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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 metasomatic process.
majority of manganese deposits known in the world
(Nikopol and Bolshe Tokmak, Ukraine; Chiatura, GEOLOGICAL SETTING
Georgia; Mangyshlak, Kazakhstan; Novaya Zemlya,
Russia; Zunyi type deposits, China; Urkut, Hungary; The Ulutelyak manganese deposit is located in the
southern part of the East European Platform 95 km
Molango, Mexico, and others), which are confined to
the Phanerozoic terrigenous and terrigenous carbon east northeast of Ufa and 14 km west of Asha (Bash
kortostan). According to different authors, estimates
ate rocks, were formed in humid settings. Theoretical
principles of manganese ore genesis in such environ of manganese reserves in this small deposit vary from
11.3 to 20 25 Mt, while estimates of the resources
ment are scrutinized in the works of N.M. Strakhov
vary from 50 to 500 Mt or more (Magadeev et al.,
and his followers in Russia and abroad.
1997; Cheban and Gareev, 1997; Margantsevye ,
However, some deposits are closely associated in 1999; Mikhailov, 1992; Zharikov, 2000). The deposit is
space with rocks of the arid lithogenesis (sulfate ter mainly represented by the manganiferous carbonate
rigenous carbonate rocks of evaporite formations). rocks and low grade manganese ores with a small
An example is provided by the Ulutelyak deposit amount of oxide carbonate and oxide ores. Since the
(Bashkirian Cis Ural region) described in the present discovery of the deposit in 1936 1940, it was studied
paper. Association of manganese rocks with carbon by many researchers (Khabakov, 1944, Betekhtin,
ate sulfate rocks allowed some researchers to identify 1946; Kheraskov, 1951; Varentsov, 1962; Makushin,
an independent manganiferous carbonate gypsum 1970; and others). The deposit was studied sufficiently
formation of the arid type (Khmelevskii, 1968; well by means of the structure, prospecting, and explo
Khmelevskii and Yanchuk, 1990). ration drilling in 1967 1970 and by the open pit min
Hence, accumulation of Mn in rocks of evaporite ing in the later period. These works made it possible to
formations took place either in arid settings (this is outline the main regularities in the geological setting
inconsistent with the theory of N.M. Strakhov) or of the deposit. They provided insight into various
manganization of the primary rocks took place during aspects of the manganiferous rocks and ores (mineral
late diagenesis (catagenesis, epigenesis). ogy, chemistry, genesis, and distribution (Sarkisyan,
In the present paper, based on the study of litholog 1945; Gribov, 1972a, 1972b, 1974, 1978, 1982;
ical features, as well as carbon and oxygen isotopic Makushin, 1970, 1972, 1975; Mizens, 1979; and oth
compositions in different types of manganese rocks ers). However, origin of the deposit and source of ore
and ores, the author attempts to elucidate the forma material remain debatable issues.
tion conditions of manganese carbonates and the The Ulutelyak manganese deposit is confined to
source of ore material for the Ulutelyak deposit. The the southeastern termination of the Verkhnyaya Kama
available data suggest that the manganiferous carbon 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 ably overlies the Artinskian carbonates in the study
nearly meridional Ryazan Okhlebinino swell. area (Makushin, 1970). The horizon is represented by
The deposit is located at the northern end of the rocks of the Ulutelyak Formation, which is marked by a
Cis Ural (Belsk) depression near the tectonic contact low angle (not more than 5) dip to southwest (Fig. 2)
with older rocks of the Karatau structural complex. (Makushin, 1970, 1975; Gribov, 1982). The Ulutelyak
The central part of the manganese ore deposit (field) is
located in the Kazayakh anticline core, which com Formation, which comprises the Lower Permian
prises the Lower Permian (Artinskian and Kugurian) (upper Artinskian lower Kungurian) rock complex at
rocks (Fig. 1). the base of the halogenic formation, is represented by
Manganese mineralization is assigned to the Kun a rhythmic alternation of two sulfate and two carbon
gurian Fillipov horizon (P1kg fl), which unconform 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 quent deformation of ore beds. The supergene trans
Formation includes the following units (from the bot formation (leaching and oxidation) of the manganif
tom to top): (i) anhydrite rocks (P 1kg fl1), thickness erous carbonates produced secondary manganese
35 40 m; (ii) manganiferous carbonates represented oxides, which fill up karst cavities and make up the
by limestones and marls (P 1kg fl2), up to 5.3 m thick; most valuable secondary oxide ores (Fig. 2).
(iii) anhydrite rocks (P 1kg fl3), up to 50 m thick; and The secondary manganese minerals include verna
(iv) manganiferous limestones (P 1kg fl4), up to 8 m dite and psilomelane (Gribov, 1972).
thick.
The manganiferous carbonate rocks of the Fillipov
horizon are differently bituminized. In some places, RESULTS OF LITHOLOGICAL
they contain fluorite mineralization (Margantsevye , AND ISOTOPIC STUDIES
1999).
Rocks of the Fillipov horizon are overlain without In order to elucidate formation conditions of man
apparent hiatus by anhydrites and gypsum of the ganese rocks and ores, we studied lithological features,
Irensk (Kungurian stage) up to 25 m thick. as well as carbon and oxygen isotopic compositions, of
The commercial manganese mineralization is rocks from both ore bearing sequences, which are rep
assigned to the clayey calcareous (marlaceous) beds resented by manganese oxide ore interbeds and ore
of the Fillipov horizon (P1kg fl2 and P1kg fl4). The low barren clayey carbonate layers, and the underlying
est Mn contents are recorded in the upper horizon and overlying beds of ore barren carbonates (flag
(5.5 8.2% as compared to 2 4% in the lower hori stones).
zon) (Makushin, 1975). Lithological features. We carried out the micro
The manganiferous carbonate rock horizons com scopic study of mainly carbonate interbeds in the ore
prise three rhythms that begin with the laminated horizon. The interbeds virtually lack manganese
marls and clayey calcareous dolomites. oxides and overlie the platy (thick bedded) carbon
They are successively replaced upsection by the ates. Organogenic remnants are ubiquitous in the
bedded lumpy clayey limestones and layered oolitic rocks. However, their maximal content is recorded in
limestones. Thickness of rhythms varies from 1.6 to the upper oxidized carbonate horizon of the ore
3.0 m. sequence. The remnants are represented by foramini
The maximal manganization is typical of the clayey fers of the families Nodosaridae and Hemigordiop
limestones in the middle part of rhythms. The highest sidae (determinations by E.Ya. Yeven), as well as inde
Mn content is recorded in the first rhythm. Manga terminable remnants of large foraminifers fusulins,
nese carbonates are represented by manganocalcite, gastropods, and ostracods (Figs. 3, 4). One can also
manganodolomite, Ca rhodochrosite, and Mg Mn see oncolites with the typical microorganic (algal)
Ca carbonate (Gribov, 1972b, 1978). internal structure (Figs. 5a, 5b).
The subsequent processes of karstification and Small fragments of carbonate material are usually
crustification in the Meso Cenozoic provoked the corroded by microbial organisms (cyano and archy
leaching of gypsum and carbonates and the conse 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 over a small distance within a single sample. Silica is
ture (quartz, feldspars, and others). recorded universally.
Rocks of the ore sequence are characterized by het The microscopic study under optical and scanning
erogeneity of the chemical composition: determina microscopes revealed that rocks are represented by the
tions with a SEM equipped microanalyzer show that silty pelitic and, partly, fine sandy material that was
contents of Fe, Mn, and Ca vary significantly even 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 tion under such conditions is strongly restricted
ably, gastropods and bivalves), microfauna (mainly fora because of an insufficient ruggedness of topography.
minifers), and other organic remnants (Figs. 3, 4), one
can also see numerous microbial structures (Figs. 6a 6e) Manganese oxides in the ore sequence represent
that represent mineralized remnants of bacterial mats. the results of oxidation of the Mn bearing carbonates
Pyrite framboids are rare (Figs. 6f 6h). (Mn calcite, dolomite, and probably manganocalcite)
under supergene conditions. They are irregularly dis
It should be noted that we did not detect any basic tributed in rocks due to the primary heterogeneity of sed
difference in the structure and composition of organic imentsboth organogenic (microbial, algal and others)
remains in the oxide and carbonate rock interbeds of nature of the primary matrix (Figs. 3a, 3f, 5, 7a 7f) and
the ore sequence and in the overlying and underlying its microclotted structure (Figs. 7g, 7h). In many
limestones. cases, such distribution in rocks is also typical of ala
bandine (Fig. 3f) (Gribov, 1972).
Thus, the high carbonate content in ore barren
interbeds, small dimension of carbonate clasts (from It is noteworthy that some sectors located near the
0.0n to n mm), lack of terrigenous admixture (quartz, ore member in the overlying platy limestones are also
feldspars, and others), presence of rare remains of sup marked by the manganization and bitumenization in
pressed macrofauna, and abundance of microbial the intergrain space of microclots (Fig. 8).
structures suggest extreme (stress) constraints of Such veinlets of the secondary, probably supergene
organic life and sedimentation in the ore bearing calcite are very rare in thin sections.
sequences in the Permian basin. Such conditions are
usually typical of the sabkha type semi isolated basins Carbon and oxygen isotopic compositions. In order to
that are dominated by the biochemogenic accumula carry out isotopic studies, we took samples of carbon
tion of sediments in the dry and warm (semiarid and ate and oxide carbonate rocks already subjected to
arid) climate with intense evaporation and active supergene alterations (they contain manganese
development of bacterial mats. The continental abla oxides) from the northern and southern quarries. We

LITHOLOGY AND MINERAL RESOURCES Vol. 47 No. 4 2012


310 KULESHOV

(a) 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
1 mm

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
1 mm flagstones and barren marlaceous interbeds in the ore
member (northern quarry). Values of 13 and 18
(b)
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
1 mm

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
1 mm characterized by the lighter isotopic compositions of
oxygen in water and carbon in the dissolved carbon
Fig. 5. Structure and pattern of manganization in oncolites dioxide (domain A in Fig. 9).
(sample 14a/ 03, crossed nicols). (a) small oncolites; (b) What is the origin of such solutions?
large oncolite.
First, the isotopic composition of primary carbon
ates could become lighter under the influence of
omitted samples containing the secondary supergene present day soil and meteoric infiltrational waters.
calcite (sinter, fissure infilling, and others). This process can be observed at present: the surface of
oxide carbonate rocks stripped in quarries is coated
Since the studied rocks contain various carbonate with manganese oxides and supergene sinter calcite in
minerals, the samples were prepared for the isotope 1 to 2 yr. The admixture of such calcite in the sample
analysis by the method of two stage decomposition in can be responsible for the distribution of 13 and 18
orthophosphoric acid. The finely ground sample was values.
first decomposed at room temperature for 1 h accord However, we can exclude this mechanism in our
ing to the standard method. It was assumed that the case because of the following reasons. First, macro
CO2 released in this process is related to the decompo and microscopic observations show that the studied
sition of calcite (Walters et al., 1972). Then, the sam samples virtually lack admixture of the secondary cal
ple was brought up to complete decomposition at cite. Second, the isotopic composition of calcite (first
100 over 1.5 h. The CO2 gas released in this process portion of 2 during the two stage decomposition of
is related to decomposition of the hardly soluble car samples in the orthophosphoric acid) in all samples is
bonates (Rosenbaum and Sheppard, 1986). They are similar (or in isotopic equilibrium) with the hardly sol
represented by manganocalcite and Mn dolomite in uble carbonate (manganocalcite, manganodolomite)
our case. in the same sample. Third, the calcite/ Mn carbonate
The obtained isotope data are presented in Figs. 9 ratio in the studied samples varies from 1 : 1 to 1 : 8,
and 10. It is evident that values of the carbon and oxy and the isotopic composition does not show any cor
gen isotopic compositions show a wide variation relation with this ratio. Had the lighter isotopic com
range. The highest 13 values (2.8 4.5 ) are typical position of Mn rich and Mn bearing carbonates been

LITHOLOGY AND MINERAL RESOURCES 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 rocks. Let us note that isolated phases of the secondary
cite, we could expect a direct correlation between the carbonate are lacking in thin sections.
degree of lightening and the content of isotopes. Mechanisms of the kinetic partitioning of isotopes
Primary nature of the established regularity is also during decarbonatization, which could explain the
suggested by the irregular distribution of 13 and 18 lighter isotopic compositions of the Mn bearing car
values along the section (Fig. 10). bonates due to removal of the heavy carbon isotope
Hence, lightening of the carbon and oxygen isoto together with carbon dioxide from the system, are not
pic compositions in the studied Mn rich and Mn supported by the geological data. Therefore, such ver
bearing carbonates is caused by another process that sions are omitted in the present paper.
predated the recent (Paleogene Quaternary) and,
possibly, even Mesozoic transformation under super
gene conditions, although we cannot also exclude the GENESIS OF MANGANESE ORES
presence of supergene calcite. AND ROCKS
The nature of transforming solutions and the Origin of the primary Mn rich and Mn bearing
mechanism of transformation are insufficiently clear. rocks in the Ulutelyak deposit is a debatable issue. The
The process can be related to the elisional oil waters sedimentary diagenetic genesis is the most widespread
that are characterized by high Mn concentrations and concept. According to (Makushin, 1970), manganif
light carbon and oxygen isotopic compositions. It erous sediments were formed in a saline and brackish
could be a nanoscale process with the recrystallization marine lagoon during minor local transgressions in the
of primary rocks and, consequently, without the alter course of the general (progressing) degradation of sea;
ation of the oxygen isotopic composition of primary 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 contamination zone (Makushin, 1975; Ivanov and
rigenous material delivered from a paleoland located Petrovskii, 1998; Golota, 2000). Mechanism of the
in the present day Karatau massif. discharge of such waters cannot also completely
explain regularities in the distribution of primary man
According to (Gribov, 1972b), rocks of the Ulute
ganese rocks in the evaporitic rock section.
lyak Formation, which enclose the Mn bearing car
bonates of the Ulutelyak deposit, were formed at the Elucidation of the genesis of manganese ores is
regressive stage of region evolution in a semiclosed closely related to solution of the issue of Mn source.
marine basin under arid conditions with a limited Based on the available literature and our original data,
input of terrigenous material and fresh waters from the one can hardly agree with the existing concepts about
Urals. The Mn bearing carbonate interbeds were the sedimentary diagenetic origin of ores and the
formed during the short term marine transgressions delivery of Mn with terrigenous material from a pale
from north, leading to some decease in water salinity. oland source located in the present day Karatau mas
The more drastic freshening of water at the Ulutelyak sif (Makushin, 1970; Gribov, 1972). The existing con
deposit was caused by intensification of the input of cepts are not supported by many facts, e.g., the
fresh waters from the Ural land, probably, due to some absence of terrigenous (silty, sandy, and coarser frac
humidification in the recharge area. Consequently, the tions) admixture in the ore sequence and the overlying
accumulation of sulfate rocks was accompanied by the section.
deposition of limestones and calcareous dolomitic
In addition, conditions of carbonate accumulation
marls (manganiferous varieties included).
in the Permian basin were such that only calcium car
It should be noted that the sedimentary diagenetic bonate was deposited by the microbial mechanism
concept cannot explain all available geological, min (mineralized bacterial mats). Organic life was devel
eralogical, and geochemical data on the Ulutelyak oping under extreme (stress) conditions macro
deposit. Therefore, researchers also call attention to fauna was represented by suppressed forms, and their
other mechanisms for the formation of manganese remnants are represented by calcium carbonate. Pri
rocks and, primarily, mechanism related to the dis mary sedimentary diagenetic ferromanganese oxides,
charge of Mn rich anoxic water in the hydrosulfuric 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 alabandine were likely formed during late diagenesis
represented as oolites and cement of terrigenous rock in sediments confined to anoxic potholes in the Per
fragments, are lacking in the Ulutelyak deposit. mian basin, where oil waters could percolate from the
According to a basically new concept, the genesis underlying oil pools. He also noted: the bivalent
of manganese deposits associated with sedimentary Mn, which was likely contained in waters of the Early
rock sequences is related to catagenetic processes. Permian basin, was transported together with oil
Possibility of the catagenetic manganese ore forma waters to the surface. The carbonate caprock above
tion in elision basins was assumed for the Mangyshlak the carbonate sulfate sequence was formed with the
and Laba deposits by V.N. Kholodov, V.I. Dvorov, and participation of oil waters due to the desulfidation of
E.A. Sokolova. However, common catagenetic (eli anhydrites and gypsum in the Mesozoic and Paleo
sional included) processes unrelated to oil formation gene (Mikhailov, 2001, p. 10).
phases can hardly provide sufficient concentrations of
components needed for the formation of ore (in par We believe that the available geological, lithologi
ticular, manganese) deposits. According to the popu cal, mineralogical, geochemical, and isotope data sug
lar point of view (Paragenezis , 1990), only waters gest that the Mn rich and Mn bearing carbonates of
enriched in carbon dioxide, methane, hydrogen sul the Ulutelyak deposit were formed after the early
fide, and other aggressive components can leach the diagenetic (i.e., catagenetic) stage. According to this
enclosing rocks and transport huge masses of ore ele concept, Mn was delivered to the primary carbonate
ments to discharge zones. This mechanism of Mn and carbonate clayey sediments together with the eli
input was demonstrated for some manganese deposits sional oil waters. This was also accompanied by input
in (Pavlov and Dombrovskaya, 1993). of the isotopically light carbon dioxide, resulting in
Participation of oil waters in the formation of man alteration of the isotopic composition of the primary
ganese carbonates was suggested for the Ulutelyak carbonate matrix. We suppose that migration pathways
deposit by B.M. Mikhailov. He believed that mangani of such waters were governed by the hypsometric posi
ferous carbonates were produced by a complicated tion of the roof of sulfate members in the Ulutelyak
mechanism: manganocalcite, manganodolomite, and 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 for the reduction of sulfates were likely delivered to
(Fig. 1). sediments together with oil waters.
It should be noted that alabandine postdated the Thus, we can suppose that the primary carbonate
manganese carbonates manganese sulfide replaced sediment were mainly represented by the mineralized
carbonate grains with the highest content of Mn at the bacterial mats of different structures (oolitic included)
stage of epigenesis (Gribov, 1972a, 1972b). In this pro with some terrigenous admixture and rare small
cess, sulfur was derived from hydrogen sulfide that was remains of macrofauna. The sediments were subjected
produced during the sulfate reduction of anhydrites to multiple alterations during both early diagenesis
and gypsum in the host section. Hydrocarbons needed (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 317

served) and late diagenesis at different stages of cat As the Usa deposit in Kuznetskii Alatau (Kuleshov
agenesis or epigenesis. Transformations after early and Bych, 2002) along with ore occurrences and small
diagenesis were likely provoked by the input of oil deposits in Pai Khoi (Kuleshov and Belyaev, 1999),
waters into sediments. The nanolevel metasomatic the Ulutelyak deposit should be assigned to the catage
transformations of primary sediments did not lead to netic type.
recrystallization of matter.
Percolation of such waters was a multistage pro ACKNOWLEDGMENTS
cess. At early stages, the waters contained Mn. There
fore, the primary calcite and dolomite were enriched The author is sincerely grateful to I.A. Iskhakov
with Mn (metasomatism). The input of hydrocarbons and V.G. Zharikov (OAO ANK Bashneft) for help in
into sediments mainly at the terminal stages of litho the organization and accomplishment of field works.
genesis promoted the reduction of sulfates and the for This work was supported by the Earth Sciences
mation of one of the latest epigenetic minerals (ala Division of the Russian Academy of Sciences (pro
bandine). gram no. 4) the Presidium of the Russian Academy of
The multistage formation of mineral phases in Sciences (program no. 27), and the Russian Founda
rocks of the Ulutelyak deposit was noted by E.M. Gri tion for Basic Research (project no. 11 05 00584 a).
bov, A.A. Makushin, and B.M. Mikhailov in the works
mentioned above. REFERENCES
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