and simple method based on adsorption chromatography on silica gel, adsorption on
molecular sieves, and inclusion in b-cyclodextrin (b-CD) was developed to separate and enrich diamondoids directly from crude oil. In this method, diamondoids ranging from adamantanes to triamantanes
were puried and isolated from the branched/cyclic hydrocarbon fraction of crude oil for further accurate
analysis of stable carbon isotope ratios (d13C) by gas chromatographyisotope ratio mass spectrometry
(GCirMS). A 5 mg/ml solution of b-CD stirred for 2 h was found to be sufcient for the inclusion of diamondoids and the inclusion complex completely breaks down by acidolysis in 1 mol/l hydrochloric acid
at 80 C for 16 h. The recovery of diamantanes was higher than that of other diamondoids. Our major
nding is that the specic inclusion effect between b-CD and diamondoids can be utilized to isolate
and concentrate diamondoid compounds from crude oil in a fast and effective way. It is a potential
method to yield the diamondoid fraction amenable for compound-specic isotope analysis (CSIA), which
markedly improves accuracy of molecular isotopic proxies of oiloil and oilsource correlation.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Diamondoids are a group of saturated cage-like hydrocarbon
compounds with a diamond structure formed by hydrocarbon
rearrangement reactions on acidic clay minerals in petroleum
source rocks (Peters et al., 2005; Wei et al., 2006b). They have
highly variable concentrations in crude oil (Dahl et al., 1999) and
occur predominantly as substituted and unsubstituted homologous series of lower diamondoids, including adamantanes,
diamantanes and triamantanes. These lower diamondoids are
common components of crude oil and extracts of coal and sedimentary rock. The higher diamondoid homologues with more than
three cages (including tetramantanes, pentamantanes, hexamantanes) are present only in trace amounts (generally less than
1 ppm) in crude oil (Wei et al., 2007a). The diamond-like structure
endows these molecules with unusually high thermal stability and
resistance to abiotic oxidation and biodegradation relative to other
crude oil components (Wingert, 1992; Lin and Wilk, 1995; Wei
et al., 2006a, 2007a). The concentrations and stable carbon isotope
ratios (d13C) of diamondoids are of particular interest in petroleum
geochemistry because they can provide a better understanding of
petroleum systems, especially for cracked and biodegraded oils.

Corresponding author. Tel./fax: +86 10 8359 8360.

E-mail address: sczhang@petrochina.com.cn (S.C. Zhang).
0146-6380/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.orggeochem.2011.02.010

For example, diamondoid parameters have been successfully used

to evaluate the degree of thermal evolution (Chen et al., 1996; Li
et al., 2000; Wei et al., 2006c, 2007b) and the extent of natural
oil cracking (Dahl et al., 1999). Combined with other biomarker
data, diamondoids also have been applied to characterize mixtures
of oil resulting from distinct migration pulses having different
maturity levels (Lin and Wilk, 1995).
In addition, d13C data of diamondoids can be used in oiloil or
oilsource correlation, especially in cases where the traditional
tri- to pentacyclic biomarkers, such as terpanes and steranes, are
absent due to thermal cracking or biodegradation. In fact, d13C
analysis of diamondoids has been regarded as one of the best
methods for correlation of oil with immature source rocks and is
almost the only geochemical method that can reliably identify different source rocks and source facies among immature source
rocks (Peters et al., 2005). It is known that some individual diamondoids were isolated from crude oil or gas condensate samples.
Adamantane was rst identied in the early 1930s in the heavy
Hodonin crude oil of eastern Czechoslovakia (Rollmann et al.,
1996). Landa and Hala (1958) and Mair et al. (1959) isolated adamantane by thiourea clathrates and azeotropic distillation, respectively. 1-Methyladamantane and 2-methyladamantane were
subsequently isolated from petroleum by thiourea clathrates and
preparative gas chromatography (Hala and Landa, 1966). Dahl
et al. (2003a) described the rst isolation and structural verication of higher diamondoids (C22 and higher polymantanes) and

L. Huang et al. / Organic Geochemistry 42 (2011) 566571

cyclohexamantane (Dahl et al., 2003b). However, those methods

required either initial samples with high concentrations of diamondoids or complex isolation conditions for each type of diamondoid, making it difcult to measure the d13C of individual
diamondoid in crude oil by gas chromatographyisotope ratio
mass spectrometry (GCirMS).
In the present paper, we report a novel method for the isolation
and concentration of diamondoids from crude oil for the GCirMS
analyses. The method is based primarily on adsorption chromatography on silica gel, adsorption on molecular sieves, and inclusion in
b-CD (Wang and Jiang, 2006). Based upon the chemical and physical properties of b-CD, we hypothesized that it would have a specic inclusion effect with the diamondoid series. The inuence of
some experimental conditions on diamondoid recovery, such as
the concentration of b-CD, inclusion time, and hydrolysis time
were systematically studied. Finally, the inuence of acidolysis
time and temperature for the isotope fractionation of diamondoids
was also studied.
2. Experimental

567

cyclohexane was used to elute the branched/cyclic hydrocarbons

fraction from the column.
2.5. Extraction of diamondoids by inclusion with b-cyclodextrin
The inclusion separation mechanism is shown schematically in
Fig. 1. In brief, approximately 20120 mg b-CD was dissolved in
20 ml deionized water (110 mg/ml), and then the branched/cyclic
hydrocarbon fraction solution was added. The mixed solution was
stirred for at least 2 h (magnetic stirrer). White precipitate formed
and was separated by centrifugation (2500 rpm for 10 min). The
precipitate was washed with cyclohexane (3  5 ml) before it
was transferred to 30 ml HCl solution (1 mol/l). The vial containing
diluted HCl solution was sealed and heated in an oven at 80 C for
at least 4 h to ensure the occurrence of b-CD acidolysis. After the
vial cooled, 10 ml cyclohexane was added to extract diamondoids
released from the inclusion complex. The cyclohexane phase was
washed with deionized water (3  10 ml) and appropriately
Na2SO4 was added to remove water in the cyclohexane phase. Finally, the sample solution was concentrated under a ow of N2
and placed in a 2 ml GCMS vial before analysis.

2.1. Materials
Silica gel (100200 mesh) was from the Qingdao Haiyang
Chemical Plant. ZSM-5 molecular sieve was the commercial product of Nankai University Catalyst Co., Ltd. Analytical grade b-CD
was puried in a recrystallization process and was purchased from
Sinopharm Chemical Reagent Co., Ltd. Chromatographic grade
cyclohexane was obtained from Thermo Fisher Scientic, Inc. Sodium sulfate (anhydrous, Na2SO4) and HCl were analytical grade
and from Beijing Chemical Works. Tricyclo[3.3.1.13,7]decane1,2,2,3,4,4,5,6,6,7,8,8,9,9,10,10-d16 (adamantane-d16) and diamantane were obtained from ISOTEC and Tokyo Kasei Kogyo Co. Ltd.,
respectively. The crude oil sample from the Tazhong 24 well in
the Tarim Basin came from section 44614483 m (the Ordovician
oil reservoir).

2.6. GCMS analyses

A Thermo Trace GC Ultra Gas Chromatograph interfaced to a
Thermo DSQ II Mass Spectrometer was used for all GCMS analyses. The GC was equipped with a 60 m J&W fused silica HP-5
capillary column (0.25 mm i.d.; 0.25 lm lm thickness of 5% phenyl-methylsilicone). Helium (He) was used as carrier gas at a constant ow of 1 ml/min. The oven temperature program was 50 C
for 5 min, 50160 C at 4 C/min and held at 160 C for 30 min,
then 160320 C at 6 C/min and held at 320 C for 15 min. The

2.2. Recrystallization of b-cyclodextrin

Approximately 100 g deionized water was added to a ask containing 19 g b-CD. The contents of the ask were stirred and heated
until the entire solid was dissolved. Vacuum ltration was used to
remove undissolved impurity when the solution was still hot. After
the ltrate cooled, b-CD precipitated. Vacuum ltration was used
to isolate the crystals, which were dried at 60 C for 24 h in a vacuum oven.
2.3. Silica gel liquid chromatography
The crude oil samples (100 mg) were separated using liquid
chromatography on activated silica gel (10 g, 180 C for 12 h).
The column length and diameter were approximately 200 mm
and 15 mm, respectively. The saturated hydrocarbon fraction was
eluted with cyclohexane (40 ml) and concentrated under a ow
of nitrogen (N2). A portion of the saturated hydrocarbon fraction
was used for gas chromatographymass spectrometry (GCMS)
analysis and the remaining fraction was subjected to ZSM-5 molecular sieving for further purication.
2.4. ZSM-5 molecular sieving liquid chromatography
The concentrated saturated hydrocarbon fraction was treated
with ZSM-5 molecular sieve (6 g, actived at 450 C for at least
8 h) column (200 mm length; 7 mm diameter) with an appropriate
N2 pressure for a convenient elution. Approximately 30 ml of

Fig. 1. Mechanism to isolate diamondoids from the crude oil based on inclusion
with b-CD.

L. Huang et al. / Organic Geochemistry 42 (2011) 566571

injection port temperature and transfer line temperature were

both 280 C. Samples (1 ll) were injected on-column using an
AS 3000 auto-sampler. The MS was operated at an ionization energy of 70 eV, a source temperature of 250 C, and scanning a
mass range of 50650 amu at a rate of about 0.4 s/scan or scanning in selective ion recording (SIR) mode, in which ions were
monitored at m/z 135, 136, 149, 163 and 177 for adamantanes,
m/z 152 for adamantane-d16, m/z 187, 188, 201 and 215 for
diamantanes, and m/z 239, 240, 244, 253 and 267 for triamantanes (Wei et al., 2006c). Adamantane-d16 was applied as an
internal standard and the internal standard method was adopted
to calculate concentrations of adamantane and alkyladamantanes.
Concentrations of diamantane and alkyldiamantanes were calculated according to their linear relationship established by measuring peak area ratios and concentration ratios of diamantane
standards in different concentrations and adamantane-d16 in constant concentrations.

3. Results and discussion

3.1. Isolation of diamondoids from crude oil

2.7. Stable carbon isotope analyses

(a)

(b)

Phytane

14

n-C18

n-C17

n-C16

Isodecane

Pentadecane

4
23

n-C15

n-C14

n-C13

Isononane

Abundance

Isooctane

n-C12

n-C11

The d13C values of diamondoids were measured using gas

chromatographycombustion isotope ratio mass spectrometry
(Thermo). All samples were rstly separated using a Thermo
Trace GC Ultra gas chromatograph equipped with an AS 3000
autosampler, a splitless injector, and a 60 m J&W fused silica
DB-1MS capillary column (0.25 mm i.d.; 0.25 lm lm thickness
of 100% methylsilicone). The oven temperature program was
50 C for 5 min, 50160 C at 4 C/min and held at 160 C for
30 min, then 160320 C at 6 C/min and held at 320 C
for 15 min. He was used as carrier gas at a constant ow of
1 ml/min. The injection port temperature was 300 C. After separation, the components were introduced into a combustion furnace (Thermo GC-combustion III Interface) where the carbon
content was converted to CO2. The temperatures of the oxidation
(NiO/CuO/Pt) and reduction reactors (Cu) were 980 C and 640 C,
respectively. The m/z 44, 45 and 46 ions were measured using a
Thermo DELTA V Advantage spectrometer and corresponding
ion signals were recorded and calculated by an ISODAT software
kit. An external reference solution containing n-C16H34,
n-C20H42, n-C24H50 and n-C28H58 alkanes was measured after
every 10 samples to enhance precision and reliability. The error
in the measurements was within 0.5.

n-C19

Native b-cyclodextrin is a cyclic oligosaccharide known to form

inclusion complexes in aqueous solutions with a variety of polar
and non-polar compounds, including aromatic hydrocarbons
(Chalumot et al., 2009) and heteroatomic compounds (Takashima
et al., 2006) in crude oil. The mechanism of complexation of cyclodextrins with guest molecules is a combination of CD-ring strain
release upon complexation, geometrical compatibility, van der
Waals forces, electrostatic and hydrophobic interactions and, in
some cases, hydrogen bonding between the cyclodextrin and the
guest molecule (Connors, 1997). Some earlier studies reported that
b-CD could form complexes with numerous compounds with specic molecular structures and diameters such as adamantane
derivatives (Vashi et al., 2001; Leggio et al., 2007). Because the solubility of the inclusion complex would be reduced compared with
that of b-CD (Khatib et al., 2010), we expected that the separation
might be achieved simply through ltration or centrifugation of
the precipitate. Thus, diamondoids can be isolated readily from
the complexes by destroying the molecular structure of b-CD by
acidolysis (Fig. 1).
The saturated hydrocarbon fraction of the crude oil was rstly
obtained by silica gel liquid chromatography to avoid interference
in the inclusion between b-CD and diamondoids (Fig. 2a). Then
n-alkanes (the main component in the saturated hydrocarbon fraction) were separated from branched/cyclic hydrocarbons by using
ZSM-5 molecular sieve liquid chromatography (Huang and
Armstrong, 2009). A chromatogram of eluant is shown in Fig. 2b.
Even though only branched/cyclic hydrocarbons were collected
in the eluting solution, there were still many components that
can interfere in the CSIA of diamondoids. Also, the molecular diameters of branched and cyclic hydrocarbons are similar, making it
difcult to obtain diamondoids from the branched/cyclic hydrocarbons by size exclusion chromatography. The specic inclusion
effect between b-CD and diamondoids makes it possible to isolate
diamondoids from the branched/cyclic hydrocarbons fraction. As
the partial total ion chromatogram (TIC) (Fig. 2c) shows, diamondoids were successfully separated from the branched/cyclic
hydrocarbon fraction by the utilization of b-CD. Most peaks of
diamondoids identied in Table 1 can be found in the TIC, and a

Pristane

568

14

7
3
13
68
2 4 5 10 12
1
9 11

20

30

(c)

16
15

20
19

17
18

40

50

60

70

Time (min)
Fig. 2. Partial TIC of (a) saturate hydrocarbon fraction, (b) branched/cyclic hydrocarbons fraction, and (c) diamondoid fraction for crude oil from the Tazhong 24 well.

569

L. Huang et al. / Organic Geochemistry 42 (2011) 566571

Table 1
The concentration of diamondoids in crude oil provided from Ordovician reservoir (44614483 m) in the Tazhong 24 well, Tarim Basin, identied by GC-MS with the recovery
and carbon isotope data ( vs. VPDB) of individual diamondoid obtained via b-CD inclusion.
Peak No.

Compounds

Abbreviations

Formula

Base peak

Concentration (mg/g)

Recovery (%)

d13C ( vs. VPDB)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

Adamantane
1-Methyladamantane
1,3-Dimethyladamantane
1,3,5-Trimethyladamantane
2-Methyladamantane
1,4-Dimethyladamantane, cis1,4-Dimethyladamantane, trans1,3,6-Trimethyladamantane
1,2-Dimethyladamantane
1,3,4-Trimethyladamantane, cis1,3,4-Trimethyladamantane, trans1,2,5,7-Tetramethyladamantane
1-Ethyl-3,5-dimethyladamantane
Diamantane
4-Methyldiamantane
1-Methyldiamantane
1,4- & 2,4-dimethyldiamantane
4,8-Dimethyldiamantane
Triamantane
9-Methyltriamantane

A
1-MA
1,3-DMA
1,3,5-TMA
2-MA
1,4-DMA (cis)
1,4-DMA (trans)
1,3,6-TMA
1,2-DMA
1,3,4-TMA (cis)
1,3,4-TMA (trans)
1,2,5,7-TeMA
1-E-3,5-DMA
D
4-MD
1-MD
1,4- & 2,4-DMD
4,8-DMD
T
9-MT

C10H16
C11H18
C12H20
C13H22
C11H18
C12H20
C12H20
C13H22
C12H20
C13H22
C13H22
C14H24
C14H24
C14H20
C15H22
C15H22
C16H24
C16H24
C18H24
C19H26

136
135
149
163
135
149
149
163
149
163
163
177
163
188
187
187
201
201
240
239

0.61
3.9
2.5
1.2
0.31
0.33
0.42
0.49
0.47
0.21
0.58
0.63
0.39
0.71
0.51
0.26
0.10
0.097

0.91
1.4
1.3
0.58
1.3
1.1
0.80
1.2
2.1
3.5
1.1
1.0
1.3
8.7
1.8
8.3
3.2
2.7
1.2
0.97

30.9
30.8
30.5
30.2
30.3
31.1

few peaks representing other components are also present. Experimental results revealed that most diamondoids in the crude oil
were isolated by the inclusion method and residual impurities in
the isolated product were rare.
In order to investigate the recoveries of diamondoids in this
method, the SIR chromatograms of diamondoids were monitored
by GCMS. The recovery was calculated by

RD %

Aa  V a
 100%
Ab  V b

where RD is the recovery of diamondoids; Aa and Va are the peak

area and solution volume of a specic diamondoid compound in
the isolated product; Ab and Vb are the peak area and solution volume of a specic diamondoid compound in the saturated hydrocarbon fraction. The data for all of the diamondoids (Fig. 3) are listed in
Table 1. The recoveries of adamantanes, diamantanes and triamantanes are in the range 0.583.5%, 1.88.7% and 0.971.2%, respectively. The recoveries of diamantanes were much higher than
those of adamantanes, suggesting that the inclusion effect between
b-CD and diamantanes are stronger than adamantanes. As for the
triamantanes, the molecular diameters are reported as at least
11 (Koegler et al., 2009), making them very difcult to be included

31.8
31.3
31.3
31.8
31.6
31.3
32.4
32.3
32.8

in the cavity of b-CD (cavity diameter: 7.8 ) (Connors, 1997), thus

explaining why the recoveries of triamantanes were much lower
than those of adamantanes and diamantanes.
3.2. Inuence of b-CD concentration, inclusion time and hydrolysis
time on recovery of diamondoids
In order to study the inuence of b-CD concentration on the
recoveries of diamondoids, various solutions with different concentrations of b-CD (110 mg/ml) were stirred with branched/cyclic hydrocarbon fractions isolated by ZSM-5 molecular sieve. The
molecular structures of A, 1-MA, 1,2-DMA, 1,3,4-TMA(cis), D and
1-MD are representative and their contents are relatively higher
than other diamondoid compounds in the isolation product of
crude oil from the Tazhong 24 well. Thus, their recovery values
were utilized as indicators of the enrichment effect under different
conditions. As shown in Fig. 4, the recoveries of diamondoids increased with increasing b-CD concentration up to 5 mg/ml. The
maximum recoveries of A, 1-MA, 1,2-DMA, 1,3,4-TMA(cis), D and
1-MD obtained under such conditions were approximately 0.22%,

8
6

3
2

10 12
9 11

13

Adamantane

5 678

1
20

22

24

26

28

30

14

1.5x107
1.0x107
5.0x106
0.0

17

16
18

15
36

Diamantane

38

40

42

44

19
20

2x105

46

Recovery (%)

Abundance

6.0x10
4.0x106
2.0x106
0.0

3x105

A
1-MA
1,2-DMA
1,3,4-TMA(cis)
D
1-MD

Triamantane

1x105

0
66

68

70

72

74

10

Concentration of -CD (mg/ml)

Time (min)
Fig. 3. Partial TIC of the nal isolation product. The numbered peaks are
diamondoids identied in Table 1.

Fig. 4. The relationship between the concentration of b-CD solution and the
recovery of diamondoids (inclusion time: 4 h; hydrolysis condition: 80 C for 16 h).
Compound abbreviations are in Table 1.

570

L. Huang et al. / Organic Geochemistry 42 (2011) 566571

0.49%, 1.1%, 2.8%, 6.5% and 6.4%, respectively. As the concentration

of b-CD increased from 6 to 10 mg/ml, a negative effect for the
recoveries of diamondoids was observed possibly because more
precipitate requires more time to complete acidolysis.
Solutions with the same concentrations of b-CD and branched/
cyclic hydrocarbon fraction obtained from oil of the Tazhong 24
well were stirred from 224 h in order to study the inuence of
inclusion time on the recoveries of diamondoids. As shown in
Fig. 5, the recoveries of A, 1-MA, 1,2-DMA, 1,3,4-TMA(cis), D and
1-MD did not increase signicantly when the solutions of b-CD
and branched/cyclic hydrocarbons fraction were stirred more than
2 h. Thus, 2 h of stirring is enough to guarantee completion of the
inclusion process.
The inuence of hydrolysis time on the recoveries of diamondoids was studied as well. Precipitates prepared using the same conditions were hydrolyzed at 80 C for 428 h. As the recoveries of A,
1-MA, 1,2-DMA, 1,3,4-TMA(cis), D and 1-MD are shown in Fig. 6.
Results indicate that the recoveries of these diamondoids were
not increased signicantly when the hydrolysis was extended beyond 16 h. Therefore, the optimal hydrolysis condition for these
inclusion compounds was selected at 80 C for 16 h.

15

A
1-MA
1,2-DMA
1,3,4-TMA(cis)
D
1-MD

Recovery (%)

12

Table 2
Carbon isotope ratio ( vs. VPDB) of d16-adamantane and diamantane before and
after isolation under different acidolysis conditions.

Condition Temperature Time (h) D16-adamantane ()

(C)
d13C
Dd13Ca

Diamantane ()
d13C

Dd13Ca

Initial
a
b
c
d

26.5
26.5
26.3
26.3
26.5

0
0.2
0.2
0

45
60
75
90

22
15
8
4

24.3
24.6
24.5
24.5
24.5

0.3
0.2
0.2
0.2

The carbon isotope ratio difference between initial and separated standards.

3.3. Isotope fractionation during isolation

It was necessary to consider the isotope fractionation of diamondoids during the isolation process because this method was
mainly developed to obtain samples for CSIA. Since the acidolysis
rate of b-CD complex at different temperatures varies, some acidolysis conditions listed in Table 2 were designed to examine
whether isotope fractionation occurs during the isolation of diamondoids. The same solutions containing commercial diamondoid
standards (adamantane-d16 and diamantane), in which the contents of adamantane-d16 and diamantane were approximately
the same as those of adamantane and diamantane in crude oils
from the Tazhong 24 well, were stirred with 5 mg/ml b-CD solutions for 4 h. After centrifugation separation, the inclusion products were dispersed in 30 ml HCl solutions (1 mol/l) and
acidolysed at various temperatures and times listed in Table 2.
Both the isolated products of standards obtained in different acidolysis conditions and initial standard solutions were analyzed by
GCirMS. Table 2 shows that the carbon isotope ratio difference
between initial and separated standards (Dd13C) in all conditions
was < 0.3, which is comparable to the repeatability of the normal
error of GCirMS measurement. Therefore, it can be concluded that
there is no signicant isotope fractionation during the isolation. In
other words, this isolation method is ideal for the CSIA of
diamondoids.

0
0

10

15

20

25

4. Conclusions

Inclusion time (hour)

Fig. 5. The relationship between inclusion time and the recoveries of diamondoids
(concentration of b-CD: 5 mg/ml; hydrolysis condition: 80 C for 16 h).

10
A
1-MA
1,2-DMA
1,3,4-TMA(cis)
D
1-MD

Recovery (%)

0
4

12

16

20

24

28

Hydrolysis time (hour)

Fig. 6. The relationship between hydrolysis time and the recoveries of diamondoids
(concentration of b-CD: 5 mg/ml; hydrolysis condition: 80 C for 4 h).

We discovered an ideal method to isolate diamondoids from

crude oil, making it possible to determine d13C values of individual diamondoids with signicantly enhanced accuracy. Using this
method, we were able to isolate lower molecular-weight diamondoids from crude oil containing many components, which
could otherwise severely interfere with the determination of isotope ratios of diamondoids. Based on 5 mg/ml b-CD solutions,
2 h inclusion time, and hydrolysis at 80 C for 16 h, the recoveries of adamantanes, diamantanes and triamantanes were in the
range 0.583.5%, 1.88.7% and 0.971.2%, respectively. Despite
the low recoveries of these diamondoids, experimental results
of isotope fractionation showed that the d13C values of diamondoids were not changed during the isolation process. Thus, this
work documents a new method for diamondoid isolation from
crude oil and provides an easy way to measure the molecular
d13C values of diamondoids. This is a critical step toward developing new molecular isotopic indicators for oiloil and oil
source rock correlation.
Acknowledgements
The National Natural Science Foundation of China (NNSFC, Project No. 40903026) is acknowledged for supporting this research.
We are grateful to Dr. Lloyd R. Snowdon, Dr. Kenneth Peters and

L. Huang et al. / Organic Geochemistry 42 (2011) 566571

two anonymous reviewers for their helpful comments and

critique.

Associate Editor Kenneth Peters

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