ISSN 00167029, Geochemistry International, 2012, Vol. 50, No. 1 pp. 74–83. © Pleiades Publishing, Ltd., 2012.

Original Russian Text © G.S. Pevneva, A.K. Golovko, 2012, published in Geokhimiya, 2012, Vol. 50, No. 1, pp. 80–90.

Geochemical Characterization of Organic Matter

from the Middle Jurassic Sediments of Western Siberia
on the Basis of the Composition of Alkylaromatic Hydrocarbons
G. S. Pevneva and A. K. Golovko
Institute of Petroleum Chemistry, Siberian Branch, Russian Academy of Sciences,
Akademicheskii pr. 4, Tomsk, 634021 Russia
email: pevneva@ipc.tsc.ru
Received April 6, 2010; accepted February 8, 2011

Abstract—The composition and distribution of alkylsubstituted bi and tricyclic aromatic hydrocarbons
were studied in dispersed organic matter (DOM) samples from four levels of the Middle Jurassic sequences
of the southeast of Western Siberia. It was shown that differences in the distribution of alkylnaphtalenes and
alkylphenanthrenes were caused by catagenetic factors, which promoted the occurrence of the secondary
reactions of isomerization, alkylation, and dealkylation. The data on the composition of saturated and alkyl
aromatic hydrocarbons were examined by principal component factor analysis, the results of which were used
to divide the samples into natural families. The grouping of DOM samples is based on the similarity of their
characteristic compositional parameters. It was shown that the families include samples from different units
occurring at different depths and mostly in widely separated localities. This indicates that sediments accumu
lated and were transformed under similar conditions at different time periods and in different parts of the
petroleumbearing regions of the southwestern part of Western Siberia.

Keywords: dispersed organic matter, composition, distribution, maturity level, alkanes, alkylnaphthalenes,
alkylphenanthrenes.
DOI: 10.1134/S0016702912010107

INTRODUCTION organic matter (OM) and thermodynamic and chemi

Western Siberia is one of the world’s largest oilpro
ducing regions. Liquid hydrocarbons are recovered
mostly from the Cretaceous and Late Jurassic
sequences. The intense exploitation of these complexes
has resulted in the exhaustion of their proven reserves,
which are almost not replenished. One of the promising
complexes for hydrocarbons in Western Siberia is the
Lower–Middle Jurassic [1]. The assessment of poten
tial resources and prediction of the composition of
hydrocarbon fluids in exploration areas require investi
gations of the hydrocarbon composition of dispersed
organic matter (DOM).
The transformation of biomolecules of buried
organic matter during sedimentation, diagenesis, and
catagenesis produces the whole spectrum of petroleum
hydrocarbons, including aromatic compounds. Aro
matic hydrocarbons are not characteristic of animal and
plant organisms. They are produced by the multistage
alteration of steroid and terpenoid structures through
the reactions of aromatization of saturated rings,
decomposition of sterane and terpane molecules owing
to the cleavage of C rings, and subsequent dealkylation
and isomerization during sedimentation [2–4]. The
investigation of the content and distribution of aromatic
hydrocarbons in oils and DOM is the main tool for the
determination of the thermal maturity level of primary
cal processes occurring in the sedimentary sequence.
The complex composition of aromatic hydrocar
bons, analytical difficulties, the poor knowledge of the
processes of their formation during diagenesis and cat
agenesis, and the absence of information on the charac
ter of molecular composition and distribution of aro
matic hydrocarbons in oils and DOM of various strati
graphic complexes hamper the use of their component
composition during geochemical investigations.
The goal of this study was to characterize the com
position and distribution of alkylated bi and tricyclic
aromatic hydrocarbons in the DOM of the Middle
Jurassic complexes of the southeastern part of Western
Siberia.
The Middle Jurassic of Western Siberia is subdivided
into four stratigraphic units: Laidinskii, Vymskii,
Leont’evskii, and Malyshevskii horizons, which have
different structural and genetic characteristics [1]. We
studied 44 DOM samples from depths of 2303–3087 m
(Table 1). The areas of DOM sampling are confined to
both positive (Aleksandrovskii, SredneVasyuganskii,
Pudinskii, and Parabel’skii megaswells and the Kaimys
ovskii arch) and negative geologic structures (Koltogor
skii megadepression and Nyurol’skaya and Ust’ Tym
skaya troughs).

74
 GEOCHEMICAL CHARACTERIZATION OF ORGANIC MATTER 75

Table 1. Geological characteristics of DOM from the Middle Jurassic sequences

Sample
Area Sampling depth, m Geologic structure
no.
Malyshevskii horizon
1 Prikoltogorskaya 2477 Koltogorskii megadepression
2 Krapivinskaya 2740 Kaimysovskii arch
3 Krapivinskaya 2743 Kaimysovskii arch
4 Yasnaya 2748 Ust’ Tymskaya trough
5 Gerasimovskaya 2843 Nyurolskaya trough
6 SeveroUrmanskaya 2863 Nyurolskaya trough
Leont’evskii horizon
7 Aleksandrovskaya 2669 Koltogorskii megadepression
8 Prikoltogorskaya 2871 Koltogorskii megadepression
9 Lymzhinskaya 2803 SredneVasyuganskii megaswell
10 Lymzhinskaya 2807 SredneVasyuganskii megaswell
11 Lymzhinskaya 2814 SredneVasyuganskii megaswell
12 Pel’ginskaya 2811 Pudinskii megaswell
13 Pel’ginskaya 2815 Pudinskii megaswell
14 Tolparovskaya 2821 Ust’ Tymskaya trough
15 Tolparovskaya 2824 Ust’ Tymskaya trough
Vymskii horizon
16 Northern 2303 Aleksandrovskii megaswell
17 Northern 2308 Aleksandrovskii megaswell
18 Vakhskaya 2477 Aleksandrovskii megaswell
19 Aleksandrovskaya 2681 Koltogorskii megadepression
20 Kolpashevskaya 2683 Parabel’skii megaswell
21 Kolpashevskaya 2719 Parabel’skii megaswell
22 Lymzhinskaya 2841 SredneVasyuganskii megaswell
23 Yasnaya 2895 Ust’ Tymskaya trough
24 Kulginskaya 2910 Nyurolskaya trough
25 Kulginskaya 2914 Nyurolskaya trough
26 Pel’ginskaya 2929 Pudinskii megaswell
Laidinskii horizon
27 Vakhskaya 2478 Aleksandrovskii megaswell
28 Vakhskaya 2485 Aleksandrovskii megaswell
29 Nadezhdinskaya 2586 Aleksandrovskii megaswell
30 Nadezhdinskaya 2591 Aleksandrovskii megaswell
31 Nadezhdinskaya 2607 Aleksandrovskii megaswell
32 Nadezhdinskaya 2617 Aleksandrovskii megaswell
33 Nadezhdinskaya 2623 Aleksandrovskii megaswell
34 Nadezhdinskaya 2624 Aleksandrovskii megaswell
35 Nadezhdinskaya 2761 Parabel’skii megaswell
36 Nadezhdinskaya 2762 Parabel’skii megaswell
37 Nadezhdinskaya 2764 Parabel’skii megaswell
38 Nadezhdinskaya 2769 Parabel’skii megaswell
39 Kolpashevskaya 2774 Parabel’skii megaswell
40 Gerasimovskaya 2843 Nyurolskaya trough
41 Gerasimovskaya 2801 Nyurolskaya trough
42 Lymzhinskaya 2950 SredneVasyuganskii megaswell
43 Yasnaya 3003 Ust’ Tymskaya trough
44 SeveroUrmanskaya 3088 Nyurolskaya trough

GEOCHEMISTRY INTERNATIONAL Vol. 50 No. 1 2012

76 PEVNEVA, GOLOVKO
METHODS
Organic components (bitumens) were extracted
with chloroform from rocks samples. The chloroform
extracted bitumens were divided into the fractions of
saturated, mono, bi, and triaromatic hydrocarbons by
aluminum oxide column chromatography (concentrate
to sorbent mass ratio of 1 : 80) using hexane as eluent.
The yield of fractions was controlled by thinlayer chro
matography using Silufol plates. The assignment of the
fractions of saturated, mono, bi, and triaromatic
hydrocarbons was performed on the basis of a compari
son of the of the Rf value (ratio of the path length of the
center of the component zone from the start line to that
of the eluent) of the fraction and Rf of individual com
pounds in a standard mixture. The latter contained n
hexylbenzene, methylnaphthalene, methylphenan
threne, and chrysene in the proportion 20 : 5 : 3 : 1.
The obtained fractions of saturated and aromatic
hydrocarbons were analyzed by chromatography–mass
spectrometry using a GSMSQP5050 Shimadzu mass
spectrometer coupled with a chromatograph. Chroma
tography was carried out using a DB5MS (J&W Scien
tific) 30 m × 0.32 mm column with a phenyl methyl
polysiloxane film under the following conditions: an
initial temperature of 50°С, a final temperature of
290°С, and a heating rate of 2°C/min. The energy of
ionizing electrons was 70 eV. The chromatograms of
hydrocarbons were recorded for the total ion current
(TIC) and characteristic fragment ions at m/z 57 for
alkanes; m/z 128, 142, 156, and 170 for alkylnaphtha
lenes; and m/z 178, 192, and 206 for alkylphenan
threnes. Individual compounds were identified by com
paring the obtained mass fragmentograms with pub
lished data and mass spectra of individual compounds
available in the Nist 107, Nist 21, and PublibWiley 229
libraries. The following compounds were identified in
the DOM bitumens: naphthalene, methyl, ethyl, pro
pyl, and butylnaphthalenes (monoalkylnaphthalenes,
AN), and isomers of di (DMN) and trimethylnaph
thalenes (TMN) in the diaromatic fraction; and
phenanthrene and isomers of methyl (MP), di
(DMP), and trimethylphenanthrenes (TMP) in the tri
aromatic fraction.
RESULTS AND DISCUSSION
nAlkanes
The beginning of the Middle Jurassic (Laidinskii
horizon) is characterized by frequent changes between
oxidizing and reducing sedimentation conditions [1],
which is indicated by a considerable scatter in the
alkane geochemical parameters. The pristane/phytane
ratio (Pr/Ph) ranges from 1.1 to 6.1 (Table 2), which
suggests unstable basin aeration. The contribution of
plankton to the formation of the primary OM of sample
nos. 28, 30–34, 37, and 43 from the Laidinskii horizon
results in a maximum in the nalkane distribution at
lowmolecularweight C13–C17 hydrocarbons. Samples
GEOCHEMISTRY INTERNATIONAL
38, 39, and 42 show the highest concentrations of C21
and C23 nalkanes (contribution of marine algae). The
other samples exhibit bimodal molecular mass distribu
tions (MMD), which comprise both lowmolecular
weight nalkanes and highmolecularweight com
pounds (vestiges of higher plants). The main parameter
for the estimation of the contribution of terrestrial
plants to primary organic material is the C17/C27
nalkane ratio. This parameter shows considerable vari
ations from 0.4 to 11.0 (Table 2). The values of CPI1 =
1.1 ± 1.6 indicate the dominance of oddnumbered
highmolecularweight nalkanes. This indicator is
most frequently used to characterize the catagenetic
maturation of organic matter: it decreases with an
increase in the maturity level of OM.
During the final stage of the formation of the Vym
skii horizon (early Bajocian), the largest depressions
(Koltogorskii depression and Nyurolskaya and Ust’
Tymskaya troughs) in the southeast of Western Siberia
were shallow freshened sea bays and estuaries [1]. The
compositions of nalkanes from most DOM samples of
the Vymskii horizon show MMD with a broad maxi
mum at C14–C21. This indicates the presence of phy
toplankton and coastal marine algae in the primary
OM. Samples 18, 21, and 25 have a distinct contribu
tion of higher plants, which is manifested by their
nalkane distribution patterns with a maximum at C23
and C25 and nC17/nC27 values. The Pr/Ph ratio ranges
from 1.0 to 9.0, and CPI1 is from 1.0 to 1.4 (Table 2).
In the middle early Bajocian (Leont’evskii horizon),
the sea level rose. The sea in the main depressions of the
southeastern part of Western Siberia was very deep, and
clay sediments were dominant. Most of the positive
structures were submerged, and, in addition to clays,
silty and fine sandy sediments accumulated there [1].
The distribution of nalkanes in most samples from the
Leont’evskii horizon shows a broad maximum at C14–
C25, which indicates a mixed type of primary OM. In
samples 8 and 15, the distinct maximum in the MMD
of nalkanes at C23–C25 indicates a contribution from
coastal marine algae and higher plants to the formation
of their primary OM. The C17/C27 values of these sam
ples are 0.7 and 0.3, respectively, whereas other samples
fall within the 2.3–9.5 interval. The wide range of
Pr/Ph values (from 2.4 to 8.9) suggests variations in the
level of aeration. The CPI1 values are from 1.1 to 1.4
(Table 2).
By the beginning of Malyshevskoe time (end of the
Bajocian and Bathonian), the decrease in sea level did
not reduce the area of water basins but made them shal
lower. All the depressions were occupied by a shallow
sea with sandy–silty–clayey sediments. The positive
structures were submarine highs with sandy–silty sedi
ments [1]. The character of nalkane distribution in the
DOM of the Malyshevskii horizon indicates that most
of the samples contain mixedtype primary OM (n
C17/nC27 = 0.6–1.1). The primary organic material
Vol. 50 No. 1 2012
 GEOCHEMICAL CHARACTERIZATION OF ORGANIC MATTER 77

Table 2. Compositional characteristics of alkanes, alkylnaphthalenes, and alkylphenanthrenes from DOM samples
Content of alkyl Content of alky

nC17/nC27
naphthalenes, % lphenanthrenes, %
Sam Depth, rel. rel.
Area
ple no. m

DNR2
DMN

TÌNR
Pr/Ph

MNR

MPI1
CPI1

TMN

DMP

TMP
MP
AN
Malyshevskii horizon
1 Prikoltogorskaya 2477 3.6 1.8 2.2 26.3 39.7 31.5 40.6 37.6 11.8 1.6 1.2 0.4 0.54
2 Krapivinskaya 2740 2.3 1.1 0.9 24.1 50.7 21.1 39.6 28.3 9.1 1.0 1.7 0.8 0.51
3 Krapivinskaya 2743 6.4 1.0 1.1 30.5 40.5 24.4 36.4 28.6 8.0 1.0 1.6 0.5 0.44
4 Yasnaya 2748 3.6 1.4 0.6 16.7 33.8 45.5 52.1 22.8 5.1 1.7 1.2 0.3 0.50
5 Gerasimovskaya 2598 10.2 1.3 1.1 24.3 36.3 31.9 48.6 20.9 6.5 2.1 1.4 0.3 0.49
6 SeveroUmanskaya 2863 3.8 1.1 0.7 29.6 37.9 26.4 41.4 19.8 8.8 2.1 1.4 0.4 0.54
Leont’evskii horizon
7 Aleksandrovskaya 2669 4.8 1.2 2.6 20.9 48.2 25.2 41.1 18.9 4.0 0.9 0.7 0.2 0.37
8 Prikoltogorskaya 2871 2.4 1.1 0.7 25.4 41.9 28.5 40.6 32.6 6.7 1.1 0.9 0.3 0.52
9 Lymzhinskaya 2803 3.3 1.4 9.5 12.2 41.7 42.7 26.3 48.6 5.0 0.7 0.7 0.3 0.84
10 Lymzhinskaya 2807 3.3 1.3 3.7 15.2 44.0 36.0 30.8 28.1 11.1 1.1 1.2 0.3 0.43
11 Lymzhinskaya 2814 3.8 1.2 4.8 7.9 37.8 30.5 37.9 36.9 5.2 0.7 0.4 0.6 0.65
12 Pel’ginskaya 2811 4.4 1.0 7.4 34.1 41.0 20.1 39.1 27.0 9.9 1.1 0.8 0.4 0.45
13 Pel’ginskaya 2815 8.9 1.0 2.2 31.1 37.8 28.0 32.1 32.3 5.6 1.2 0.7 0.2 0.38
14 Tolparovskaya 2821 7.1 1.2 2.3 15.3 39.7 41.1 43.4 30.9 5.7 0.9 0.9 0.2 0.48
15 Tolparovskaya 2824 2.5 1.2 0.3 22.5 40.6 32.0 37.7 23.5 8.7 1.0 2.1 0.4 0.45
Vymskii horizon
16 Northern 2303 6.3 1.2 3.1 25.9 47.2 23.6 37.4 33.3 6.2 1.1 0.7 0.3 0.47
17 Northern 2308 4.5 1.0 2.3 13.0 46.7 37.1 34.7 27.2 8.1 1.1 0.8 0.2 0.35
18 Vakhskaya 2477 1.0 1.4 0.3 41.7 37.3 14.6 40.1 19.9 10.1 1.4 2.4 0.6 0.56
19 Aleksandrovskaya 2681 4.8 1.0 2.6 31.3 44.7 21.6 39.7 33.5 6.7 1.3 2.5 0.4 0.52
20 Kolpashevskaya 2683 8.1 1.1 2.7 30.6 33.8 25.4 34.9 33.4 4.6 1.7 1.2 0.4 0.54
21 Kolpashevskaya 2719 5.5 1.2 0.9 14.7 45.3 37.0 38.2 30.7 11.1 0.8 0.7 0.3 0.45
22 Lymzhinskaya 2841 2.7 1.0 1.9 19.2 56.4 19.0 29.8 42.9 7.3 1.5 1.1 0.7 0.26
23 Yasnaya 2895 9.0 1.2 3.7 10.1 48.3 39.0 38.9 41.2 6.8 0.9 1.5 0.5 0.79
24 Kulginskaya 2910 6.6 1.2 1.3 27.8 39.3 29.2 44.9 32.6 2.4 0.9 0.6 0.3 0.75
25 Kulginskaya 2914 3.8 1.3 0.7 23.9 43.6 29.4 38.6 27.6 7.9 0.9 1.1 0.5 0.45
26 Pel’ginskaya 2929 6.2 1.1 1.5 25.4 45.6 26.6 34.7 38.7 6.6 1.2 0.9 0.4 0.58
Laidinskii horizon
27 Vakhskaya 2478 5.4 1.1 1.6 28.1 42.3 22.6 40.8 36.0 3.2 0.8 1.7 0.7 0.60
28 Vakhskaya 2485 4.5 1.0 2.7 31.7 34.7 23.3 39.1 35.8 5.1 1.3 2.6 0.2 0.56
29 Nadezhdinskaya 2586 3.0 1.1 3.1 34.1 39.0 21.8 47.1 29.5 3.3 1.6 3.1 0.3 0.69
30 Nadezhdinskaya 2591 3.3 1.4 3.7 13.5 45.1 38.2 41.7 29.3 4.9 1.0 1.0 0.4 0.61
31 Nadezhdinskaya 2607 4.7 1.3 9.6 7.0 41.5 48.1 34.1 49.5 4.3 0.7 0.7 0.3 0.67
32 Надеждинская 2617 4.2 1.4 5.0 15.2 45.8 36.8 45.6 36.5 3.0 1.0 1.2 0.6 0.65
33 Nadezhdinskaya 2623 2.4 1.1 11.0 17.6 47.3 32.7 42.9 38.3 3.7 1.1 1.2 0.5 0.68
34 Nadezhdinskaya 2624 2.7 1.2 2.4 31.7 41.6 21.8 45.6 27.1 7.3 1.2 1.9 0.6 0.63
35 Kolpashevskaya 2761 6.2 1.6 2.6 31.4 42.2 21.3 41.5 26.7 6.8 1.15 1.2 0.5 0.59
36 Kolpashevskaya 2762 2.6 1.4 3.5 23.9 42.3 29.2 46.5 28.5 5.0 1.4 2.6 0.2 0.77
37 Kolpashevskaya 2764 1.1 1.2 2.3 24.6 34.8 32.4 35.0 30.3 4.8 1.4 0.9 0.2 0.65
38 Kolpashevskaya 2769 2.1 1.3 0.8 16.6 39.6 38.9 32.0 32.5 5.6 1.1 1.5 0.3 0.72
39 Kolpashevskaya 2774 2.4 1.2 0.4 10.1 35.5 51.0 39.2 32.8 4.0 0.9 1.5 0.3 0.62
40 Герасимовская 2843 6.1 1.2 0.6 40.3 35.8 17.6 30.5 39.6 6.0 1.2 1.5 0.3 0.88
41 Gerasimovskaya 2801 5.2 1.6 1.7 27.5 33.0 30.5 36.5 37.1 6.4 1.4 1.7 0.3 0.55
42 Lymzhinskaya 2950 2.2 1.1 1.7 18.9 50.9 26.6 42.1 32.0 5.9 1.4 1.1 0.3 0.56
43 Yasnaya 3003 3.7 1.2 9.6 5.6 42.5 48.6 59.3 27.5 3.2 0.9 0.9 0.6 0.54
44 SeveroUmanskaya 3088 3.4 1.3 0.9 27.4 44.4 21.3 38.2 29.3 6.6 1.3 2.4 0.7 0.55
Note: CPI1 = 1/2[(C25 + C27 + C29 + C31)/(C24 + C26 + C28 + C30) + (C25 + C27 + C229 + C31)/(C26 + C28 + C30 + C32)]; methyl
naphthalene ratio MNR = 2methylnaphthalene/1methylnaphthalene; dimethylnaphthalene ratio DNR2 = (2,6 + 2,7dime
thylnaphthalene)/1,5dimethylnaphthalene; trimethylnaphthalene ratio TMNR = 1,3,6trimethylnaphthalene/(1,2,5 + 1,3,6
trimethyl naphthalene); and methylphenanthrene index MPI1 = 1.5([2MP] + [3MP])/([P] + [1MP] + [9MP]).

GEOCHEMISTRY INTERNATIONAL Vol. 50 No. 1 2012

78 PEVNEVA, GOLOVKO
accumulated mainly under oxidizing conditions
(Pr/Ph = 2.3–6.4). In most of the DOM samples, high
molecularweight nalkanes are dominated by oddcar
bonnumber homologues with CPI1 = 1.0–1.8.
Thus, the distribution of normal and isoprenoid
alkanes in DOM is mainly controlled by the type of pri
mary OM and sedimentation conditions.
Alkylnaphthalenes
Naphthalene and its alkylsubstituted homologues
were identified in the biaromatic hydrocarbon fraction.
The mean contents of unsubstituted naphthalene in the
samples are (% relative) 2.3 (0.1–7.5) for the Laidinskii
horizon, 1.3 (0.1–6.8) for the Vymskii horizon, 0.7
(0.2–2.4) for the Leont’evskii horizon, and 1.8 (1.0–
5.0) for the Malyshevskii horizon. Monoalkylnaphtha
lenes are represented by methyl, ethyl, propyl, and
butylnaphthalenes. Metylnaphthalenes are most abun
dant among them. In most samples, the content of ther
modynamically more stable βsubstituted monoalkyl
naphthalenes is higher than the contents of less stable
αisomers.
In most of the DOM samples from the four units,
dimethylnaphthalenes form the sequence 1,3(α1,β1
isomer) ≥ 1,6(α1,β2isomer) ≥ 2,6 + 2,7 (β1,β2iso
mer) > 2,3(β1,β1isomer) > 1,5(α1,β2isomer) > 1,2
(α1,β1isomer) > 1,7(α1,β2isomer) > 1,8(α1,α2iso
mer) > 1,4(α1,α1isomer) (subscript indicates the
HO 1,2,5
R 1,3,6
1,2,7
The analysis of data on the group assignment of
alkylnaphthalenes revealed the following concentration
sequence of alkylnaphthalenes for most of the samples
of the Laidinskii, Vymskii, and Leont’evskii horizons
and samples 1 and 5 from the Malyshevskii horizon:
dimethylnaphthalenes > trimethylnaphthalenes >
monoalkylnaphthalenes (Table 2). Samples 27–29, 34,
and 35 from the Laidinskii horizon; 15, 19, 20, and 22
from the Vymskii horizon; 12 and 13 from the
Leont’evskii horizon; and 2, 3, and 6 from the Maly
GEOCHEMISTRY INTERNATIONAL
number of the aromatic ring of naphthalene [4]). The
dimethylnaphthalenes are dominated by isomers with
substituents on different rings, which is probably related
to the tendency of molecules to occur in a thermody
namically stable state. A symmetric arrangement of
alkyl substituents results in some resonance stabiliza
tion of naphthalene molecules.
The following sequence of trimethylnaphthalenes
was observed in the DOM samples: 1,2,5(α1,β1,β2iso
mer) > 1,3,6(α1,β1,β2isomer) > 1,4,6(α1,α1,β2iso
mer) > 1,3,7(α1,β1,β2isomer) > 1,6,7(α1,β2,β2iso
mer) > 2,3,6(β1,β1,β2isomer) > 1,2,7(α1,β1,β2iso
mer) > 1,2,6(α1,β1,β2isomer) > 1,2,4(α1,β1,α1
isomer).
One of the hypothetical scenarios of the formation
of trimethylnaphthalenes [5, 6] is discussed below.
According to this scenario, 1,2,5(α,β,αisomer) and
1,2,7(α,β,βisomer) trimethylnaphthalenes are pri
mary. During the subsequent stages of catagenetic mat
uration, 1,3,6(α,β,β isomer), 1,3,7(α,β,βisomer),
and 2,3,6(β,β,βisomer) trimethylnaphthalenes are
formed owing to isomerization reactions.
The trimethylnaphthalenes of Jurassic DOM are
dominated by 1,2,5trimethylnaphthalene, which is
thermodynamically one of the least stable isomers. For
comparison, it should be noted that the concentration
of this component in oils is lower than those of 1,3,6,
1,3,7, and 2,3,6trimethylnaphthalenes [7, 8].
1,3,7
2,3,6
shevskii horizon show a different sequence: dimethyl
naphthalenes > monoalkylnaphthalenes > trimethyl
naphthalenes. Trimethylnaphthalenes dominate over
both dimethyl and monoalkylnaphthalenes in sam
ples 31, 39, and 43 from the Laidinskii horizon and
sample 4 from the Malyshevskii horizon. In a few sam
ples (sample 40 from the Laidinskii horizon and sample
18 from the Vymskii horizon), the concentration of
monoalkylnaphthalenes is higher than those of dime
thyl and trimethylnaphthalenes.
Vol. 50 No. 1 2012
 GEOCHEMICAL CHARACTERIZATION OF ORGANIC MATTER
One of the most important processes accompanying
catagenetic maturation is the isomerization of substi
tuted naphthalenes containing alkyl groups in αposi
tions into thermodynamically more stable species with
substitution in βpositions. The relationships of these
isomers is used as a basis for diagnostic geochemical
indicators of the maturity level of OM [4, 9–12]. For
instance, the methylnaphthalene ratio, MNR =
2methylnaphthalene (βisomer)/1methylnaphtha
lene (αisomer); dimethylnaphthalene ratio, DNR2 =
(2,6 + 2,7dimethylnaphthalenes)/1,5dimethylnaph
thalene; trimethylnaphthalene ratio, TMNR = 1,3,6
trimethylnaphthalene/(1,3,6 + 1,2,5trimethylnaph
thalenes); and others. Higher values of these geochem
ical parameters correspond to higher maturity levels.
The values of parameters based on the compositions of
alkylnaphthalenes are given in Table 2. For most of the
samples, the naphthalene parameters tend to increase
with increasing depth. However, these parameters may
show a considerable scatter, and the alkylnaphthalene
compositional parameters should be used for the esti
mation of the degree of maturation together with data
on the composition of saturated and triaromatic hydro
carbons.
Thus, alkylated biaromatic hydrocarbons in DOM
of various genetic types are represented by a single set of
individual alkylnaphthalenes. The differences in the
group composition of alkylnaphthalenes (contents of
compounds with different numbers of substituents in
the molecule) is related mainly to catagenetic factors,
although some authors noted that the composition of
alkylnaphthalenes depends to some extent on the type
of the primary OM, although less strongly than the
composition of saturated hydrocarbons [4, 9, 10, 13–
15]. Geochemical parameters based on the composi
tion of naphthalenes can be used for estimating the
maturity level of DOM together with the compositions
of other hydrocarbon classes.
Alkylphenanthrenes
The content of phenanthrene in our samples is
strongly variable (% relative): 16.9 (6.5–30) in the Lai
dinskii horizon, 20.4 (11.6–29.7) in the Vymskii hori
zon, 24.3 (8.6–34.5) in the Leont’evskii horizon, and
24.0 (14.0–33.0) in the Malyshevskii horizon.
Anthracene is much less abundant than phenanthrene:
the phenanthrene to anthracene ratio is 15.7 (0.6–49.0)
in the DOM of the Laidinskii horizon, 4.1 (1.0–13.1) in
the Vymskii horizon, 19.6 (7.2–48.9) in the
Leont’evskii horizon, and 12.0 (6.8–23.6) in the Maly
shevskii horizon. Anthracene was not detected in the
DOM of the Laidinskii horizon from the Nadezhdin
skaya area (samples 29–34).
In all samples, the contents of αisomers (9 and
1methylphenanthrenes), whose methyl substituents
occur in thermodynamically less favorable positions,
are higher than those of thermodynamically more stable
βmethylphenanthrenes (2 and 3methylphenan
GEOCHEMISTRY INTERNATIONAL Vol. 50 No. 1
79
threnes). Among αisomers, 1methylphenanthrene,
which is characteristic of continental OM, is more
abundant in most samples than 9methylphenanthrene,
which is indicative of marine facies [7]. In samples 34,
38, 40 (Laidinskii horizon), 24, 25 (Vymskii horizon),
9, 14 (Leont’evskii horizon), 2, 4, 6, and 7 (Maly
shevskii horizon), the concentration of 9meth
ylphenanthrene is higher than that of 1methylphenan
threne by a factor of 1.2–1.5. The nalkane signature of
these samples (bimodal MMD) indicates that their OM
is of mixed origin.
The samples show minor differences in dimeth
ylphenanthrene composition. The group composition
of alkyl phenanthrenes of all DOM samples is the fol
lowing: methylphenanthrenes > dimethylphenan
threnes > trimethylphenanthrenes (Table 2). The differ
ences in the alkylphenenthrene group composition of
DOM samples are less pronounced than those of alkyl
naphthalenes.
Thus, DOM samples from a single unit show most
significant variations in the contents of phenanthrene
and α and βisomers of methylphenanthrenes. The
proportion of these components is widely used in
geochemistry for the estimation of the maturity level of
OM [4, 7, 16–20]. Variations in the contents of phenan
threne and α and βisomers of methylphenanthrenes
are related to secondary reactions of isomerization,
alkylation, and dealkylation during the catagenetic
maturation of primary OM. The enrichment of βiso
mers (3 and 2methylphenanthrenes) relative to αiso
mers (9 and 1methylphenanthrenes) suggests an
increase in the degree of OM maturation. In addition,
owing to catagenetic factors, the isomerization is
accompanied by alkylation–dealkylation reactions,
which affect the content of unsubstituted phenan
threne. The methylphenanthrene index (MPI1 [4]) of
DOM from our samples was calculated from their alky
lphenanthrene compositions (Table 2). According to
this parameter, the DOM samples of the Laidinskii
horizon are more mature compared with samples from
other Middle Jurassic units.
In order to distinguish similarities and differences in
the composition of hydrocarbons from the DOM of the
Middle Jurassic sequences, their individual composi
tions were examined by principal component factor
analysis [21, 22]. The matrix included data on the indi
vidual composition of alkanes (contents of С11–С32
nalkanes, Pr, and Ph), alkylnaphthalenes (contents of
naphthalene and 26 of its alkylsubstituted isomers),
and alkylphenanthrenes (contents of phenanthrene and
22 of its alkylsubstituted isomers) in 44 DOM samples.
Figure 1 shows the distribution of the DOM samples in
the coordinates of the first two principal components.
The samples cluster into natural families. The composi
tional characteristics of alkanes, alkylnaphthalenes, and
alkylphenanthrenes of particular DOM families were
estimated by comparing geochemical parameters cal
culated from the compositions of these components
2012
80
Horizons:: Laidinskii
16.3
9.8 Family I
31
3 6 9
3.2
F2 15 2 24
14
–3.4
13
Family III 44
–10 18
20
22
–16.6
–14.4 4.2
Fig. 1. Distribution of DOM samples in the coordinates of the first two principal components (sample numbers are the same as
in Table 1).
and/or ratios of some alkylnaphthalenes and alky
lphenanthrenes.
The first family includes 19 DOM samples: ten from
the Laidinskii horizon (27–29, 32–35, 37, 40, 41), five
from the Vymskii horizon (16, 19, 20, 24, 26), two from
the Leont’evskii horizon (12 and 13), and two from the
Malyshevskii horizon (1 and 3) (Fig. 1). These samples
were recovered from depths of 2302–2928 m. The first
family was distinguished primarily on the basis of the
contents of lowmolecularweight nalkanes, naphtha
lene, and 2 and 1methylnaphthalenes.
The MMD of nalkanes in the DOM of most sam
ples of the first family display maximum at lowmolec
ularweight hydrocarbons С12, С15, and С16 (Fig. 2a),
and their mean nC17/nC27 value is 3.1 (Table 3). This
family is enriched in naphthalene compared with the
DOM of two other groups and shows high contents of 2
and 1methylnaphthalenes (Fig. 2b). The mean ratio of
the sum of 2 and 1methylnaphthalenes to the sum of
1,3 and 1,6dimethylnaphthalenes is 1.2 (Table 3).
The alkylnaphthalene group composition of the first
family is the following: dimethylnaphthalenes >
monoalkylnaphthalenes > trimethylnaphthalenes. The
quantitative estimation of the contents of each group of
alkylnaphthalenes was based on their ratios. The appro
priate parameters for the first family are AN/DMN =
0.7, AN/TMN = 1.2, and DMN/TMN = 1.6. The
mean phenanthrene content is 16.9 (11.6–28.1)% rela
tive (Fig. 2c). In these samples, methylphenanthrenes
are more abundant than dimethyl isomers: the ratio of
the total content of methylphenanthrenes to that of
dimethylphenanthrenes (MP/DMP) is 1.2. A combi
nation of the geochemical parameters that are used for
the estimation of the degree of catagenetic maturity of
PEVNEVA, GOLOVKO
Leont’evskii Malyshevski Vymskii
8
7
11 Family II
16
34 23
36 30 37
38 32
1 39 28
2917
25
26 40 19
12 43 10 35 27
4
21
5
33
22.6 40.4 56.4
F1
OM (methylnaphthalene, dimethylnaphthalene, trim
ethylnaphthalene, and methylphenanthrene ratios) [4,
10–12, 15, 19] indicates moderately high degrees of the
catagenetic maturity of the samples of this family. It
should be noted that the samples of the first family were
collected both in positive (Aleksandrovskii and Parabel
skii megaswells) and negative geologic structures
(Nyurol’skaya and Ust’ Tymskaya troughs).
The second family includes ten samples: two from
the Laidinskii horizon (35 and 44), three from the
Leont’evskii horizon (7, 8, and 15), three from the
Malyshevskii horizon (2, 5, and 6), and two from the
Vymskii horizon (18 and 25) (Fig. 1). The sampling
depth ranges from 2478 to 3088 m. Most of the samples
were collected at negative geologic structures (Table 1).
The second family comprises DOM samples with simi
lar dominant amounts of phenanthrene, 1,3dimethyl
naphthalene, and С23–С26 nalkanes.
Most of the samples of this family show nalkane
MMD with maximum at С23–С26 (Fig. 2a), which is
related to the contribution of higher plants. Similar to
the first family, Pr/Ph varies significantly from 1.0 to
10.2. The composition of alkylnaphthalenes from the
samples of the second family shows lower contents of
methylnaphthalenes and naphthalene and higher con
tents of 1,3 and 1,6dimethylnaphthalenes compared
with the samples of the first family (Table 3, Fig. 2b). As
a result, the ratio of 2 and 1methylnaphthalenes to the
sum of 1,3 and 1,6dimethylnaphthalenes is lower
than in the DOM of the first family (0.9 on average).
The group composition of alkylnaphthalenes of the sec
ond family is similar to that of the first family: dimeth
ylnaphthalenes are more abundant than monoalkyl
and trimethylnaphthalenes. The two families have also
GEOCHEMISTRY INTERNATIONAL Vol. 50 No. 1 2012
 GEOCHEMICAL CHARACTERIZATION OF ORGANIC MATTER 81

Family I Family II Family III (a)

10

8
Content, % rel.

0
11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
Carbon number

14 Family I Family II Family III

(b)
12

10
Content, % rel.

0
N

1,4DMN

1,5DMN

1,6,7TMN
1,2,6TMN

2BuN
1BuN
2MN

2EN
1EN
2,6DMN

1,3DMN
1,6DMN

2,3DMN

1,2DMN
1,8DMN

1PrN

1,3,6TMN
1,4,6TMN
2,3,6TMN
1MN

2,7DMN

2PrN

1,3,7TMN

1,2,7TMN

1,2,4TMN
1,2,5TMN
30 Family III
Family I Family II
25
(c)
20
Content, % rel.

15

10

0
DMP6

DMP9

DMP111
P

DMP1
A

DMP2
DMP3
DMP4
DMA1
DMP5
3MP

DMP7
2MP
2MA
9MP

9MA
DMP0

DMP8

DMA2
DMP10
DMA3
1MP

Fig. 2. Averaged molecular mass distribution of (a) nalkanes, (b) alkylnaphthalenes, and (c) alkylphenanthrenes for the distin
guished DOM families.

GEOCHEMISTRY INTERNATIONAL Vol. 50 No. 1 2012

82 PEVNEVA, GOLOVKO

Table 3. Characteristics of DOM families from the Middle Jurassic sequences

Family
Parameter
first second third
4.9 4.0 4.1
Pr/Ph
(1.1–8.9) (1.0–10.2) (2.1–9.0)
1.2 1.3 1.2
CPI1
(1.0–1.8) (1.1–1.6) (1.0–1.4)
3.1 1.1 3.6
nC17/nC27
(1.17.4) (0.3–2.6) (0.9–9.6)
0.7 0.7 0.3
AN/DNM
(0.3–1.1) (0.4–1.1) (0.1–0.4)
1.2 1.2 0.4
AN/TMN
(0.4–2.3) (0.8–2.9) (0.1–1.0)
1.6 1.8 1.2
DMN/TMN
(1.1–2.1) (1.1–2.6) (0.6–3.0)
1.2 0.9 0.2
(2 + 1methylnaphthalenes)/(1,6 + 1,3dimethylnaphthalenes)
(0.9–1.9) (0.4–1.6) (0.1–0.4)
1.2 1.2 0.9
MNR = 2methylnaphthalene/1methylnaphthalene
(0.9–1.7) (0.9–2.1) (0.3–1.5)
2.5 1.5 1.0
DNR2 = (2,6 + 2,7DMN)/1,5DMN
(0.9–3.1) (1.1–2.4 ) (0.7–1.5)
0.4 0.5 0.4
TMNR = (1,3,6TMN)/(1,3,6 + 1,2,5TMN)
(0.2–0.7) (0.2–0.8) (0.30.6)
0.59 0.48 0.55
MPI1 = (2 + 3MP)/(P + 9MP + 1MP)
(0.2–0.9) (0.3–0.6) (0.3–0.8)
1.2 1.6 1.2
MP/DMP
(0.8–1.6) (1.2–2.2) (0.5–2.3)

similar AN/DMN, AN/TMN, and DMN/TMN val
ues (Table 3). The content of phenanthrenes in the sam
ples of this families are higher than those in the DOM
samples of two other families and averages 29.5 (22.4–
34.2)% relative (Fig. 2c). The content of meth
ylphenanthrenes is significantly higher than that of
dimethylphenanthrenes (MP/DMP = 1.6). The meth
ylnaphthalene, dimethylnaphthalene, and methylphe
nenthrene ratios characterizing the maturity level of
OM are higher in the samples of this family compared
with the DOM of the first family.
The third family (16 samples) includes six samples
from the Laidinskii horizon (30, 31, 39, 39, 42, 43), four
samples from the Vymskii horizon (17, 21–23), three
samples form the Leont’evskii horizon (10, 11, 14), and
one sample from the Malyshevskii horizon (4) (Fig. 1),
which were recovered from depths of 2308–3003 m.
The distinguishing of the third family was based on the
contributions of phenanthrene, 9 and 1meth
ylphenanthrenes, and highmolecularweight n
alkanes. The broad maximum at С14–С25 in the MMD
of nalkanes from the majority of samples indicates a
mixed primary OM (Fig. 2a). Similar to the samples of
the above families, the third family shows widely scat
tered Pr/Ph values ranging from 2.1 to 9.0 (Table 3).
The composition of alkylnaphthalenes from the DOM
of the third family showed the minimum contents of 2
and 1methylnaphthalenes. The mean ratio of 2 and 1
methylnaphthalenes to the sum of 1,3 and 1,6dimeth
ylnaphthalenes is 0.2. The group composition of alkyl
naphthalenes of this family is different from that of
other families: dimethylnaphthalenes > trimethylnaph
thalenes > monoalkylnaphthalenes. The values
AN/DMN = 0.3, AN/TMN = 0.4, and DMN/TMN
= 1.2 indicate that the content of monoalkylnaphtha
lenes (AN) in the DOM of this family is lower com
pared with the DOM of other families. The mean
phenanthrene content in the samples of this family is
18.4 (7.4–29.4)% relative. The enrichment of meth
ylphenanthrenes over dimethylphenanthrenes is less
significant than in the other families (MP/DMP = 1.2).
The samples of this family are less mature compared
with the DOM of other families, which is indicated by
the maturity indicators calculated from the composi
tions of methylnaphthalenes, dimethylnaphthalenes,
and methylphenanthrenes.
CONCLUSIONS
The investigation of alkane distribution in DOM
from four Middle Jurassic units revealed both similari
ties and differences in their compositions, which are
related to the type of primary OM and sedimentation
conditions during its burial.

GEOCHEMISTRY INTERNATIONAL Vol. 50 No. 1 2012

 GEOCHEMICAL CHARACTERIZATION OF ORGANIC MATTER
A comparison of the compositions of bi and trialkyl
aromatic hydrocarbons in the DOM samples from the
four Middle Jurassic units formed in organic materials
of different types did not distinguish any unequivocal
indicator for the nature of primary organic material.
Almost identical associations of individual alkylnaph
thalenes were observed in all of the samples.
The differences in the distribution of alkylnaphtha
lenes and alkylphenanthrenes are related to the influ
ence of catagenetic factors, which promote the occur
rence of secondary reactions of isomerization, alkyla
tion, and dealkylation.
The analysis of data on the composition of saturated
and alkylsubstituted aromatic hydrocarbons by the
principal component method allowed us to divide the
DOM samples from the rocks of the four Middle Juras
sic units into natural families. The grouping was based
on the similarity of characteristic parameters of the
composition of samples owing to the similar conditions
of sedimentation of similar organic materials. Samples
from different units and depths usually occurring far
apart may be assigned to a single group. This suggests
that similar sedimentation conditions existed in differ
ent time periods and in different areas of the petroleum
bearing regions of the southeast of Western Siberia.
ACKNOWLEDGMENTS
This study was carried out within integration project
no. 36 of the Siberian Branch of the Russian Academy
of Sciences entitled “Fundamental Geological,
Geochemical, Biochemical, and Chemical Catalytic
Principles of the Theory of Petroleum Formation in the
Sedimentary Shell of the Earth”.
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