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Russian Geology and Geophysics 55 (2014) 13161320
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A natural oil seep in the floodplain of the Amga River (Siberian Platform)
A.F. Safronov *, O.N. Chalaya, I.N. Zueva, A.R. Aleksandrov
Institute of Oil and Gas Problems, Siberian Branch of the Russian Academy of Sciences, ul. Oktyabrskaya 1, Yakutsk, 677980 Russia
Received 11 June 2013; accepted 3 September 2013

Abstract

A natural oil seep has been revealed in the floodplain of the middle stream of the Amga River, in zone of the exposure of Middle Cambrian
sediments. A distinctive feature of saturated hydrocarbons of this oil is the absence of 12- and 13-methylalkanes, biomarkers that are present
in oils of the VendianCambrian deposits of the NepaBotuobiyan petroliferous province. In this feature the studied seep oil is similar to the
Middle Cambrian oil from hydrogeologic wells (1-P and 1-T) drilled earlier downstream of the Amga River.
2014, V.S. Sobolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved.

Keywords: natural oil seep; chemical-bitumen analysis; chloroform bitumens; 12- and 13-methylalkanes

Introduction content of insoluble organic residue (kerogen). They included

Hydrogeologic wells 1-P and 1-T drilled at depths of 83
and 282 m, respectively, on the right bank of the Amga River
in the 19701980s stripped Middle Cambrian oil-saturated
dolomites of the Tankhai Formation (Fig. 1). The hypothesis
of the presence of an oil pool in this area was put forward.
The pool was conventionally named Bologurskaya (Kashirtsev
et al., 2004).
The shallow occurrence of oil-saturated dolomites impelled
the planned exploration of the area for natural oil seeps. The
search was crowned with success in 2012: A seeping oil show
was discovered in 60 km from the well 1-P upstream of the
Amga River, in the left-bank floodplain. This oil seep includes
occasional oxidized-oil shows up to 3040 cm across (Fig. 2),
oil coating on the floodplain shingle, and 40 100 m oil film
on water.
Materials and methods
cold extraction with chloroform followed by hot extraction
with the same solvent for the separation of components
remained in the solution. For comparison, direct hot extraction
with chloroform was performed. The group hydrocarbon (HC)
composition of chloroform-extracted bitumens was determined
by column chromatography with silica gel sorbent. The
structural-group composition of bitumens was examined by
FTIR spectroscopy, using a Protg 460 spectrometer. The
composition of saturated HCs was studied by gas chromatog-
raphy-mass spectrometry, using an Agilent 6890 gas chroma-
tograph with an Agilent 5973N high-efficiency mass-selective
detector. The chromatograph was equipped with a 30 m long
quartz capillary column 0.25 in diameter impregnated with the
HP-5MS phase. Helium was used as a carrier gas at a flow
rate of 1 ml/min. Operating conditions: vaporizer temperature
320 C, programmed temperature rise from 100 to 300 C at
a rate of 6 C/min, and ionizing voltage 70 eV.

The object of study was oil-saturated dolomitized limestone

of Middle Cambrian age sampled on the left bank of the Amga
River.
Analyses were carried out following the conventional
technique of bituminological research into organic matter of
rocks (Uspenskii et al., 1966) with determination of the
* Corresponding author.
E-mail address: a.f.safronov@ipng.ysn.ru (A.F. Safronov)
1068-7971/$ - see front matter D 201 4, V.S. So bolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.rgg.2014.10.006
Geochemical studies and discussion
The chemical-bitumen analysis of the samples performed
at the Institute of Oil and Gas Problems, Yakutsk, demon-
strated that the discovered oil show is not of technogenic
nature. The analyzed oil-saturated dolomitized limestone con-
tains 1.11% kerogen and 0.44% Corg.
The yield and group and HC compositions of chloroform-
extracted bitumens (CEB) are listed in Table 1. The studied
 A.F. Safronov et al. / Russian Geology and Geophysics 55 (2014) 13161320
Fig. 1. Map of the location of natural oil seep in the middle stream of the Amga
River. 1-T and 1-P are wells that stripped Middle Cambrian oil-saturated dolo-
mites of the Tankhai Formation. 13, wells: 1, test; 2, prospecting and survey;
3, hydrogeologic; 4, natural oil seep.
Fig. 2. Fragment of natural oil seep in the floodplain of the Amga River.
sample is characterized by a high yield of CEB, 0.1546
0.2295%.
The yield of components separated by hot extraction after
the cold one is an order of magnitude lower, 0.0265%, which
suggests the epigenetic nature of the sample bitumen. This is
confirmed by high CEB values, 3552%, and the similar
group compositions of bitumens separated by cold and hot
extraction. The extracts contain mostly asphaltresin compo-
nents, 69.8370.72%. Hydrocarbon compounds amount to
1317
Fig. 3. IR spectra of CEB separated by: 1, cold extraction; 2, cold extraction
followed by hot extraction; 3, direct hot extraction with chloroform.
Fig. 4. Comparison of relative absorption coefficients of bitumens separated by:
1, cold extraction; 2, cold extraction followed by hot extraction; 3, direct hot
extraction with chloroform.
~30%. According to the classification by Uspenskii et al.
(1964), such bitumens belong to asphalts.
Naphthene-aromatic compounds are predominant in the HC
composition of the studied CEB; they amount to 62.32%. The
content of methane-naphthene HCs is 37.68%.
The IR spectra of bitumens separated by cold and hot
extraction are rather similar (Fig. 3). Aromatic HCs are
predominant in the structural-group composition of bitumens,
as evidenced from the intense absorption band of arenes at
1600 cm1 and the characteristic bands of nonsubstituted
hydrogen atoms in aromatic rings at 750, 810, and 880 cm1.
The portions of aliphatic compounds with long methylene
chains are much lower: These structural groups show a weak
absorption band at 720 cm1 near the most intense absorption
band of aromatic compounds at 750 cm1. The bitumens also
have a high portion of carbonyl groups (band at 1700 cm1).
Figure 4 presents the relative absorption coefficients of the
major structural groups, which are commensurate for the two
extracts. The domination of aromatic cycles over aliphatic
structures and the large number of compounds with carbonyl
1318 A.F. Safronov et al. / Russian Geology and Geophysics 55 (2014) 13161320

Table 1. Geochemical characteristics of chloroform-extracted bitumens

Type Yield Group composition of CEB, %
of extraction of CEB, %
oils resins asphalt components

benzene alcohol-benzene Total asphaltogenic acids asphaltenes Total

Cold 0.2295 29.28 16.50 26.21 42.71 0.30 27.71 28.01

Hot, after cold 0.0265 15.41 9.52 47.62 57.14 1.68 25.77 27.45
Hot 0.1546 30.17 18.28 28.11 46.39 1.17 22.27 23.44

Table 2. Composition of saturated hydrocarbons of CEB from Middle Cambrian deposits

Composition Methane-naphthene HCs Oils

c.e. h.e. after c.e. h.e.

Composition of saturated alkanes

Group composition of alkanes (%) per identified alkanes:
n-alkanes 64.28 71.22 49.97
Isoprenoids 23.24 17.90 26.91
2- and 3-methylalkanes 12.48 10.88 23.12
12- and 13-methylalkanes
IBP-n-C20/n-C21-EBP 2.05 0.60 4.65
Prevailing n-alkanes n-C16,15,17 n-C1517 and n-C2527 n-C15
CPI over the entire series 1.12 1.02 1.09
Isoalkanes/n-alkanes 0.36 0.25 0.54
Pristane/phytane 1.23 1.43 1.07
Pristane/norpristane 1.34 1.21 1.11
i-C19/n-C17 0.82 0.86 0.74
i-C20/n-C18 1.03 1.14 1.27
i-C19 + i-C20/n-C17 + n-C18 0.90 1.13 1.21
i-C19 + i-C20/i-C15-i-C18 1.46 1.55 1.08
Composition of polycyclic saturated HCs
Hopanes, moretanes, and cheilanthanes (m/z 191):
Ts/Tm 0.56 N.d. 0.73
Moretanes/hopanes 0.07 N.d. 0.06
Tricyclanes/hopanes 0.51 N.d. 0.37
Hopane/adiantane 2.59 N.d. 2.46
Homohopane index 0.12 N.d. 0.11
Diahopane C30/hopane C29 (Ts) 0.08 N.d. 0.06
Steranes (m/z 217): N.d.
C28/C29 0.66 N.d. 1.00
DS/RS 0.31 N.d. 0.25

Note. c.e., Cold extraction; h.e., hot extraction; IBP, initial boiling point; EBP, end boiling point; CPI, carbon preference index; DS/RS, diasteranes/regular
steranes. N.d., Not determined.

groups, together with the above-considered group component
composition, permit the studied bitumens to be referred to as
asphalts. The original oil might have lost a considerable
amount of light fractions, which led to the residual accumu-
lation of asphaltresin components.
The CEB separated by cold and following hot extraction
differs in composition from the above-described extracts in
twice lower content of oils (15.41%). The average molecule
of this bitumen has considerably more long-chain aliphatic
fragments and oxygen-containing groups and bonds. The
 A.F. Safronov et al. / Russian Geology and Geophysics 55 (2014) 13161320 1319

Fig. 5. Mass fragmentograms (m/z 57) of saturated hydrocarbons in bitumens separated by cold extraction (A), cold extraction followed by hot extraction (B), and
direct hot extraction (C).

oxygen-containing compounds are more diverse in composi-
tion. This difference is particularly distinct in the IR spectra
of benzene and alcoholbenzene resins, which have absorption
bands of not only organic acids (1710 cm1) but also esters,
ketones (1170, 1250, and 1740 cm1), and quinines
(1660 cm1).
The bitumens separated by cold and hot extraction are
similar in composition and the distribution pattern of saturated
HCs (Table 2, Fig. 5). They show a predominance of
n-alkanes, which are, in turn, dominated by low-molecular
homologues, with the maximum content of n-C1517. The CPI
of the bitumens is close to unity. Isoprenoids amount to
23.2426.91%; the isoalkanes/n-alkanes ratio is 0.360.54.
No 12- and 13-methylalkanes were found among the isoal-
kanes (Table 2).
The terpane HCs are mostly tricyclic compounds, amount-
ing to 25.6332.36%. The portion of hopanes is 63.27
69.94%, with hopane dominating over adiantane. Among the
homohopanes, S-isomers are more abundant than R-isomers,
thus reflecting domination of geohopanes over biohopanes.
The steranes are mostly ethylcholestanes and ethyldiacholes-
tane (Table 2).
The saturated hydrocarbons of the CEB separated by cold
and following hot extraction differ in composition from the
1320 A.F. Safronov et al. / Russian Geology and Geophysics 55 (2014) 13161320
above-described extracts in higher portions of n-alkanes
(71.22%), lower portions of isoalkanes, a predominance of
high-molecular homologues among n-alkanes, and IBP al-
kanesn-C20/n-C21EBP alkanes = 0.66 as compared with
2.05 and 4.65 of the above CEB. The distribution pattern of
n-alkanes shows the major peak in the low-molecular region,
at n-C1517, and the second intense peak in the high-molecular
region, at n-C2527 (Table 2, Fig. 5).
Conclusions
The performed studies of dolomitized limestone from the
Middle Cambrian sediments have shown that its bitumens are
similar in the composition and distribution of saturated HCs
to oils of VendianCambrian deposits of the NepaBotuobiyan
petroliferous area. A distinctive feature of the bitumens is the
absence of 12- and 13-methylalkanes, biomarkers specific for
the above oils. In this feature the bitumens are similar to the
Middle Cambrian oil from the Bologurskaya BH-1-P, which
is assigned to the second family of oils in Middle Cambrian
sediments, genetically related to the pyroshale formation of
the YudomaOlenek facies area (Kashirtsev et al., 2004).
In contrast to the oil from the Bologurskaya BH-1-P,
referred to as malthas, the studied bitumens from dolomitized
limestone sampled in the Amga River floodplain are asphal-
tenes. The composition and distribution of aliphatic HCs mark
no significant bacterial oxidation. This indicates the recent
seeping of oil.
The oil shows revealed in the Amga basin are genetically
related to each other. Note that this is the second natural oil
seep in the eastern Siberian Platform. The first one was
discovered by K.K. Makarov in the field of Middle Cambrian
sediments in the basin of the upper stream of the Olenek River
(Arga-Sala River area), on the southern slope of the Anabar
anteclise, in the 1960s (Makarov and Kosolapov, 1967).
Makarov associated this oil show with the oil pool in the
Markha bar.
References
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Editorial responsibility: V.A. Kashirtsev