ISSN 0024 4902, Lithology and Mineral Resources, 2012, Vol. 47, No. 4, pp. 305 318.

Pleiades Publishing, Inc., 2012.

Original Russian Text V.N. Kuleshov, 2012, published in Litologiya i Poleznye Iskopaemye, 2012, No. 4, pp. 345 359.

New Data on Formation Conditions and Origin of Manganese

Carbonate Ores in the Ulutelyak Deposit (Bashkortostan)
V. N. Kuleshov
Geological Institute, Russian Academy of Sciences, Pyzhevskii per. 7, Moscow, 119017 Russia
e mail: kuleshov@ginras.ru
Received June 2, 2010

Abstract The carbon and oxygen isotopic compositions in rocks and ores of the Ulutelyak (Bashkortostan)
manganese deposit of the Lower Permian (P 1kg) are studied. Values of 13C, (PDB) and 18O,
(SMOW) show the following range: from 3.8 to 3.3 and from 22.0 to 29.6, respectively, in manganese oxide
carbonate ores; from 2.7 to 4.1 and from 28.8 to 29.7, respectively, in non ore carbonate clayey interbeds of
the ore member; and from 2.8 to 4.5 and from 29.5 to 30.0, respectively, in the underlying and overlying lime
stones. Lithological features and isotope data suggest that manganese carbonates were formed at the postsed
imentary stage of rock transformation due to metasomatic replacement of the primary cyanobacterial sedi
mentary carbonates by the elisional manganiferous solutions.
DOI: 10.1134/S0024490212040037

INTRODUCTION ate rocks in this deposit were formed by the elisional

At present, it has been reliably established that the
majority of manganese deposits known in the world
(Nikopol and Bolshe Tokmak, Ukraine; Chiatura,
Georgia; Mangyshlak, Kazakhstan; Novaya Zemlya,
Russia; Zunyi type deposits, China; Urkut, Hungary;
Molango, Mexico, and others), which are confined to
the Phanerozoic terrigenous and terrigenous carbon
ate rocks, were formed in humid settings. Theoretical
principles of manganese ore genesis in such environ
ment are scrutinized in the works of N.M. Strakhov
and his followers in Russia and abroad.
However, some deposits are closely associated in
space with rocks of the arid lithogenesis (sulfate ter
rigenous carbonate rocks of evaporite formations).
An example is provided by the Ulutelyak deposit
(Bashkirian Cis Ural region) described in the present
paper. Association of manganese rocks with carbon
ate sulfate rocks allowed some researchers to identify
an independent manganiferous carbonate gypsum
formation of the arid type (Khmelevskii, 1968;
Khmelevskii and Yanchuk, 1990).
Hence, accumulation of Mn in rocks of evaporite
formations took place either in arid settings (this is
inconsistent with the theory of N.M. Strakhov) or
manganization of the primary rocks took place during
late diagenesis (catagenesis, epigenesis).
In the present paper, based on the study of litholog
ical features, as well as carbon and oxygen isotopic
compositions in different types of manganese rocks
and ores, the author attempts to elucidate the forma
tion conditions of manganese carbonates and the
source of ore material for the Ulutelyak deposit. The
available data suggest that the manganiferous carbon
metasomatic process.
GEOLOGICAL SETTING
The Ulutelyak manganese deposit is located in the
southern part of the East European Platform 95 km
east northeast of Ufa and 14 km west of Asha (Bash
kortostan). According to different authors, estimates
of manganese reserves in this small deposit vary from
11.3 to 20 25 Mt, while estimates of the resources
vary from 50 to 500 Mt or more (Magadeev et al.,
1997; Cheban and Gareev, 1997; Margantsevye ,
1999; Mikhailov, 1992; Zharikov, 2000). The deposit is
mainly represented by the manganiferous carbonate
rocks and low grade manganese ores with a small
amount of oxide carbonate and oxide ores. Since the
discovery of the deposit in 1936 1940, it was studied
by many researchers (Khabakov, 1944, Betekhtin,
1946; Kheraskov, 1951; Varentsov, 1962; Makushin,
1970; and others). The deposit was studied sufficiently
well by means of the structure, prospecting, and explo
ration drilling in 1967 1970 and by the open pit min
ing in the later period. These works made it possible to
outline the main regularities in the geological setting
of the deposit. They provided insight into various
aspects of the manganiferous rocks and ores (mineral
ogy, chemistry, genesis, and distribution (Sarkisyan,
1945; Gribov, 1972a, 1972b, 1974, 1978, 1982;
Makushin, 1970, 1972, 1975; Mizens, 1979; and oth
ers). However, origin of the deposit and source of ore
material remain debatable issues.
The Ulutelyak manganese deposit is confined to
the southeastern termination of the Verkhnyaya Kama
depression located between the Bashkir and Tatar

305
306 KULESHOV

100

+5
0
21
5.4
9
I 14 17 5.9 A
4.8 5.3
25
5 7.1
P 1kg2
0 II 6.7 18 + 250
6.3
0
11 16 + 20
20
6.7 6.5 23 +1
50 P1a
100 III 22 P 1kg1
6.8
33
27 31
7.5
29 13 12
7.4 34
IV 15 452
7.3
200 34 8 7.5
28 4.9
V 5.5 30
00 0
+2 + 10
26
6.6

1 0 1 2 km

9
18

Fig. 1. Geostructural map of the manganese ore zone near the Karatau ore node. Modified after (Makushin, 1970, 1975). (1) Ter
rane of the Kungurian limestone marl dolomite anhydrite facies (ore barren members); (2) rocks of the Iren Formation
(P 1kg2); (3) manganiferous rocks of the Ulutelyak Formation; (4) zone of the transgressive occurrence of carbonate members of
the Ulutelyak Formation on the Artinskian rocks; (5) Artinskian limestones (P 1a); (6) geological boundaries; (7) Karatau anti
clinorium; (8) contours of local synsedimentary structures of the Ulutelyak time; (9) contour of the positive synsedimentary
structure of the late Ulutelyak time; (10) prospecting wells in 1968 1970 (numerator shows the well number; denominator, thick
ness of the upper ore horizon, m); (11) boundaries of the structural facies blocks and their numbers; (12) prospecting wells with
the emission of hydrocarbon gases in 1967; (13, 14) wells recovering low (13) and intense (14) alabandine mineralization; (15, 16)
zone of maximal Mn contents in the lower (15) and upper (16) ore horizons; (17) profile; (18) stratoisohypse of the Artinskian
section roof.

arches. It is separated from the Ural Foredeep by the
nearly meridional Ryazan Okhlebinino swell.
The deposit is located at the northern end of the
Cis Ural (Belsk) depression near the tectonic contact
with older rocks of the Karatau structural complex.
The central part of the manganese ore deposit (field) is
located in the Kazayakh anticline core, which com
prises the Lower Permian (Artinskian and Kugurian)
rocks (Fig. 1).
Manganese mineralization is assigned to the Kun
gurian Fillipov horizon (P1kg fl), which unconform
ably overlies the Artinskian carbonates in the study
area (Makushin, 1970). The horizon is represented by
rocks of the Ulutelyak Formation, which is marked by a
low angle (not more than 5) dip to southwest (Fig. 2)
(Makushin, 1970, 1975; Gribov, 1982). The Ulutelyak
Formation, which comprises the Lower Permian
(upper Artinskian lower Kungurian) rock complex at
the base of the halogenic formation, is represented by
a rhythmic alternation of two sulfate and two carbon
ate members.

LITHOLOGY AND MINERAL RESOURCES Vol. 47 No. 4 2012

 NEW DATA ON FORMATION CONDITIONS AND ORIGIN 307

Scale: horizontal 0 100 200 300 400 m

vertical 0 20 40 60 80 m

1 2 3 4 5 6 7 8 9

Fig. 2. Type geological section of the Ulutelyak ore field. After (Mikhailov, 2001). (1) Deluvial and alluvial loam and sandy loam
(Q2 4); (2) loess type loam cover and sandy loam at the base (N 2 Q); (3) powdery and dense silicified manganese ores (Pg3
N 1); (4) deluvial rubbly oxidized manganese ores; (5) semioxidized bouldery rubbly ores of the caprock and karst depressions
(K Pg); (6) manganiferous limestones; (7) gypsum and anhydrites; (8) limestones and marls; (9) wells.

The base of the Fillipov horizon in the Ulutelyak
Formation includes the following units (from the bot
tom to top): (i) anhydrite rocks (P 1kg fl1), thickness
35 40 m; (ii) manganiferous carbonates represented
by limestones and marls (P 1kg fl2), up to 5.3 m thick;
(iii) anhydrite rocks (P 1kg fl3), up to 50 m thick; and
(iv) manganiferous limestones (P 1kg fl4), up to 8 m
thick.
The manganiferous carbonate rocks of the Fillipov
horizon are differently bituminized. In some places,
they contain fluorite mineralization (Margantsevye ,
1999).
Rocks of the Fillipov horizon are overlain without
apparent hiatus by anhydrites and gypsum of the
Irensk (Kungurian stage) up to 25 m thick.
The commercial manganese mineralization is
assigned to the clayey calcareous (marlaceous) beds
of the Fillipov horizon (P1kg fl2 and P1kg fl4). The low
est Mn contents are recorded in the upper horizon
(5.5 8.2% as compared to 2 4% in the lower hori
zon) (Makushin, 1975).
The manganiferous carbonate rock horizons com
prise three rhythms that begin with the laminated
marls and clayey calcareous dolomites.
They are successively replaced upsection by the
bedded lumpy clayey limestones and layered oolitic
limestones. Thickness of rhythms varies from 1.6 to
3.0 m.
The maximal manganization is typical of the clayey
limestones in the middle part of rhythms. The highest
Mn content is recorded in the first rhythm. Manga
nese carbonates are represented by manganocalcite,
manganodolomite, Ca rhodochrosite, and Mg Mn
Ca carbonate (Gribov, 1972b, 1978).
The subsequent processes of karstification and
crustification in the Meso Cenozoic provoked the
leaching of gypsum and carbonates and the conse
quent deformation of ore beds. The supergene trans
formation (leaching and oxidation) of the manganif
erous carbonates produced secondary manganese
oxides, which fill up karst cavities and make up the
most valuable secondary oxide ores (Fig. 2).
The secondary manganese minerals include verna
dite and psilomelane (Gribov, 1972).
RESULTS OF LITHOLOGICAL
AND ISOTOPIC STUDIES
In order to elucidate formation conditions of man
ganese rocks and ores, we studied lithological features,
as well as carbon and oxygen isotopic compositions, of
rocks from both ore bearing sequences, which are rep
resented by manganese oxide ore interbeds and ore
barren clayey carbonate layers, and the underlying
and overlying beds of ore barren carbonates (flag
stones).
Lithological features. We carried out the micro
scopic study of mainly carbonate interbeds in the ore
horizon. The interbeds virtually lack manganese
oxides and overlie the platy (thick bedded) carbon
ates. Organogenic remnants are ubiquitous in the
rocks. However, their maximal content is recorded in
the upper oxidized carbonate horizon of the ore
sequence. The remnants are represented by foramini
fers of the families Nodosaridae and Hemigordiop
sidae (determinations by E.Ya. Yeven), as well as inde
terminable remnants of large foraminifers fusulins,
gastropods, and ostracods (Figs. 3, 4). One can also
see oncolites with the typical microorganic (algal)
internal structure (Figs. 5a, 5b).
Small fragments of carbonate material are usually
corroded by microbial organisms (cyano and archy
bacteria, calcimicrobes, micromicells, and others).

LITHOLOGY AND MINERAL RESOURCES Vol. 47 No. 4 2012

308 KULESHOV

(a) (b) 0.1 mm

0.1 mm
0.1 mm

0.1 mm

(c) (d)

0.1 mm
0.1 mm

0.1 mm 0.1 mm

0.1 mm (e) (f) 0.05 mm

0.1 mm

0.05 mm

Fig. 3. Remnants of small Mn bearing ostracod and foraminifer tests. Photomicrographs of thin sections (crossed nicols). (a)
Foraminifera (sample 14a/ 03); (b) fragment of ostracod test (sample 14a/ 03); (c) Ostracoda (sample 8/ 03); (d) Ostracoda (sam
ple 3/ 04); (e) Foraminifera (sample 10/ 03); (f) cluster of remnants of small foraminifers (?) (sample 10/ 03).

The studied samples virtually lack the clastic admix
ture (quartz, feldspars, and others).
Rocks of the ore sequence are characterized by het
erogeneity of the chemical composition: determina
tions with a SEM equipped microanalyzer show that
contents of Fe, Mn, and Ca vary significantly even
over a small distance within a single sample. Silica is
recorded universally.
The microscopic study under optical and scanning
microscopes revealed that rocks are represented by the
silty pelitic and, partly, fine sandy material that was
appreciably recrystallized. In addition to rare clasts of

LITHOLOGY AND MINERAL RESOURCES Vol. 47 No. 4 2012

 NEW DATA ON FORMATION CONDITIONS AND ORIGIN 309

(a) 30 m (b) 30 m

(c) 3 m (d) 10 m

Fig. 4. Organogenic remnants in the manganese carbonate (sample 14a/ 03) and oxide carbonate (samples 10/ 03 and 14/ 03)
rocks (SEM microphotographs taken by E.A. Zhegallo and E.Ya. Shkolnik). (a) Foraminifera (sample 14a/ 03); (b) Foraminifera
(sample 14/ 03); (c) transverse section of Foraminifera (sample 10/ 03); (d) Foraminifera (?) (sample 10/ 03).

indeterminable remnants of small macrofauna (prob
ably, gastropods and bivalves), microfauna (mainly fora
minifers), and other organic remnants (Figs. 3, 4), one
can also see numerous microbial structures (Figs. 6a 6e)
that represent mineralized remnants of bacterial mats.
Pyrite framboids are rare (Figs. 6f 6h).
It should be noted that we did not detect any basic
difference in the structure and composition of organic
remains in the oxide and carbonate rock interbeds of
the ore sequence and in the overlying and underlying
limestones.
Thus, the high carbonate content in ore barren
interbeds, small dimension of carbonate clasts (from
0.0n to n mm), lack of terrigenous admixture (quartz,
feldspars, and others), presence of rare remains of sup
pressed macrofauna, and abundance of microbial
structures suggest extreme (stress) constraints of
organic life and sedimentation in the ore bearing
sequences in the Permian basin. Such conditions are
usually typical of the sabkha type semi isolated basins
that are dominated by the biochemogenic accumula
tion of sediments in the dry and warm (semiarid and
arid) climate with intense evaporation and active
development of bacterial mats. The continental abla
tion under such conditions is strongly restricted
because of an insufficient ruggedness of topography.
Manganese oxides in the ore sequence represent
the results of oxidation of the Mn bearing carbonates
(Mn calcite, dolomite, and probably manganocalcite)
under supergene conditions. They are irregularly dis
tributed in rocks due to the primary heterogeneity of sed
imentsboth organogenic (microbial, algal and others)
nature of the primary matrix (Figs. 3a, 3f, 5, 7a 7f) and
its microclotted structure (Figs. 7g, 7h). In many
cases, such distribution in rocks is also typical of ala
bandine (Fig. 3f) (Gribov, 1972).
It is noteworthy that some sectors located near the
ore member in the overlying platy limestones are also
marked by the manganization and bitumenization in
the intergrain space of microclots (Fig. 8).
Such veinlets of the secondary, probably supergene
calcite are very rare in thin sections.
Carbon and oxygen isotopic compositions. In order to
carry out isotopic studies, we took samples of carbon
ate and oxide carbonate rocks already subjected to
supergene alterations (they contain manganese
oxides) from the northern and southern quarries. We

LITHOLOGY AND MINERAL RESOURCES Vol. 47 No. 4 2012

310
(a)
1 mm
1 mm
(b)
1 mm
1 mm
Fig. 5. Structure and pattern of manganization in oncolites
(sample 14a/ 03, crossed nicols). (a) small oncolites; (b)
large oncolite.
omitted samples containing the secondary supergene
calcite (sinter, fissure infilling, and others).
Since the studied rocks contain various carbonate
minerals, the samples were prepared for the isotope
analysis by the method of two stage decomposition in
orthophosphoric acid. The finely ground sample was
first decomposed at room temperature for 1 h accord
ing to the standard method. It was assumed that the
CO2 released in this process is related to the decompo
sition of calcite (Walters et al., 1972). Then, the sam
ple was brought up to complete decomposition at
100 over 1.5 h. The CO2 gas released in this process
is related to decomposition of the hardly soluble car
bonates (Rosenbaum and Sheppard, 1986). They are
represented by manganocalcite and Mn dolomite in
our case.
The obtained isotope data are presented in Figs. 9
and 10. It is evident that values of the carbon and oxy
gen isotopic compositions show a wide variation
range. The highest 13 values (2.8 4.5 ) are typical
LITHOLOGY AND MINERAL RESOURCES
KULESHOV
of carbonates in the underlying and overlying flag
stones. These values are appreciably higher than those
in the normal marine carbonates and typical of car
bonates formed in the shallow water semi isolated
continental basins under the semiarid and arid condi
tions.
The sulfur isotopic composition of anhydrites in
the upper sequence (anhydrite quarry; 34S 14.3
14.5 ) is typical of sulfates of this age.
Carbon and oxygen isotopic compositions of car
bonate matter in the oxide carbonate ores are charac
terized by sufficiently wide variations: from 3.8 to
3.3 for 13 and from 22.0 to 29.6 for 18; i.e.,
they are generally enriched in light isotopes of carbon
and oxygen, relative to the overlying and underlying
flagstones and barren marlaceous interbeds in the ore
member (northern quarry). Values of 13 and 18
show direct correlation samples with the heavy car
bon isotopic composition are characterized by the
highest 18 values and vice versa (Figs. 9, 10). The
domain of heavy isotopic composition includes not
only carbonates from the underlying and overlying
flagstones and barren carbonate interbeds in the
northern quarry, but also some oxide carbonate sam
ples from the ore horizon in the southern quarry.
The lighter carbon and oxygen isotopic composi
tions of manganese carbonates are most likely related
to the presence of late (authigenic) carbonate. It could
be formed as the result of percolation of specific solu
tions in the primary sediments (rocks?): the solutions
contained a small amount of 2; moreover, they were
characterized by the lighter isotopic compositions of
oxygen in water and carbon in the dissolved carbon
dioxide (domain A in Fig. 9).
What is the origin of such solutions?
First, the isotopic composition of primary carbon
ates could become lighter under the influence of
present day soil and meteoric infiltrational waters.
This process can be observed at present: the surface of
oxide carbonate rocks stripped in quarries is coated
with manganese oxides and supergene sinter calcite in
1 to 2 yr. The admixture of such calcite in the sample
can be responsible for the distribution of 13 and 18
values.
However, we can exclude this mechanism in our
case because of the following reasons. First, macro
and microscopic observations show that the studied
samples virtually lack admixture of the secondary cal
cite. Second, the isotopic composition of calcite (first
portion of 2 during the two stage decomposition of
samples in the orthophosphoric acid) in all samples is
similar (or in isotopic equilibrium) with the hardly sol
uble carbonate (manganocalcite, manganodolomite)
in the same sample. Third, the calcite/ Mn carbonate
ratio in the studied samples varies from 1 : 1 to 1 : 8,
and the isotopic composition does not show any cor
relation with this ratio. Had the lighter isotopic com
position of Mn rich and Mn bearing carbonates been
Vol. 47 No. 4 2012
 NEW DATA ON FORMATION CONDITIONS AND ORIGIN 311

(a) 10 m (b) 10 m

(c) 10 m (d) 10 m

(e) 30 m (f) 10 m

(g) 10 m (h) 3 m

Fig. 6. Mineralized microbial remnants (a e) and pyrite framboids (f h) in carbonate rocks (SEM microphotographs taken by
E.A. Zhegallo and E.Ya. Shkolnik). (a c) Sample 11/ 04; (d, e) sample 13/ 04; (f) sample 15/ 03; (g, h) sample 14/ 03.

LITHOLOGY AND MINERAL RESOURCES Vol. 47 No. 4 2012

312 KULESHOV

(a) (b)

0.2 mm
0.1 mm

0.1 mm 0.2 mm

(c) (d)
1 mm

0.2 mm

1 mm 0.2 mm

(e) 0.2 mm (f)

0.2 mm
0.1 mm

0.1 mm

(g) (h)
0.2 mm

0.1 mm

0.2 mm 0.1 mm

LITHOLOGY AND MINERAL RESOURCES Vol. 47 No. 4 2012

 NEW DATA ON FORMATION CONDITIONS AND ORIGIN 313

Fig.7. Manganiferous organogenic remnants and carbonate matrix of the Ulutelyak deposit. (a) Ostracod test, sample 15/ 04
(crossed nicols); (b) ostracod test, sample 15/ 04 (parallel nicols); (c) algal texture, sample 8/ 04 (parallel nicols); (d) algal texture,
sample 8/ 04 (parallel nicols); (e) algal texture, sample 12/ 04 (crossed nicols); (f) algal (?) texture, sample 15/ 04 (crossed nicols);
(g) manganized cyanobacterial (?) matrix, sample 3/ 04 (crossed nicols); (h) manganized cyanobacterial (?) matrix, sample 5/ 04
(crossed nicols).

related to the presence of secondary (supergene) cal
cite, we could expect a direct correlation between the
degree of lightening and the content of isotopes.
Primary nature of the established regularity is also
suggested by the irregular distribution of 13 and 18
values along the section (Fig. 10).
Hence, lightening of the carbon and oxygen isoto
pic compositions in the studied Mn rich and Mn
bearing carbonates is caused by another process that
predated the recent (Paleogene Quaternary) and,
possibly, even Mesozoic transformation under super
gene conditions, although we cannot also exclude the
presence of supergene calcite.
The nature of transforming solutions and the
mechanism of transformation are insufficiently clear.
The process can be related to the elisional oil waters
that are characterized by high Mn concentrations and
light carbon and oxygen isotopic compositions. It
could be a nanoscale process with the recrystallization
of primary rocks and, consequently, without the alter
ation of the oxygen isotopic composition of primary
rocks. Let us note that isolated phases of the secondary
carbonate are lacking in thin sections.
Mechanisms of the kinetic partitioning of isotopes
during decarbonatization, which could explain the
lighter isotopic compositions of the Mn bearing car
bonates due to removal of the heavy carbon isotope
together with carbon dioxide from the system, are not
supported by the geological data. Therefore, such ver
sions are omitted in the present paper.
GENESIS OF MANGANESE ORES
AND ROCKS
Origin of the primary Mn rich and Mn bearing
rocks in the Ulutelyak deposit is a debatable issue. The
sedimentary diagenetic genesis is the most widespread
concept. According to (Makushin, 1970), manganif
erous sediments were formed in a saline and brackish
marine lagoon during minor local transgressions in the
course of the general (progressing) degradation of sea;
i.e., regressive stage of the region development (Gri

(a) (c)
1 mm
1 mm

1 mm 1 mm

(b) (d)
0.2 mm

0.2 mm

0.2 mm 0.2 mm

Fig. 8. Character of manganization of the carbonate matrix in the overlying platy carbonate rocks in the Ulutelyak deposit. (a, b)
Sample 15/ 03 (crossed nicols); (c, d) sample 18/ 03 (crossed nicols).

LITHOLOGY AND MINERAL RESOURCES Vol. 47 No. 4 2012

314 KULESHOV

18O, (SMOW)
32
Evaporites

30 Marine Marine
diagenetic sedimentary
carbonates carbonates

28

26

24

22

20
4 2 0 2 4 6
13C, (PDB)
1 2 3 4

Fig. 9. Distribution of 13 and 18 values in rocks of the Ulutelyak manganese deposit. (1) Underlying flagstone (northern
quarry); (2) block of manganese oxide carbonate ores in the northern quarry; (3) block of manganese oxide carbonate ores in
the southern quarry; (4) overlying flagstone (northern quarry). Zone A is the inferred source of the isotopically light carbon dioxide.

bov, 1982). The source of Mn was represented by ter
rigenous material delivered from a paleoland located
in the present day Karatau massif.
According to (Gribov, 1972b), rocks of the Ulute
lyak Formation, which enclose the Mn bearing car
bonates of the Ulutelyak deposit, were formed at the
regressive stage of region evolution in a semiclosed
marine basin under arid conditions with a limited
input of terrigenous material and fresh waters from the
Urals. The Mn bearing carbonate interbeds were
formed during the short term marine transgressions
from north, leading to some decease in water salinity.
The more drastic freshening of water at the Ulutelyak
deposit was caused by intensification of the input of
fresh waters from the Ural land, probably, due to some
humidification in the recharge area. Consequently, the
accumulation of sulfate rocks was accompanied by the
deposition of limestones and calcareous dolomitic
marls (manganiferous varieties included).
It should be noted that the sedimentary diagenetic
concept cannot explain all available geological, min
eralogical, and geochemical data on the Ulutelyak
deposit. Therefore, researchers also call attention to
other mechanisms for the formation of manganese
rocks and, primarily, mechanism related to the dis
charge of Mn rich anoxic water in the hydrosulfuric
contamination zone (Makushin, 1975; Ivanov and
Petrovskii, 1998; Golota, 2000). Mechanism of the
discharge of such waters cannot also completely
explain regularities in the distribution of primary man
ganese rocks in the evaporitic rock section.
Elucidation of the genesis of manganese ores is
closely related to solution of the issue of Mn source.
Based on the available literature and our original data,
one can hardly agree with the existing concepts about
the sedimentary diagenetic origin of ores and the
delivery of Mn with terrigenous material from a pale
oland source located in the present day Karatau mas
sif (Makushin, 1970; Gribov, 1972). The existing con
cepts are not supported by many facts, e.g., the
absence of terrigenous (silty, sandy, and coarser frac
tions) admixture in the ore sequence and the overlying
section.
In addition, conditions of carbonate accumulation
in the Permian basin were such that only calcium car
bonate was deposited by the microbial mechanism
(mineralized bacterial mats). Organic life was devel
oping under extreme (stress) conditions macro
fauna was represented by suppressed forms, and their
remnants are represented by calcium carbonate. Pri
mary sedimentary diagenetic ferromanganese oxides,
typical of the well known manganese deposits (Chia

LITHOLOGY AND MINERAL RESOURCES Vol. 47 No. 4 2012

 NEW DATA ON FORMATION CONDITIONS AND ORIGIN 315

Normal marine carbonates

2/ 04
3/ 04

7/ 04
8/ 04

9/ 04
10/ 04

12/ 04

12/ 04
cm
0
13/ 0410
20
30
4 2 0 2 422 24 26 28 30
13C, (PDB) 18O, (SMOW)
5

Fig. 10. Distribution of 13 and 18 values in the manganese oxide carbonate rocks from a separate boulder in the southern
quarry at the Ulutelyak deposit. (1 5) Structures of manganese oxide carbonate rocks: (1) sparsely oolitic bedded, (2) thin bed
ded with clayey admixture, (3) bedded fine oolitic, (4) fine oolitic, (5) coarse bedded.

tura, Nikopol, Mangyshlak, and so on) and usually
represented as oolites and cement of terrigenous rock
fragments, are lacking in the Ulutelyak deposit.
According to a basically new concept, the genesis
of manganese deposits associated with sedimentary
rock sequences is related to catagenetic processes.
Possibility of the catagenetic manganese ore forma
tion in elision basins was assumed for the Mangyshlak
and Laba deposits by V.N. Kholodov, V.I. Dvorov, and
E.A. Sokolova. However, common catagenetic (eli
sional included) processes unrelated to oil formation
phases can hardly provide sufficient concentrations of
components needed for the formation of ore (in par
ticular, manganese) deposits. According to the popu
lar point of view (Paragenezis , 1990), only waters
enriched in carbon dioxide, methane, hydrogen sul
fide, and other aggressive components can leach the
enclosing rocks and transport huge masses of ore ele
ments to discharge zones. This mechanism of Mn
input was demonstrated for some manganese deposits
in (Pavlov and Dombrovskaya, 1993).
Participation of oil waters in the formation of man
ganese carbonates was suggested for the Ulutelyak
deposit by B.M. Mikhailov. He believed that mangani
ferous carbonates were produced by a complicated
mechanism: manganocalcite, manganodolomite, and
alabandine were likely formed during late diagenesis
in sediments confined to anoxic potholes in the Per
mian basin, where oil waters could percolate from the
underlying oil pools. He also noted: the bivalent
Mn, which was likely contained in waters of the Early
Permian basin, was transported together with oil
waters to the surface. The carbonate caprock above
the carbonate sulfate sequence was formed with the
participation of oil waters due to the desulfidation of
anhydrites and gypsum in the Mesozoic and Paleo
gene (Mikhailov, 2001, p. 10).
We believe that the available geological, lithologi
cal, mineralogical, geochemical, and isotope data sug
gest that the Mn rich and Mn bearing carbonates of
the Ulutelyak deposit were formed after the early
diagenetic (i.e., catagenetic) stage. According to this
concept, Mn was delivered to the primary carbonate
and carbonate clayey sediments together with the eli
sional oil waters. This was also accompanied by input
of the isotopically light carbon dioxide, resulting in
alteration of the isotopic composition of the primary
carbonate matrix. We suppose that migration pathways
of such waters were governed by the hypsometric posi
tion of the roof of sulfate members in the Ulutelyak
Formation. The latter position generally mimicked

LITHOLOGY AND MINERAL RESOURCES Vol. 47 No. 4 2012

316 KULESHOV

Isotopic compositions of carbon, oxygen, and sulfur in rocks of the Ulutelyak manganese deposit
13C, 18O,
Analysis no. Sample no. Characteristics of sample
(PDB) (SMOW)
Severnyi quarry
5218 9/ 03 Underlying carbonates (lower flagstone); calcite 2.8 29.2
Carbonate oxide rock (ore) boulder
5220 11/ 03 Interbed of thin bedded oxide carbonate rock, 0.30 m above the 3.7 28.8
boulder base
5221 12/ 03 0.55 m upsection, clayey marly interbed; calcite 2.7 28.0
5222 13/ 03 0.25 m upsection, carbonate oxide rock; calcite 2.9 29.7
5223 14/ 03 0.50 m upsection, oolitic oxide carbonate rock; calcite 3.8 22.3
5224 15/ 03 Underlying "platy" carbonate; calcite 3.1 29.5
5225 16/ 03 The same 4.5 29.9
5227 18/ 03 '' 4.4 29.7
5228 19/ 03 '' 4.4 30.0
Yuzhnyi quarry
Autonomous block of the manganese oxide carbonate ore
5411 2/ 04 Sparsely oolitic bedded oxide carbonate rock, 20 cm below the up 0.7 23.1
per edge of the block; manganocalcite
5412 3/ 04 The same, 10 cm upsection; manganocalcite 2.5 28.7
5414 5/ 04 The same, with patches of friable manganese oxides and secondary 3.3 29.4
calcite crystals; manganocalcite
5416 7/ 04 Clay rich thin bedded interbed with manganese oxides, 25 m 1.2 26.9
downsection; manganocalcite
5417 8/ 04 Thin bedded oxide carbonate rock, 15 cm downsection; manga 2.3 27.8
nocalcite
5418 9/ 04 Clayey interbed, 30 cm downsection; manganocalcite 2.4 24.2
5419 10/ 04 Horizon of thin bedded oxide carbonate rocks, 20 cm downsec 0.1 26.1
tion; manganocalcite
5420 11/ 04 Bedded fine oolitic oxide carbonate rock, 30 cm downsection, 3.0 29.7
oxidized interbed; manganocalcite
11/ 04 The same, unoxidized interbed; manganocalcite 1.6 28.2
5421 12/ 04 Oxidized fine oolitic carbonate rock, 35 cm downsection; manga 1.1 27.6
nocalcite
5422 13/ 04 Coarse bedded oxide carbonate rock, 30 cm downsection, boul 0.3 22.5
der base; manganocalcite
5426 17/ 04 Carbonate of separate oxide carbonate rock boulder, 20 cm 4.1 29.6
downsection; manganocalcite
5428 19/ 04 The same, 25 cm downsection; manganocalcite 1.9 22.0
34S,
Anhydrite quarry
1/ 03 Anhydrite, quarry floor, near the water edge 14.5
5/ 03 Anhydrite, quarry wall, 10.5 m upsection 14.3

the stratoisohypse of the Artinskian sequence roof
(Fig. 1).
It should be noted that alabandine postdated the
manganese carbonates manganese sulfide replaced
carbonate grains with the highest content of Mn at the
stage of epigenesis (Gribov, 1972a, 1972b). In this pro
cess, sulfur was derived from hydrogen sulfide that was
produced during the sulfate reduction of anhydrites
and gypsum in the host section. Hydrocarbons needed
for the reduction of sulfates were likely delivered to
sediments together with oil waters.
Thus, we can suppose that the primary carbonate
sediment were mainly represented by the mineralized
bacterial mats of different structures (oolitic included)
with some terrigenous admixture and rare small
remains of macrofauna. The sediments were subjected
to multiple alterations during both early diagenesis
(when link with the bottom and silt waters was still pre

LITHOLOGY AND MINERAL RESOURCES Vol. 47 No. 4 2012

 NEW DATA ON FORMATION CONDITIONS AND ORIGIN
served) and late diagenesis at different stages of cat
agenesis or epigenesis. Transformations after early
diagenesis were likely provoked by the input of oil
waters into sediments. The nanolevel metasomatic
transformations of primary sediments did not lead to
recrystallization of matter.
Percolation of such waters was a multistage pro
cess. At early stages, the waters contained Mn. There
fore, the primary calcite and dolomite were enriched
with Mn (metasomatism). The input of hydrocarbons
into sediments mainly at the terminal stages of litho
genesis promoted the reduction of sulfates and the for
mation of one of the latest epigenetic minerals (ala
bandine).
The multistage formation of mineral phases in
rocks of the Ulutelyak deposit was noted by E.M. Gri
bov, A.A. Makushin, and B.M. Mikhailov in the works
mentioned above.
Manganese oxides in rocks of the Ulutelyak deposit
are secondary minerals. Although contents of these
minerals in rocks are low, they are represented by
diverse (sinter, earthy, and powdery) segregations in
the intergrain space. In oxide ores, one can see the
layer by layer manganization that inherits the primary
microbial organogenic structure. Thin sections con
tain sectors with virgin organogenic remnants.
CONCLUSIONS
The results of microscopic and isotopic geochem
ical studies unraveled some typical formation condi
tions of the carbonate material that hosts manganese
oxides in the Ulutelyak deposit.
As was established in previous works (Makushin,
1970; Gribov, 1972; and others) and confirmed by our
original data, the ore hosting carbonate rocks were
deposited in a shallow water semi isolated basin
under semiarid and arid conditions. This fact allowed
some researchers (Khmelevskii, 1968; Makushin,
1970; Gribov, 1972; Khmelevskii and Yanchuk, 1990)
to recognize an autonomous manganiferous carbon
ate gypsum formation of the arid type.
The formation of manganiferous carbonates and
manganese sulfides is a secondary process, which is
likely related to the discharge of elisional oil waters
that percolated in the sulfate carbonate sequence of
the Lower Permian evaporite section. These solutions
delivered the bivalent Mn. Initially, the ore enclosing
rocks were represented by the organogenic (mainly
mineralized microbial) calcium carbonates and the
subordinate magnesium carbonates with an insignifi
cant terrigenous (probably, eolian) admixture.
Some researchers assume that the extremely shal
low water Kungurian paleobasin incorporated an
anoxic zone with hydrosulfuric contamination and
high concentrations of Mn that was transported from
the surrounding peneplain. This assumption is not
supported by factual data at least for the studied rocks.
LITHOLOGY AND MINERAL RESOURCES Vol. 47
317
As the Usa deposit in Kuznetskii Alatau (Kuleshov
and Bych, 2002) along with ore occurrences and small
deposits in Pai Khoi (Kuleshov and Belyaev, 1999),
the Ulutelyak deposit should be assigned to the catage
netic type.
ACKNOWLEDGMENTS
The author is sincerely grateful to I.A. Iskhakov
and V.G. Zharikov (OAO ANK Bashneft) for help in
the organization and accomplishment of field works.
This work was supported by the Earth Sciences
Division of the Russian Academy of Sciences (pro
gram no. 4) the Presidium of the Russian Academy of
Sciences (program no. 27), and the Russian Founda
tion for Basic Research (project no. 11 05 00584 a).
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