GEOLOGICA CARPATHICA, DECEMBER 2008, 59, 6, 503—514
www.geologicacarpathica.sk
Stratiform manganese mineralization in the Paleogene and
Jurassic shale formations of the Western Carpathians:
mineralogy, geochemistry and ore-forming processes
IGOR ROJKOVIČ
1
, JÁN SOTÁK
2
, PATRIK KONEČNÝ
3
and PETER ČECH
3
1
Faculty of Natural Sciences, Comenius University, Mlynská dolina, 842 15 Bratislava, Slovak Republic; rojkovic@cem.sk
2
Geological Institute of the Slovak Academy of Science, Severná 5, 974 01 Banská Bystrica, Slovak Republic; sotak@savbb.sk
3
State Geological Institute of Dionýz Štúr, Mlynská dolina 1, 817 04 Bratislava, Slovak Republic; peter.cech@gssr.sk
(Manuscript received May 5, 2008; accepted in revised form September 29, 2008)
Abstract: Manganese mineralization is bound to Paleogene (Oligocene; Rupelian) and Jurassic (Toarcian, Aalenian
and Bathonian—Callovian) shales. Mineralization is represented by manganese carbonates (rhodochrosite, kutnohorite
and Mn-calcite). Mn-oxyhydroxides (pyrolusite, manganite and rancieite) were formed later during supergene pro-
cesses by oxidation of manganese carbonates. Paleogene and Jurassic black shales with abundant framboidal pyrite are
enriched in organic matter. The average content of organic carbon is 1.04 wt. % in Paleogene shale and 1.11 wt. % in
Jurassic shale. The Si/Al ratios of 3.09 in Paleogene shale and 4.04 in Jurassic shale are close to typical marine-
sediments and hydrogeneous-detrital manganese accumulations. The distribution of the rare earth elements in the shale
suggests continental source and formation in more reducing environment than the Jurassic manganese crusts. Cobalt,
copper and nickel contents of mineralized shale are distinctly lower than in oxidic ores in the Jurassic manganese crusts
of Western Carpathians. Isotopic composition of calcite in sediments shows positive values
δ
13
C in most samples of
Paleogene and Jurassic carbonates. Increased manganese content in Mn-carbonates is closely associated with distinctly
negative values of
δ
13
C down to —9.9 in Paleogene carbonates and down to —11.2 in Jurassic carbonates. The dominant
negative
δ
13
C composition suggests early-diagenetic origin of Mn-carbonates affected by organic carbon.
Key words: geochemistry, black shale, diagenetic carbonates, supergene oxyhydroxides, C and O isotopes.
Introduction
The origin of manganese deposits is closely related to marine
facies and it reflects important events in the geological histo-
ry of the Earth like transgressions and anoxic events in the
ocean (Pratt et al. 1991; Corbin et al. 2000). Mn-oxyhydrox-
ides are deposited in oxic environment of shallow water
close to shore while carbonates form in more off-shore envi-
ronment at reduced conditions of deeper ocean (Roy 1997).
Hence, manganese can be sensitive indicator of the oxic-an-
oxic conditions of the basin.
The manganese mineralization of the Western Carpathians
was exploited in the past. Most deposits and occurrences
were studied before 1960. The main reason for this study
was to provide new data and methods not used before.
The origin of Oligocene manganese ores was explained in
terms of re-deposition of clastic or pelitic rocks (Ilavský
1979), chemical precipitation (Munk 1932; Řezáč 1959;
Pícha 1964) in an alkaline environment (Pouba 1956) ac-
companied by biochemical processes (Munk 1932; Řezáč
1959), turbidite currents (Marschalko 1959), and a tectonic
activity (Pouba 1956). A possible source of mineralization
was lateritic weathering (Pícha 1964), Permian basic volca-
nic rocks of the Hronic Unit (Ilavský 1950; Cambel 1959),
granite of the Nízke and Vysoké Tatry Mts (Munk 1932),
and weathered siderite-sulphide deposits of the Spišsko-Ge-
merské Rudohorie Mts (Marschalko 1959; Řezáč 1959). Al-
ternation of oxidic and carbonate ores was explained in
terms of the allogenic origin of oxides and authigenic origin
of carbonate, as well as by the recurrent pH and oxic-anoxic
conditions (Pícha 1964).
The origin of Jurassic manganese ores near Borinka, Led-
nické Rovne and Zázrivá was mostly related to sedimentary
processes (Polák 1955, 1956, 1957). Despite the low content
of organic carbon, mineralization in Branisko was closely re-
lated to sedimentation in epicontinental anoxic environment
(Polák & Širáňová 1993). The oxidic ore of the Lednické
Rovne deposit was attributed to oxidation of primary rhodo-
chrosite (Kantor in Andrusov et al. 1955).
Manganese crusts and nodules, formed during ocean high-
stands and corresponding to recent hard grounds, were also
found in the Jurassic limestone of the West Carpathian Klip-
pen Belt (Rojkovič et al. 2003a).
Geological setting
The stratiform manganese deposits and occurrences of the
Western Carpathians are hosted in the Paleogene, Jurassic
and Paleozoic black shale formations (Fig. 1, Table 1). The
Paleogene manganese ore occurs in the Central Carpathian
Paleogene Basin (CCPB), overlying pre-Tertiary tectonic
units south of the Pieniny Klippen Belt. The flysch sedi-
ments of the basin are represented mainly by shale and sand-
stone with conglomerate layers superimposed on the pre-
Cenozoic tectonic units of the Inner Carpathians. The CCPB
504
ROJKOVIČ, SOTÁK, KONEČNÝ and ČECH
accommodates a subsiding area of a destructive plate-margin
(Soták et al. 2001). The manganese layers are bound to a Low-
er Oligocene sequence (Soták et al. 2001, 2004). Their age is
defined by biostratigraphic Zones P18—P19 (Dentoglobigerina
tapuriensis—D. selli) and NP21—NP23 (Ericsonia subdis-
ticha—Reticulofenestra ornata). The position of the manga-
nese layers is equivalent to large manganese deposits of the
Eastern Paratethys (Muzylev 1998; Varentsov 2002).
The manganese ore in a horizon up to 3 m thick was mined in
the Poprad Basin in the Kišovce-Švábovce area (Fig. 2). Thin
bands of oxidic ore with pyrolusite, manganite, marcasite and
clay-sandy intercalations alternate here with carbonate bands
composed of Mn-calcite, rhodochrosite, pyrite and clay miner-
als due to rhythmic sedimentation (Konta 1951). The average
manganese content varied from 10 to 23 wt. % (Ilavský &
Polák 1967). Occurrences of the manganese ore in the Lower
Oligocene sequence near Michalová, Konská, Stránske, Bziny,
Pucov and Ráztočno villages are less important.
The Jurassic manganese mineralization is related mostly to
Toarcian-Aalenian shales. The Toarcian dark grey to black
Fig. 1. Deposits and occurrences of the manganese mineralization of the Western Carpathians. GPS locations and a complete list of samples
are enclosed in the Electronic Supplement of this paper (Annexes 1 and 2) at www.geologicacarpathica.sk.
Fig. 2. Geological cross-section of
the Kišovce—Švábovce deposit
(modified according to Ilavský &
Polák 1967). 1 – manganese ore,
2 – Oligocene shale, 3 – Eocene
conglomerate, 4 – Permian volca-
nic rocks, 5 – Permian sediments.
Period Epoch Age
Geological
Unit
Locality
Paleogene
Oligocene Rupelian Central
Carpathian
Paleogene
Kišovce-Švábovce,
Konská, Stránske, Bziny,
Pucov, Michalová
Jurassic
Middle Jurassic
Bathonian–Callovian
Klippen Belt
Šarišské Jastrabie
Aalenian
Klippen
Belt
Lednické Rovne,
Zázrivá 2, 3
Lower Jurassic
Toarcian
Tatricum envelope
Borinka
Toarcian
Veporicum envelope
Branisko, Dikula
Toarcian
Krížna Unit
Zázrivá 1
Table 1: Stratigraphic position of manganese mineralization in black shales of Western Carpathians.
505
MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES (WESTERN CARPATHIANS)
shale with beds of black sandy crinoid limestone with manga-
nese layers in the lower part are characteristic of the Marianka
Formation (Plašienka 1987). The Marianka Formation be-
longs to the marginal halfgraben on the northern edge of the
Tatric Unit and it is analogous to the Lower Austroalpine mar-
gin of the Eastern Alps (Plašienka 1987). Its age corresponds
to Early to Middle Toarcian according to ammonites and be-
lemnites (Rakús 1994). The Toarcian age based on the struc-
tural position and the lithostratigraphic content is presumed
also for the grey shale near Dikula (Plašienka 1995) and the
Branisko Mts (Polgári et al. 1992; Polák & Širáňová 1993).
The manganese mineralization in the black shale of the Klip-
pen Belt is younger. The manganese mineralization is bound
to the Skrzypny Formation of Aalenian age near Lednické
Rovne and Zázrivá (Wierzbowski et al. 2004), and to the Late
Bathonian—Early Callovian Sokolica Formation near Šarišské
Jastrabie village (Rojkovič et al. 2003b).
Methods
Outcroping ore layers and surrounding rocks were sam-
pled in rock profiles near Bziny, Dikula, Marianka, Pucov,
Šarišské Jastrabie and Zázrivá villages. Other samples were
collected from old mining dumps or rare outcrops (Fig. 3).
A total of 120 samples were studied in polished thin sec-
tions using polarizing microscope in transmitted and reflect-
ed light and scanning electron microscopy (SEM). The car-
bonates and oxyhydroxides were analysed in the polished
thin sections using wave-dispersion X-ray microanalysis
(WDX). WDX analyses of Al, Ba, Ca, Fe, K, Mg, Mn, Na, Si
and Sr were carried out using a CAMECA SX100 electron
microprobe at the State Geological Institute of Dionýz Štúr
in Bratislava. The following natural and synthetic standards
were used for calibration to calibrate the systems: Al
2
O
3
,
BaSO
4
, wollastonite, hematite, orthoclase, MgO, rhodonite,
albite, SiO
2
and SrTiO
3
.
Operating conditions were: 1—3
µm
beam diameter, 15—20 kV accelerating voltage, 19.9—20 nA
sample current. Detection limits were better than 0.1 wt. %.
The relative standard deviation ranged from ± 5 % (for
1 wt. %) to ± 25 % (for 0.1 wt. %). The raw data were con-
verted to oxides using PAP correction.
X-ray diffraction (XRD) analysis of a total of 67 samples of
separated mineral grains was done on a Phillips PW 1710 dif-
fractometer at the Geological Institute of the Slovak Academy
of Science in Bratislava. Samples with a high content of Fe
were analysed using K
α irradiation (λα
1
= 1.78896 m
—10
,
λα
2
= 1.79285 m
—10
). The CuK
α irradiation (λα
1
= 1.54060 m
—10
,
λα
2
= 1.54439 m
—10
) was used for other samples. Accelerating
voltage 35 kV and beam current 20 mA were used in the range
from 4 to 60 °2
Θ with 0.02 °2Θ increment.
The chemical composition of a total of 108 rock and ore
samples was analysed by atomic emission spectroscopy with
inductively coupled plasma (AES-ICP) at Geoanalytical
Laboratories of the State Geological Institute of Dionýz Štúr
in Spišská Nová Ves. Rare earth elements (REE) were analy-
sed using the same method in a total of 14 samples. Rock-
Eval pyrolysis was used to determine organic carbon (TOC)
content using the C-MAT STROHLEIN apparatus at the
Geological Institute of Slovak Academy of Science in Ban-
ská Bystrica in a total of 95 samples.
Carbon and oxygen isotopes were studied in a total of 53
samples. 20 mg of powdered rock was dissolved at 95 °C in
phosphorus acid with a density of 1.88 g/cm
3
in a closed re-
action vessel (McCrea 1950). The released CO
2
was cleaned
in cooling traps and sealed in glass capillary. The
13
C/
12
C
and
18
O/
16
O isotope ratios were measured using a Finnigan
MAT 250 mass spectrometer at State Geological Institute of
Dionýz Štúr in Bratislava, and expressed as ‰ deviation
from V-SMOW (oxygen) and V-PDB (carbon) standards.
The oxygen isotope ratio was corrected to the chemical com-
position of carbonate and the fractionation between CO
2
and
H
3
PO
4
(Rosenbaum & Sheppard 1986).
Results
Petrology and mineralogy
The mineralized rocks are represented mainly by shale, in
which carbonates, quartz, micas, chlorite and clay minerals are
the most abundant phases. The dominant fine-grained carbon-
ates form elongated aggregates or thin layers, parallel to the
bedding and thin pyrite layers (Fig. 4). The fine-grained rocks
contain parallel oriented quartz, micas and chlorite. Thin sandy
intercalations contain fragments of quartz, carbonates, sericite
schist, basalt, quartzite, plagioclase and muscovite. Rounded
sections of foraminifers, and very rare fragments of coalified
plants were also found. Accessory tourmaline, rutile and zircon
were common. Carbonates and quartz also form veinlets.
The manganese ores in Oligocene and Jurassic shales are
composed of carbonates and oxyhydroxides. The primary
minerals are represented by Mn-calcite, kutnohorite
and rhodochrosite. The Mn-oxyhydroxides correspond to
pyrolusite, rancieite and manganite. The manganese miner-
als are accompanied by pyrite, marcasite, goethite and iron
oxyhydroxides.
Fig. 3. Outcrop of the Paleogene (Rupelian) shale with layer of
manganese mineralization (interval with manganese mineralization
is marked by arrows; samples By 9.4—9.5 m).
506
ROJKOVIČ, SOTÁK, KONEČNÝ and ČECH
The carbonates are represented by calcite, Mn-calcite, do-
lomite, kutnohorite and rhodochrosite. Fine-grained aggre-
gates show zoning in back-scattered electron images. The
zoned aggregates are composed of a low-manganese phase
in cores and a high-manganese phase in rims. The central
part is composed of calcite, Mn-calcite or dolomite and the
external part of kutnohorite and rhodochrosite (Fig. 5).
These carbonates were also confirmed by X-ray diffraction.
Re-crystallized coarser grained carbonates often fill interi-
ors of foraminifers and radiolarians (Fig. 6). Veinlets of cal-
cite, Mn-calcite and quartz cut older lenticular fine-grained
carbonate aggregates.
The carbonates of Jurassic and Paleogene manganese ores
show large variability of Ca and Mn contents (Table 2,
Fig. 7). The chemical composition of rhodochrosite corre-
sponds to Ca-rhodochrosite. The Mg content reflects the ra-
Fig. 4. Oval carbonate aggregates (light), rare quartz fragments
(white) and foraminifers (round section) in shale. Kišovce, Kiš-3,
transmitted light, parallel nicols.
Fig. 6. Calcite (cal) with framboidal pyrite (py) fill foraminifera.
Zoned carbonate aggregates are represented by calcite (cal) and kut-
nohorite (kh) in the centre and by rhodochrosite (rh) in the margin.
Kišovce, Kiš-2, SEM-BEI.
Fig. 5. Zoned carbonates consist of rhodochrosite (rh) on the pe-
riphery, kutnohorite (kh) between and calcite (cal) in the centre.
Small grains of pyrite (py) are disseminated in the rock. Borinka,
Jurassic shale, HN1-6a, SEM, BEI.
Fig. 7. The chemical composition of carbonates in Oligocene and
Jurassic rocks.
507
MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES (WESTERN CARPATHIANS)
tio of dolomite fragments observed in the core of carbonate
aggregates. Average MgO contents correspond to 2.19 wt. %
in the Paleogene ores and 2.38 wt. % of MgO in the Jurassic
ores. The Paleogene and the Jurassic carbonates show dis-
tinctly different Fe contents. While the average FeO content
is 1.13 wt. % in the Paleogene ores, the Jurassic ores are sig-
nificantly enriched up to 3.93 wt. %. The increased iron con-
tent in the Jurassic ores may reflect an enrichment due to
mobilization of iron from rock-forming minerals during the
Alpine orogeny.
Pyrolusite Mn
4+
O
2
was identified in the reflected light by
the highest reflectivity among the manganese minerals,
strong anisotropy (yellow—dark brown) and characteristic
yellow colour. Elongated grains, 0.01 to 0.1 mm in diameter,
are disseminated in rock or they form aggregates with radial
texture and veinlets, replacing carbonate minerals (Fig. 8).
Pyrolusite also forms thin crusts along fissures and on the
surface of rocks. The average chemical composition of anal-
ysed pyrolusite (Table 3) corresponds to the formula:
Mn
4+
0.985
Ca
0.005
Fe
3+
0.004
Mg
0.003
Si
0.006
Al
O.002
O
2
.
Rancieite (Ca, Mn
2+
)Mn
4+
4
O
9
· 3(H
2
O) and pyrolusite are
the most abundant secondary manganese minerals. Rancieite
was firstly described in the Liassic shale of the Branisko Mts
by Polgári et al. (1992). Rancieite shows distinct bireflectance
Table 2: Chemical composition of carbonates (WDX analyses in
weight %)*.
Paleogene Jurassic
average minimum maximum average minimum maximum
CaO
36.24 5.68
56.40
29.86 0.55
59.42
MgO 2.20 0.11
22.10
2.40 0.00
21.65
FeO
1.12 0.00
6.46
3.92 0.00
32.79
MnO 17.09 0.00
54.59
21.64 0.00
53.74
SrO
0.10 0.00
0.70
0.13 0.00
2.51
BaO
0.01 0.00
0.11
0.01 0.00
0.34
CO
2
42.17 37.39
48.63
41.94 36.61
48.69
Total 98.93
99.90
n
104
164
n — number of analyses. * — complete list of analyses is involved as Elec-
tronic Supplement of this paper (Table 2a,b) at www.geologicacarpathica.sk.
Ranciete Pyrolusite
Manganite
average minimum maximum average minimum maximum average minimum maximum
MnO
2
79.57 75.69
84.98 98.11 94.72 100.00
Mn
2
O
3
88.83
88.06
89.91
CaO
6.53
2.68 11.40 0.35
0.00 1.70 0.10
0.00 0.25
Fe
2
O
3
1.01
0.24 6.82 0.37
0.14 3.09 0.19
0.15 0.23
MgO
0.81
0.00 3.16 0.03
0.00 0.29 0.02
0.00 0.03
SiO
2
0.25
0.00 3.36 0.40
0.07 0.92 0.47
0.21 0.84
Na
2
O
0.14
0.00
0.71
K
2
O
0.48
0.08 1.13 0.01
0.00 0.03 0.00
0.00 0.02
BaO
0.06
0.00 0.49 0.00
0.00 0.01 0.00
0.00 0.01
SrO
0.11
0.00
0.30
Al
2
O
3
0.19
0.00 1.83 0.13
0.00 0.41 0.07
0.01 0.21
P
2
O
5
0.03
0.00
0.29
Total
89.55
99.40
89.69
n
129
44
9
n — number of analyses. * — complete list of analyses is involved as Electronic Supplement of this paper (Table 3a,b,c) at www.geologicacarpathica.sk.
Table 3: Chemical composition of ranciete, pyrolusite and manganite (WDX analyses in weight %)*.
Fig. 8. Aggregate of pyrolusite (pl) in goethite (goe). Borinka,
Toarcian shale, BaCDH1, SEM-BEI.
Fig. 9. Radial aggregates of needle-shaped rancieite (light grey) as-
sociated with goethite (white). Bziny, Oligocene shale, sample
By 9,5b, SEM-BEI.
508
ROJKOVIČ, SOTÁK, KONEČNÝ and ČECH
and strong anisotropy (bright yellow—dark grey). Colloform
zoned aggregates, as well as needle-shaped radial aggregates
fill cavities and fissures in rocks and replace zoned carbonate
aggregates (Fig. 9). Their average chemical composition cor-
responds to the formula: Mn
total
4.099
Ca
0.521
Fe
3+
0.057
Mg
0.090
Si
0.019
Na
0.020
K
0.046
Ba
0.002
Sr
0.005
Al
0.017
P
0.002
O
9.000
. Mn
4+
and
Mn
2+
were not distinguished by WDX and they are involved
together as total Mn. X-ray diffraction analysis (XRD) con-
firmed only the strongest lines of rancieite in a few samples.
Manganite Mn
3+
O(OH) shows reflectance lower than that
of pyrolusite, and strong anisotropy. Aggregates of elongat-
ed and isometric grains (0.05 to 0.3 mm in size) fill fissures.
Its chemical composition corresponds to the formula:
Mn
3+
1.973
Ca
0.003
Fe
3+
0.004
Si
0.014
Al
0.002
O
3
. Mn
3+
represents to-
tal Mn.
Pyrite
FeS
2
forms framboids, spheroids, euhedral grains (0.05
to 2 mm in size), zoned aggregates and thin veinlets. Framboids
and re-crystallized spherical grains are frequently disseminated
or form clusters. Pyrite grains and aggregates are concentrated
into thin bands rarely up to 10 cm thick. Pyrite forms pseudo-
morphs after foraminifers, replacing and rimming them.
Marcasite FeS
2
forms lath-shaped crystals along fissures
in pyrite aggregates.
Goethite
α-Fe
3+
O(OH) and iron oxyhydroxides often in-
tergrow or rim manganese oxyhydroxides. They fill fissures
and cavities. They replace or rim carbonates and pyrite.
Their chemical composition shows large variability of man-
ganese and iron content due to the close intergrowths of their
oxyhydroxides.
Geochemistry of manganese ores
The dominant components of the Jurassic and the Paleogene
shale are Al
2
O
3
, SiO
2
and CaO (Table 4). SiO
2
content in the
shale varies from 3.42 to 49.99 wt. % (average 27.60 wt. % in
the Paleogene shale and 28.35 wt. % in the Jurassic shale).
Al
2
O
3
varies from 0.60 to 17.12 wt. % in the shale (average
7.90 wt. % in the Paleogene shale and 6.20 wt. % in the Juras-
sic shale). The Si/Al ratio corresponds to 3.09 in the Paleo-
gene shale and 4.04 in the Jurassic shale (Fig. 10). The MnO
content in the Jurassic manganese ores reaches up to
34.06 wt. % and up to 43.23 wt. % in the Paleogene ores.
The Fe
2
O
3
content (total Fe including Fe
2+
and Fe
3+
)
reaches up to 25.28 wt. % in the Paleogene shale and
35.67 wt. % in the Jurassic shale (average 7.38 wt. % in the
Paleogene shale and 8.49 wt. % in the Jurassic shale). The
Paleogene shale
Jurassic shale
average
average
Mn < 1%
Mn > 1%
total
minimum
maximum
Mn < 1%
Mn > 1%
total
minimum
maximum
SiO
2
35.92
23.12
27.60
3.42
49.99
35.93
23.91
28.35
4.55
49.12
TiO
2
0.50
0.31
0.37
0.07
0.7
0.47
0.20
0.30
0.04
0.73
Al
2
O
3
10.60
6.38
7.90
1.57
17.12
10.29
3.81
6.20
0.6
15.73
Fe
2
O
3
total
5.52
8.75
7.38
2.16
25.28
4.64
9.97
8.49
0.98
35.67
MnO
0.43
15.44
8.86
0.04
43.23
0.23
14.41
9.17
0.132
34.06
MgO
2.75
2.31
2.42
0.55
14.91
2.48
3.26
2.97
0.15
9.79
CaO
20.40
17.80
18.30
2.29
39.66
22.36
18.15
19.70
1.31
40.22
Na
2
O
0.63
0.34
0.44
0.06
2.37
0.71
0.35
0.48
0.02
1.38
K
2
O
2.03
1.17
1.48
0.22
3.3
1.97
0.73
1.19
0.03
5.52
P
2
O
5
0.15
0.39
0.28
0.06
2.56
0.15
0.47
0.31
0
2.56
H
2
O-
1.49
2.29
1.89
0.08
7.81
0.32
0.98
0.74
0.01
8.5
LOI
20.87
22.70
21.24
11.18
40.28
20.46
23.20
22.19
9.52
38.67
B
19
97
92
10
245
92
75
77
2
357
Ba
335
352
334
20
1354
202
346
293
15
2119
Co
16
29
23
2
88
17
49
37
3
191
Cr
79
72
73
22
155
58
27
39
3
93
Cu
42
34
36
6
82
42
30
34
2
84
La
27
26
26
9
83
22
56
40
9
186
Mo
2
9
9
2
111
2
4
3
2
13
Ni
54
71
62
8
186
47
37
41
4
108
Pb
16
18
16
3
43
27
23
25
6
75
Sr
602
664
619
218 1147
1422 321 779 136 2750
V
121
100
106
27
274
91
55
68
3
253
Y
23
24
23
7
39
22
36
32
10
98
Zr
97
78
89
18
299
74
81
86
10
290
Th
9
9
9
2
17
9
7
8
2
14
U
4
4
4
2
9
3
3
3
2
6
TC
5.32
5.36
5.35
0.12
11.13
5.77
6.46
6.21
0.12
11.62
TOC
0.70
1.17
1.04
0.005
5.27
0.67
1.37
1.11
0.1
4.42
TIC
4.62
4.19
4.31
0
10.93
5.10
5.07
4.67
0.04
11.12
CO
2
carb
16.93
13.46
14.04
0.03
40
18.68
17.08
18.34
7.649
30.27
n
26
36
62
17
19
46
Fe
2
O
3
total — total Fe including Fe
2+
and Fe
3+
, LOI — loss of ignition, n — number of analyses, TC — total carbon, TOC — organic carbon,TIC — inor-
ganic carbon. * — complete list of analyses is involved as Electronic Supplement of this paper (Table 4a,b) at www.geologicacarpathica.sk.
Table 4: Chemical composition of the Paleogene and Jurassic shale with manganese mineralization (oxides and C in weight %, elements in
ppm)*.
509
MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES (WESTERN CARPATHIANS)
Fig. 10. A plot of Si and Al concentrations, showing an average Si/Al
ratio 3.1 for Paleogene shale and 4.0 for Jurassic shale. The bound-
ary between hydrothermal deposits and hydrogeneous detrital sedi-
ments according to Crerar et al. (1982).
Fig. 11. Average contents of elements and oxides in the studied rocks.
Fig. 12. The distribution pattern of REE in the Jurassic mineralized
shale. Ba – Borinka, Dik – Dikula, LR – Lednické Rovne, Ma – Ma-
rianka, SJ – Šarišské Jastrabie, Za – Zázrivá potok, ZaK – Záz-
rivá, Kozinská. Chondrite values according to Evensen et al. (1978).
Fig. 13. The distribution pattern of REE in the Oligocene mineral-
ized shale. By – Bziny, Kiš – Kišovce, Ko – Konská, Ra –
Ráztočno, St – Stránske. Chondrite values according to Evensen
et al. (1978).
Fe content reflects mostly presence of pyrite and goethite in
the manganese ores bound to the Jurassic and the Paleogene
shale (Table 4). The Mn/Fe ratio in the Paleogene is 1.33
and in the Jurassic shale is 1.20.
Black and dark grey shales are enriched in organic matter
with the average content of organic carbon corresponding to
1.04 wt. % in the Paleogene strata and 1.11 wt. % in the Ju-
rassic strata (Fig. 11).
Trace elements are bound in alumosilicates, carbonates or
accessory minerals. V, Cr are related to alumosilicates, Zr,
Ti,
Th, B to clastic accessory minerals (e.g. rutile, monazite, tour-
maline) and Sr to calcite due to isomorphism with Ca. Shales
show low contents of Ni, Co and Cu (total 121 ppm in the Pa-
leogene shale and 112 ppm in the Jurassic shale). The rare
earth elements (REE) distribution pattern shows only weak
positive or absent Ce-anomaly (Figs. 12, 13, Table 5).
Stable isotopes
The stable isotope composition of carbonates reflects vari-
ability in their origin and development (Table 6). The carbon
isotope composition reflects different formation conditions
of carbonates and manganese. Calcite shows
δ
13
C values
close to 0 in Paleogene as well as in Jurassic samples. The
Mn-carbonates represented mainly by rhodochrosite
and kutnohorite are characterized by more distinct negative
δ
13
C values (down to —9.9 in the Paleogene shale and —11.2
in the Jurassic shale). The correlation coefficient of
δ
13
C val-
ues to MnO corresponds to —0.76. Negative
δ
13
C values are
characteristic for Mn-carbonates in all stratigraphic levels
(Fig. 14).
Discussion
The Central Carpathian Paleogene Basin is related to the
maximum of the Early Oligocene transgression, a global an-
oxic event and the beginning of the isolation of the Para-
tethys (Soták et al. 2001). The Sinemurian-Toarcian north-
west Neotethyan margins with adjacent grabens were filled
with deep-water black mudstone and organic-rich shale fa-
sample/chondrite
510
ROJKOVIČ, SOTÁK, KONEČNÝ and ČECH
cies (Golonka & Ford 2000). Dark grey Toarcian shale with
manganese layers in the lower part of the Marianka Forma-
tion belongs to marginal halfgraben of the northern edge of
the Tatricum and is analogous to the Lower Austroalpine
margin of the Eastern Alps (Plašienka 1987). During Toar-
cian times, the anoxic environment was formed in the Tethys
Table 5: REE content in Jurassic and Paleogene mineralized shales (in ppm).
Ocean (Bellanca et al. 1999; Corbin et al. 2000). Manganese
horizons related to the black shale were formed in rift basins
of the continental margin, occurring recently also in Austria,
Germany, Hungary, Italy and Switzerland (German 1972;
Cseh-Németh et al. 1980; Jenkyns et al. 1991). The deposits
on the margins of black shale facies formed during high sea
level stands in narrow time intervals, when ocean anoxia was
widespread (Force & Cannon 1988).
The studied Jurassic and Paleogene shales contain abun-
dant carbonate aggregates often elongated along bedding,
parallel to thin pyrite layers. The carbonate aggregates are
zoned with the central part represented by calcite, Mn-calcite
or dolomite and the external part composed of kutnohorite
and rhodochrosite. Mn-enrichment in external phases sug-
gests later diagenetic enrichment. Primary rhodochrosite can
be formed in a transition zone to deeper sea, under more re-
ducing conditions in shale, sandstone and bituminous shale
with pyrite (Borchert 1980).
Pyrite framboids are often concentrated into thin bands or
form pseudomorphs after foraminifers, replacing and rimming
them. It also suggests formation during diagenesis in a reduc-
ing environment. The framboidal texture suggests a diagenetic
origin in sense of the “organic globule” model (Rickard 1970).
The origin of the framboidal pyrite is associated with consid-
Jurassic shale with manganese mineralization
Sample
Ba 1
Dik 7
LR 2
Ma-P-2m
SJ 1
Za 6
ZaK 9
Y
59.00 19.00 21.00 18.00 79.00 98.00
La
27.00 70.00 28.00 16.00 57.00 93.00 93.00
Ce
97.00 85.00 84.00 47.00 204.00 417.00 330.00
Pr
5.00 14.20 5.00 6.00 19.00 26.00 28.00
Nd
17.00 46.20 18.00 16.00 81.00
115.00 116.00
Sm
6.00 11.20 8.00 3.80 24.00 26.00 32.00
Eu
1.00 2.30 0.80 0.70 6.10 7.90 9.80
Gd
5.90 10.10 5.20 3.30 28.30 29.50 41.90
Tb
0.70 1.40 0.70 0.60 3.50 3.50 5.10
Dy
5.30 5.30 4.70 2.30 22.80 26.50 38.80
Ho
1.00 1.30 0.90 0.60 4.20 5.30 7.20
Er
2.50 3.50 2.30 1.80 8.50
10.80 14.50
Tm
0.25 0.30 0.50 0.10 1.00 1.30 1.60
Yb
2.20 2.20 2.40 1.30 6.60 7.00 8.50
Lu
0.33 0.26 0.37 0.23 1.03 0.95 1.13
Paleogene shale with manganese mineralization
Sample By
1 By-P-9,50 By-P-11 Kiš-1
Ko-1
Ra-2
St-5
Y
31.00 39.00 36.00
37.00 22.00 32.00
La
29.00 30.00 29.00 9.00 48.00 24.00 25.00
Ce
111.00 106.00 160.00 20.00 76.00 62.00 120.00
Pr
4.90 5.80 5.70 2.00 9.00 5.50 5.00
Nd
16.00 18.90 15.40
33.00 14.60 15.70
Sm
3.40 4.30 3.80 4.00
10.00 3.60 3.50
Eu
0.80 1.10 0.80 0.20 1.60 0.70 0.80
Gd
3.60 4.70 3.60 1.60 8.90 3.20 3.90
Tb
0.50 0.70 0.60 0.25 1.10 0.60 0.60
Dy
9.00 3.60 2.00 1.70 7.60 4.90 3.50
Ho
0.60 0.80 0.40 0.30 1.50 0.60 0.70
Er
1.80 2.40 1.10 0.80 4.00 1.80 2.20
Tm
0.30 0.20 0.10 0.25 0.60 0.10 0.20
Yb
1.70 1.50 0.50 0.70 3.20 1.30 1.50
Lu
0.25 0.24 0.04 0.11 0.55 0.20 0.25
Jurassic: Ba — Borinka, Dik — Dikula, LR — Lednické Rovne, Ma — Marianka (non-mineralized shale), SJ — Šarišské Jastrabie, Za — Zázrivá
potok, ZaK — Zázrivá Kozinská. Paleogene: By — Bziny, Kiš — Kišovce, Ko — Konská, Ra — Ráztočno, St — Stránske.
Fig. 14. Correlation of carbon isotope ratios and MnO contents.
511
MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES (WESTERN CARPATHIANS)
Table 6: Isotopic composition of oxygen and carbon in carbonates of the manganese ores and accompanying rocks.
Sample Locality
Age Rock
δ
18
O
PDB
δ
13
C
PDB
δ
18
O
SMOW
MnO
Ba 4
Borinka Toarcian marl
shale
–7.2
–11.2
23.4
24.66
Ba 5
Borinka Toarcian marl
shale
–4.7
–10.0
26.1
21.14
Ba 6a,
Borinka Toarcian marl
shale
–6.2
–1.6
24.5
3.66
ByP 1
Bziny Oligocene
shale
–4.3
–2.2
26.4
1.00
ByP11, 10
Bziny Oligocene
shale
–3.7
–1.1
27.0
0.65
ByP 14
Bziny Oligocene
shale
–7.7
1.4
22.9
0.94
ByP 18
Bziny Oligocene
shale
–3.8
–0.6
27.0
0.45
ByP 5
Bziny Oligocene
shale
–6.3
–3.0
24.4
1.28
ByP 7
Bziny Oligocene
shale
–4.0
–1.0
26.7
0.51
ByP 8
Bziny Oligocene
shale
–5.0
–2.4
25.7
1.31
ByP 9,5
Bziny Oligocene
shale
–8.0
–6.4
22.6
14.09
Kiš 1
Kišovce Oligocene
shale
–2.9
–3.3
27.9
29.88
KišHo1
Hozelec Oligocene shale
–3.7
–9.9
27.1
29.15
KišŠv 2
Švábovce Oligocene shale –2.3
–1.9
28.4
21.65
KišŠv 7
Švábovce Oligocene shale –4.0
–5.8
26.3
32.57
LR 3
Lednické Rovne
Aalenian
marl shale
–2.0
4.0
28.8
3.08
Ma 0 m
Marianka Toarcian marl
shale
–7.4
1.3
23.2
0.16
Ma 1, 5 m
Marianka Toarcian limestone
–7.5
1.3
23.1
0.28
Ma P 1 m
Marianka Toarcian marl
shale
–7.3
1.3
23.3
0.17
Ma P 2
Marianka Toarcian marl
shale
–4.4
–1.0
26.3
0.23
Ma P 3
Marianka Toarcian marl
shale
–7.2
1.3
23.4
0.18
Ma P 3, 4
Marianka Toarcian limestone
–6.5
1.3
24.1
0.26
Ma P 4
Marianka Toarcian marl
shale
–7.3
1.3
23.3
0.18
Ma P 5
Marianka Toarcian marl
shale
–7.4
1.3
23.2
0.19
Ma P 6
Marianka Toarcian marl
shale
–7.3
1.2
23.3
0.17
Ma P 7
Marianka Toarcian marl
shale
–7.4
1.3
23.2
0.17
Ma P 8 m
Marianka Toarcian marl
shale
–7.1
1.3
23.5
0.13
Ma P 8, 10
Marianka Toarcian limestone
–7.7
1.2
23.0
0.27
Ma P 9 m
Marianka Toarcian marl
shale
–7.2
1.1
23.5
0.16
Ma 9.5 m
Marianka Toarcian marl
shale
–7.5
1.2
23.1
0.21
Mich 11
Michalová Oligocene shale –3.3
–9.5
27.5
30.54
P1
Pucov Oligocene
marl
–4.3
0.5
26.5
0.06
P2
Pucov Oligocene
marl
–5.1
0.8
25.7
0.05
P3
Pucov Oligocene
marl
–5.2
0.2
25.5
0.08
P4
Pucov Oligocene
marl
–4.4
0.4
26.4
0.04
P5
Pucov Oligocene
marl
–6.3
0.0
24.4
0.06
P6
Pucov Oligocene
shale
–4.2
–0.1
26.5
0.20
P7
Pucov Oligocene
shale
–5.3
–1.4
25.4
0.19
P8
Pucov Oligocene
shale
–5.0
–0.7
25.8
0.39
P9
Pucov Oligocene
shale
–5.1
–0.7
25.7
0.31
P10
Pucov Oligocene
shale
–4.3
–0.9
26.5
0.74
P11
Pucov Oligocene
shale
–4.4
–0.8
26.3
0.86
P11a
Pucov Oligocene
shale
–4.1
–8.0
26.7
1.21
P 12a
Pucov Oligocene
shale
–2.1
–6.0
28.7
8.52
P 13a
Pucov Oligocene
shale
–4.5
–0.9
26.2
1.63
Ra 1
Ráztočno Oligocene shale
–4.2
–0.9
26.5
0.73
Ra 2
Ráztočno Oligocene shale
–4.2
–1.1
26.5
5.95
ŠJ 9
Šarišské Jastrabie
Bathonian–Callovian
shale
–1.6
–7.5
29.2
20.59
ŠJ 16
Šarišské Jastrabie
Bathonian–Callovian
shale
–1.9
–7.2
28.9
29.72
Za 1
Zázrivá Toarcian marl
shale
–5.3
0.6
25.4
9.11
Za 6
Zázrivá Toarcian marl
shale
–5.2
–9.9
25.5
13.17
ZaH 11
Zázrivá 2
Aalenian
marl shale
–5.4
–2.7
25.3
0.68
ZaH 19
Zázrivá 2
Aalenian
marl shale
–3.4
–6.9
27.3
14.20
erable concentration of hydrogen sulphide derived from de-
composition of organic matter or bacterial activity (Kříbek
1977). Honjo et al. (1965) confirmed an influence of gravita-
tion on framboids of the early-diagenetic stage. Concentration
of the framboidal pyrite in the bottom of foraminifers is evi-
dent (Fig. 6).
The average chemical composition of the Jurassic Western
Carpathians manganese ores is similar to the chemical com-
position of the primary carbonate ores in Alps (German
1972) and to the Úrkút deposit in Hungary (Cseh-Németh et
al. 1980). An average Si/Al ratio corresponding to 3.09 in
the Paleogene and 4.04 in Jurassic shales are close to marine
sediments with an average Si/Al=3 according to Turekian &
Wedepohl (1961). The Si/Al ratio is much higher for manga-
nese crusts of hydrothermal origin. Crerar et al. (1982) report
on the Si/Al ratio of about 6 for the boundary between hy-
drothermal and hydrogeneous-detrital manganese accumula-
tions, and the Si/Al ratio of about 35 for manganiferous
cherts of the Franciscan assemblage. However, Toth (1980)
determined the Si/Al ratio of 5.1 for Fe-Mn crusts of proba-
ble hydrothermal origin. The studied samples show larger
dispersion of the Si/Al values even in the same locality. A
512
ROJKOVIČ, SOTÁK, KONEČNÝ and ČECH
few samples overlap the field of hydrothermal deposits, but
most samples from the same locality are consistent with a
hydrogeneous-detrital origin. Increased Si content in some
samples may indicate some distal influence of hydrothermal
source which was suggested in a Toarcian manganese car-
bonate-silicate deposit of the Krížna Unit in the Polish Tatra
Mountains (Jach & Dudek 2005). The REE distribution is
very close to that of manganese ores in the Jurassic shale of
the Northern Calcareous Alps (Rantitsch et al. 2003). The
REE distribution pattern with absent negative Ce-anomaly
suggests sedimentation in seawater and continental sources
(Ohta et al. 1999). Distinctly higher La/Ce ratio of manga-
nese ores in the Jurassic (La/Ce = 0.366) as well as in the Pa-
leogene shale (0.343) compared to the manganese crusts on
the Jurassic limestone (0.121) suggests reducing conditions
of manganese ores hosted in shales (Fig. 15). La/Ce ratio
0.25 was recorded in the sub-marine manganese-iron crusts
enriched by Ce
4+
(Toth 1980). Both types are far away from
the La/Ce ratio of 2.8 diagnostic of sea-water and typical of
hydrothermal deposits (Nath et al. 1997).
The manganese ores of the Paleogene and Jurassic shales
can be distinguished according to 10-times lower content of
Ni, Co and Cu compared to the oxidic manganese nodules
and crusts on the Jurassic limestone of the Western Car-
pathians containing up to 1255 ppm (Rojkovič et al. 2003a).
Similar low content of Ni, Co, Pb and Cu suggests sedimen-
tation of the manganese ore in a shallow sea (Roy 1980). Mn
content is higher than that of iron in the studied ores (aver-
age Mn/Fe = 1.33 in the Paleogene shale and 1.20 in the Ju-
rassic shale). This is in agreement with diagenetic origin and
sedimentation in a shallow sea. In contrast, higher Mn/Fe,
Mn/Co, Mn/Ni, Mn/Cu and Mn/Pb ratios are diagnostic of
the open-sea sediments (Roy 1980).
The shales associated with manganese mineralization rep-
resent sedimentary rocks enriched with organic matter, with
the average content of organic carbon 1.04 wt. % in Paleo-
gene and 1.11 wt. % in Jurassic shales. Oxidic manganese
ore in nodules and crusts on the Jurassic limestone showed
only 0.20 wt. % of C
org
. This corresponds to an average con-
tent of organic carbon about 2.1 wt. % in the continental
shelf and 0.17 wt. % in deep ocean nodules (Manheim
1965). The reducing environment of the Paleogene and Ju-
rassic shales was confirmed by the association of manganese
carbonates, the presence of framboidal pyrite and mainly by
the increased content of organic carbon.
Manganese carbonates are characterized by distinct nega-
tive values of
δ
13
C (up to —11 ‰) in the Paleogene and Ju-
rassic shales. The negative values of
δ
13
C in carbonates of
the black shale (—9.9 in Paleogene and —11.2 in Jurassic car-
bonates) are related to increased Mn contents (Fig. 14). The
manganese rich carbonates were formed with the distinct as-
sistance of organic carbon.
The isotopic composition is similar to that of the early-di-
agenetic Lower Oligocene ores at Nikopol in Ukraine with
δ
13
C values from —4.9 to —26.4 ‰ (Kuleshov 2003). The
younger generation of the late-diagenetic (catagenetic) car-
bonates enriched in
12
C is more significantly affected by the
organic matter, as known in the Chiaturi and Mangyshlak
deposits, where the values of —34.5 and —32.9 m, respective-
ly, have been reported (Kuleshov 2003). Such values have
not been determined in the West Carpathian manganese ores.
The carbon isotope composition of the studied manganese
ores suggests formation during early-diagenetic processes,
similar to that in the Nikopol manganese deposit. No signifi-
cant difference in the oxygen isotopic composition was ob-
served in the studied ores, similar to the Mn ores of the
Black Sea coast (Kuleshov 2003).
The early-diagenetic formation of Mn-carbonates resulting
from bacterial reduction of manganese in a near-surface en-
vironment was confirmed by negative
δ
13
C values in the
Lower Jurassic manganese ore of the Krížna Unit of the
Tatra Mountains in Poland (Krajewski et al. 2001). Similar-
ly, Polgári et al. (1991) suggest bacterial reduction during
very early burial for the Jurassic manganese carbonates at
Úrkút in Hungary. Okita et al. (1988) documented a correla-
tion between
δ
13
C values and manganese content of carbon-
ates from the Molango deposit in Mexico. The manganese
content increased with decreasing
δ
13
C values from normal
seawater values in calcite close to 0 ‰ to as low as —16 ‰
for rhodochrosite. These data were interpreted as those rep-
resenting manganese reduction via organic matter oxidation
(Okita 1992). The manganese ore of the Taoijang deposit in
China with negative
δ
13
C values also suggests biogeochemi-
cal enrichment during diagenesis (Fan et al. 1992). More
negative
δ
13
C values in rhodochrosite compared to those in
kutnohorite or calcite are similar to the manganese ores of
the south-western Taurides in Turkey (Öztrük & Hein 1997).
The above mentioned data suggest an early-diagenetic for-
mation of the studied manganese carbonates in the reducing
conditions of black shales. Abundant organic detritus caused
reduction of Mn
4+
and Fe
3+
to Mn
2+
and Fe
2+
, which dis-
solved in pore water and ascended to the sediment-water
boundary (Huckriede & Meischner 1996).
Manganese carbonates were formed due to early-diagenet-
ic microbial reduction of manganese oxides by organic mat-
Fig. 15. Correlation of La and Ce in mineralized Jurassic shale and
crusts, and in Oligocene shale (modified after Toth 1980).
513
MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES (WESTERN CARPATHIANS)
ter (Okita 1992; Öztürk & Frakes 1995; Roy 1997; Öztürk &
Hein 1997; Gutzmer & Beukes 1998; Tang & Liu 1999).
The Mn-carbonates were later replaced by oxyhydroxides
during weathering of the primary carbonate mineralization.
Hence, they represent secondary mineralization, formed due
to the oxidation of primary carbonates, as in the Alps (Beran
et al. 1983).
Conclusions
The manganese mineralization of Paleogene and Jurassic
shales is bound to horizons with increased content of organic
carbon formed in an anoxic environment. The mineraliza-
tion is represented by manganese carbonates (rhodochrosite,
kutnohorite and Mn-calcite). Mn-oxyhydroxides (pyrolusite,
manganite and rancieite) were formed later during supergene
processes by oxidation of the Mn-carbonates.
The Si/Al ratios are close to marine-sediments and hydro-
geneous-detrital manganese accumulations. The distribution
of rare earth elements confirms manganese sedimentation in
sea from a continental source in a reducing environment.
Low Ni, Co and Cu contents, increased organic carbon and
isotopic composition suggest early-diagenetic accumulation
accompanied by bacterial activity.
The isotopic composition of Paleogene and Jurassic calcite
mostly shows positive
δ
13
C values. Manganese carbonates
hosted in shales of the same ages are typical of distinctly
negative
δ
13
C values in all stratigraphic levels. The dominant
negative
δ
13
C values corroborate the early-diagenetic origin
of manganese carbonates affected by organic carbon.
Acknowledgments: This study was supported by Project
No. 0503 of the Ministry of the Environment of the Slovak
Republic and by Project VEGA No. 1/1026/04. We thank E.
Harčová for help with isotope analysis. The critical com-
ments of M. Polgári (Institute for Geochemical Research of
HAS, Budapest, Hungary), J. Hladil (CAS, Prague, Czech
Republic) and an anonymous reviewer significantly im-
proved the manuscript.
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GEOLOGICA CARPATHICA, 59, 6 (2008); ROJKOVIČ et al.: STRATIFORM MANGANESE MINERALIZATION IN
THE PALEOGENE AND JURASSIC SHALE FORMATIONS OF THE WESTERN CARPATHIANS: MINERALOGY,
GEOCHEMISTRY AND ORE-FORMING PROCESSES; ELECTRONIC SUPPLEMENT, E1–E16
www.geologicacarpathica.sk
Annexe 1: Localization of stratiform manganese mineralization of the Western Carpathians.
Locality Description
Longitude
Latitude
Borinka — Pod
Zámčiskom
Gamekeeper’s lodge, E of Borinka village, 200 m N old mining works
17º06´29´´
17º06´31´´
48º15´20´´
48º15´24´´
Borinka — Červený
domček
3.5 km N of Borinka village, 50 m E of source Červený domček 17º04´55´´
48º17´46´´
Borinka — Lipníky
6.5 km NNE from Borinka village, 5.5 km ESE from Lozorno village, 800 m NE
of Lipníky dam
17º06´58´´ 48º18´59´´
Bziny
Area “Ohrady”, 1 km SE of the church in Bziny village, outcrop
19º19´50´´
49º13´22´´
Kišovce — (Hozelec)
500 m E of eastern margin of Gánovce village. Dump 300 m S of ground elevation
700.9 and 100 m NE of travertine occurrence
20º20´19´´ 49º01´40´´
Kišovce — (Hôrka)
900 m N of road Poprad — Spišská Nová ves, dump W of mining building
20º23´19´´
49º01´07´´
Konská
200 m WSW from the church in Konská village
18º41´21´´
49º06´46´´
Lednické Rovne
W of Lednické Rovne village, 750 m NW of St. Anna church and 500 m SW from
Sedlačka hill 387.3 m. Old mining works
18º14´42´´ 49º05´34“
Mariánka
Outcrop 1.4 km ENE from church in Marianka village
17º04´25´´
48º15´01´´
Michalová
Kubická, dump of “New adit”, 30 m S of brook, 100 m NE of railway
19º45´38´´
48º46´32´´
Michalová
Kubická, dump of “Manganese adit” N of brook and 200m NNE of “New adit”,
250 m NE of railway
19º45´32´´ 48º46´34´´
Pucov
Outcrop 600 m N of Pucov village, 500 m SE of Muráň hill 719.5 m
19º22´51´´
49º13´24´´
Ráztočno
Outcrop NE of village Ráztočno 150 m
18º46´15´´ 48º46´18´´
Stránske
20 m W of SW margin of cemetery in Stránske village, fragments in field-path
18º41´59´´ 49º06´58´´
Šarišské Jastrabie
Outcrop in Vesné brook, 200 m E of Šarišské Jastrabie, 150 m NNW of ground
elevation 605.5 m
20º55´32´´ 49º14´28´´
Švábovce
Dump, on SE margin of abandoned mining plant
20º22´12´´ 49º02´06´´
Zázrivá 1, Zázrivská
dolina
Outcrop on the eastern bank of Zázrivá Brook, 5.5 km S of the church in Zázrivá
village
19º09´39´´ 49º13´42´´
Zázrivá 2 — Kozinská Dump, 250 m E of Zázrivá village, 500 m NW of the Hryzeň hill 779.8 m
19º11´49´´
49º17´32´´
Zázrivá 3 — Havrania Dump, 500 m SE from cross-road in Havrania village 19º11´27´´
49º17´45´´
ROJKOVIČ et al.: MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES;
ELECTRONIC SUPPLEMENT
E2
Annexe 2: List of samples. Part 1 from 3.
No.
Locality
No. of Sample
Source Description
Results
polished
thin section
(TS)
AES-ICP
(ICP)
C, REE
1 Borinka-Pod Zámčiskom
Ba1
dump
Mn ore
TS
AES-ICP
C, REE
2 Borinka-Pod Zámčiskom Ba4
dump
Mn
ore
TS
AES-ICP
C
3 Borinka-Červený domček Ba5
dump
Mn
ore
TS
AES-ICP
C
4 Borinka (Lozorno-Lipníky)
Ba6a
dump
Mn ore
TS
5 Borinka (Lozorno-Lipníky)
Ba6b
dump
Mn ore
TS
ICP
C
6 Borinka-Červený domček BaČD1 dump Mn
ore N,TS
7 Borinka-Červený domček
BaČD5 dump Mn
ore TS
8 Borinka-Červený domček BaČD7 dump Mn
ore TS
9
Červený domček, Mn pingy,
70 m E, of source
BaČD8 dump Mn-ore TS
10
Červený domček, Mn old
mine-works, 70 m E of source
BaČD9 dump Mn-ore TS
11 Borinka-Červený domček BaČD H14
dump
Mn ore
AES-ICP
C
12 Borinka-Červený domček BaČD H29
dump
Mn ore
AES-ICP
C
13 Borinka-Pod Zámčiskom
BaHN 6A
dump
Mn ore
AES-ICP
C
14 Borinka-Pod Zámčiskom BaHR26
dump
Mn
ore
TS
15 Borinka-Pod Zámčiskom BaHR28
dump
Mn
ore
TS
16 Borinka (Lozorno-Lipníky)
BaL4
dump
Mn ore
TS
AES-ICP
C
17 Borinka (Lozorno-Skala)
BaSA 4
dump
Mn ore
AES-ICP
C
18 Bziny
By 1
outcrop
Mn ore
TS3x
ICP
C, REE
19
Bziny, profil, 1 km SE from church,
field path
By-P-O outcrop marl
shale
AES-ICP C
20
Bziny, profile, 1 km SE from church,
field path
By-P-1 outcrop marl
shale TS
AES-ICP
C
21
Bziny, profile, 1 km SE from church,
field path
By-P-2 outcrop marl
shale
AES-ICP
C
22
Bziny, profile, 1 km SE from church,
field path
By-P-3 outcrop marl
shale
AES-ICP
C
23
Bziny, profile, 1 km SE from church,
field path
By-P-4 outcrop marl
shale
AES-ICP
C
24
Bziny, profile, 1 km SE from church,
field path
By-P-5 outcrop marl
shale TS
AES-ICP
C
25
Bziny, profile, 1 km SE from church,
field path
By-P-6 outcrop marl
shale
AES-ICP
C
26
Bziny, profile, 1 km SE from church,
field path
By-P-7 outcrop marl
shale TS
AES-ICP
C
27
Bziny, profile, 1 km SE from church,
field path
By-P-8 outcrop sandy
shale TS
AES-ICP
C
28
Bziny, profile, 1 km SE from church,
field path
By-P-9 outcrop marl
shale
AES-ICP
C
29
Bziny, profile, 1 km SE from church,
field path
By-P-9,40 outcrop
marl shale with
Mn oxides
TS AES-ICP C,
30
Bziny, profile, 1 km SE from church,
field path
By-P-9,50 outcrop
marl shale with
Mn oxides
AES-ICP
C,
REE
31
Bziny, profile, 1 km SE from church,
field path
By-P-10 outcrop marl
shale
AES-ICP C
32
Bziny, profile, 1 km SE from church,
field path
By-P-11 outcrop
marl shale with
Mn oxides
TS AES-ICP
C,
REE
33
Bziny, profile, 1 km SE from church,
field path
By-P-11,10 outcrop marl
shale
TS AES-ICP C
34
Bziny, profile, 1 km SE from church,
field path
By-P-12 outcrop marl
shale
AES-ICP C
35
Bziny, profile, 1 km SE from church,
field path
By-P-13 outcrop marl
shale
AES-ICP C
36
Bziny, profile, 1 km SE from church,
field path
By-P-14 outcrop marl
shale TS AES-ICP C
37
Bziny, profile, 1 km SE from church,
field path
By-P-15 outcrop marl
shale
AES-ICP C
38
Bziny, profile, 1 km SE from church,
field path
By-P-16 outcrop marl
shale
AES-ICP C
39
Bziny, profile, 1 km SE from church,
field path
By-P-17 outcrop marl
shale
AES-ICP C
Explanations: TS — polished thin section, V — thin section, AES-ICP — atomic emission spectroscopy with induction coupled plasma, C — rock-
Eval pyrolysis for organic carbon, REE — rare earth elements analysed by atomic emission spectroscopy with induction coupled plasma.
ROJKOVIČ et al.: MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES;
ELECTRONIC SUPPLEMENT
E3
Annexe 2: Continued. Part 2 from 3.
No.
Locality
No. of Sample
Source Description
Results
polished
thin section
(TS)
AES-ICP
(ICP)
C, REE
40
Bziny, profile, 1 km SE from church,
field path
By-P-18 outcrop marl
shale
AES-ICP C
41
Bziny, profile, 1 km SE from church,
field path
By-P-19 outcrop marl
shale
AES-ICP C
42
Bziny, profile, 1 km SE from church,
field path
By-P-20 outcrop marl
shale
AES-ICP C
43 Dikula, Baniská
Dik 1
outcrop
Mn ore
AES-ICP
C
44 Dikula, Baniská
Dik 2
outcrop
Mn ore
AES-ICP
C
45 Dikula, Baniská
Dik 3
outcrop
Mn ore
AES-ICP
C
46 Dikula, Baniská
Dik 4
outcrop
Mn ore
AES-ICP
C
47 Dikula, Baniská
Dik 5
outcrop
Mn ore
AES-ICP
C
48 Dikula, Baniská
Dik 6
outcrop
Mn ore
AES-ICP
C
49 Dikula, Baniská
Dik 7
outcrop
Mn ore
AES-ICP
C, REE
50 Kišovce (Hozelec)
Ho 1
dump
Mn ore
TS
C
51 Kišovce (Hozelec)
Ho 2
dump
sandstone
TS
ICP
C
52 Kišovce (Hozelec)
Ho 3
dump
Mn ore
TS
ICP
C
53 Kišovce (Hozelec)
Ho 4
dump
Mn ore
TS
54 Kišovce
Kiš 1
dump
Mn ore
TS
AES-ICP
C, REE
55 Kišovce
Kiš 2
dump
Mn ore
TS
AES-ICP
C
56 Kišovce
Kiš 3
dump
Mn ore
TS
57 Kišovce
Kiš 10
dump
Mn ore
TS
58 Kišovce
Kiš 11
dump
Mn ore
TS
59 Kišovce
Kiš 12
dump
Mn ore
TS
AES-ICP
ICP,C
60 Kišovce
Kiš 13
dump
Mn ore
TS
61 Kišovce Kiš
14
dump
sandstone
TS
62 Kišovce
Kiš 15
dump
Mn ore
TS
AES-ICP
C
63 Kišovce
Kiš 16
dump
Mn ore
TS
AES-ICP
C
64 Kišovce (Švábovce)
ŠV 1
dump
Mn ore
TS
65 Kišovce (Švábovce)
Šv 2
dump
Mn ore
TS
AES-ICP
C
66 Kišovce (Švábovce)
Šv 4
dump
Mn ore
TS
AES-ICP
C
67 Kišovce (Švábovce)
Šv 5
dump
Mn ore
TS
68 Kišovce (Švábovce)
Šv 6
dump
Mn ore
TS
69 Kišovce (Švábovce)
Šv 7
dump
Mn ore
TS
AES-ICP
C
70 Kišovce (Švábovce)
Šv 8
dump
Mn ore
TS
AES-ICP
C
71 Kišovce (Švábovce)
Šv 9
dump
Mn ore
TS
72 Konská
Ko-1
debris
Mn ore
TS
AES-ICP
C, REE
73 Konská Ko-2
debris
Mn
ore
TS
74 Konská Ko
3
debris
shale
TS
75 Konská Ko
4
debris
sandstone
TS
76 Konská Ko
5
debris
shale
TS
77 Konská Ko
6
debris
shale
TS
78 Konská Ko
7
debris
shale
TS
79 Konská Ko
8
debris
shale
80
Konská, 200 m W from church road,
20 m S, path and W outcrop
Ko-9 outcrop
sandy
shale TS
81
Konská, 200 m W from church road,
11 m S, path and W outcrop
Ko-10 outcrop sandy
shale
82 Lednické Rovne
LR 1
dump
Mn ore
TS
83 Lednické Rovne
LR 2
dump
Mn ore
TS
AES-ICP
C, REE
84 Lednické Rovne
LR 3
dump
Mn ore
TS2x
AES-ICP
C
85 Lednické Rovne
LR 4
dump
Mn ore
TS3x
86 Marianka, outcrop
Ma-P-0m
outcrop
black shale,
direction 134/35º
AES-ICP C
87 Marianka, outcrop
Ma-P-1m
outcrop
black shale
AES-ICP
C
88 Marianka, outcrop
Ma-P-1.5–1.6m
outcrop
limestone
TS
AES-ICP
C
89 Marianka, outcrop
Ma-P-2m
outcrop
black shale
AES-ICP
C, REE
90 Marianka, outcrop
Ma-P-3m
outcrop
black shale
AES-ICP
C
91 Marianka, outcrop
Ma-P-3.4–3.43m
outcrop
limestone
TS
AES-ICP
C
92 Marianka, outcrop
Ma-P-4m
outcrop
black shale
AES-ICP
C
93 Marianka, outcrop
Ma-P-5m
outcrop
black shale
AES-ICP
C
94 Marianka, outcrop
Ma-P-6m
outcrop
black shale
AES-ICP
C
95 Marianka, outcrop
Ma-P-7m
outcrop
black shale
AES-ICP
C
Explanations: TS — polished thin section, V — thin section, AES-ICP — atomic emission spectroscopy with induction coupled plasma, C — rock-
Eval pyrolysis for organic carbon, REE — rare earth elements analysed by atomic emission spectroscopy with induction coupled plasma.
ROJKOVIČ et al.: MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES;
ELECTRONIC SUPPLEMENT
E4
Annexe 2: Continued. Part 3 from 3.
No.
Locality
No. of Sample
Source Description
Results
polished
thin section
(TS)
AES-ICP
(ICP)
C, REE
96 Marianka, outcrop
Ma-P-8 m
outcrop
black shale
AES-ICP
C
97 Marianka, outcrop
Ma-P-8.10–8.16 m
outcrop
limestone
TS
AES-ICP
C
98 Marianka, outcrop
Ma-P-9 m
outcrop
black shale
AES-ICP
C
99 Marianka, outcrop
Ma-P-9.5 m
outcrop
black shale
AES-ICP
C
100 Marianka
Ma 11
outcrop
Mn ore
AES-ICP
C
101 Marianka
Ma 12
outcrop
Mn ore
AES-ICP
C
102 Michalová Mich
2
dump
sandstone
TS
103 Michalová Mich
3
dump
shale
TS
104 Michalová Mich
4
dump
shale
TS
105 Michalová Mich
5
dump
shale
TS
106 Michalová
Mich 8
dump
Mn ore
TS
AES-ICP
C
107 Michalová
Mich 9
dump
Mn ore
TS
AES-ICP
C
108 Michalová
Mich 11
dump
Mn ore
TS
AES-ICP
C
109 Pucov P11R1
outcrop
Mn
ore
TS
C
110 Pucov P11R2
outcrop
Mn
ore
TS
C
111
Ráztočno, 150 m from northern
margin of village, NE from parting of
footpath, direction 60 degree, 100 m
Ra-1 outcrop
Fe-Mn oxides in
shale
TS AES-ICP C
112
Ráztočno, 150 m from northern
margin of village, NE from parting of
footpath, direction 20 degree, 90 m
Ra-2 outcrop
Fe-Mn oxides in
shale
TS AES-ICP
C,
REE
113 Stránske
St 1
debris
Mn ore
TS
AES-ICP
C
114 Stránske
St 2
debris
Mn ore
115 Stránske, 20 m SW from cemetery
St-3
fragments
marl shale with
Mn-Fe oxides
116 Stránske, 20 m SW from cemetery
St-4
fragments
“
117 Stránske, 20 m SW from cemetery
St-5
fragments
“
TS
AES-ICP
C, REE
118 Šarišské Jastrabie
ŠJ 1
outcrop
shale
N, TS
AES-ICP
C, REE
119 Šarišské Jastrabie
ŠJ-2
outcrop
Mn ore
TS
120 Šarišské Jastrabie
ŠJ-3
outcrop
Mn ore
TS
121 Šarišské Jastrabie
ŠJ 5
outcrop
radiolarite
TS
AES-ICP
C
122 Šarišské Jastrabie
ŠJ 6
outcrop
radiolarite
TS
123 Šarišské Jastrabie
ŠJ 7
outcrop
radiolarite
TS
124 Šarišské Jastrabie
ŠJ 8
outcrop
shale
TS
AES-ICP
C
125 Šarišské Jastrabie
ŠJ 9
outcrop
shale
TS
AES-ICP
C
126 Šarišské Jastrabie
ŠJ 10
outcrop
Mn ore
TS
127 Šarišské Jastrabie
ŠJ 11
dump
Mn ore
TS
128 Šarišské Jastrabie
ŠJ 13
outcrop
radiolarite
TS
129 Šarišské Jastrabie
ŠJ 14
outcrop
radiolarite
TS
AES-ICP
C
130 Šarišské Jastrabie
ŠJ 15
outcrop
shale
TS
AES-ICP
C
131 Šarišské Jastrabie
ŠJ 16
outcrop
shale
TS
AES-ICP
C
132 Zázrivská dolina
Za 1
outcrop
Mn ore
TS
AES-ICP
C
133 Zázrivská dolina
Za 2
outcrop
Mn ore
TS
AES-ICP
C
134 Zázrivská dolina
Za 4
outcrop
Mn ore
TS2x
135 Zázrivská dolina
Za 5
outcrop
shale
TS
136 Zázrivská dolina
Za 6
outcrop
Mn ore
TS
AES-ICP
C, REE
137 Zázrivská dolina
Za 7
outcrop
Mn ore
TS
AES-ICP
C
138 Zázrivská dolina
Za 8
outcrop
shale
TS
139 Zázrivská dolina
Za 10
outcrop
Mn ore
TS
140 Zázrivá-Kozinská
Za 9 K
dump
Mn ore
TS
AES-ICP
C, REE
141 Zázrivská dolina
Za 3
dump
Mn ore
TS
142 Zázrivá-Kozinská ZaK
15
dump
shale
TS
143 Zázrivá-Havrania
ZaH 11
dump
Mn ore
TS2x
AES-ICP
C
144 Zázrivá-Havrania
ZaH 12
dump
Mn ore
TS
145 Zázrivá-Havrania
ZaH 13
dump
Mn ore
TS
146 Zázrivá-Havrania ZaH
16
dump
shale
TS
147 Zázrivá-Havrania ZaH
17
dump
shale
TS
148 Zázrivá-Havrania ZaH
18
dump
shale
TS
149 Zázrivá-Havrania
ZaH 19
dump
Mn ore
TS
AES-ICP
C
150 Zázrivá-Havrania
ZaH 20
dump
Mn ore
TS
Explanations: TS — polished thin section, V — thin section, AES-ICP — atomic emission spectroscopy with induction coupled plasma, C — rock-
Eval pyrolysis for organic carbon, REE — rare earth elements analysed by atomic emission spectroscopy with induction coupled plasma.
ROJKOVIČ et al.: MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES;
ELECTRONIC SUPPLEMENT
E5
Table 2a: Chemical composition of the Jurassic carbonates (WDX analyses in weight %). Part 1 from 3.
No. Sample
CaO
MgO
FeO
MnO
SrO
BaO
CO
2
Total
1
Dik5.1
54.46 1.12 0.00 0.07
0.00
0.00 44.01 99.66
2
Dik5.2
28.18 6.51 5.96 16.65
0.03
0.02 43.23
100.59
3
Dik5.3
17.16 1.08 0.49 43.14
0.04
0.00 41.73
103.64
4
Dik5.4
17.94 1.47 0.64 39.36
0.00
0.00 40.49 99.90
5
Dik5.5
17.57 1.30 1.20 38.61
0.03
0.00 39.91 98.62
6
Dik5.6
28.96 6.96 5.88 15.74
0.00
0.01 43.69
101.24
7
dik5.7
27.74 5.80 5.43 17.14
0.04
0.01 42.08 98.24
8
Dik5.7a
27.21 5.90 5.80 19.11
0.00
0.00 43.21
101.22
9
Dik5.8
53.04 3.11 0.15 0.30
0.00
0.00 45.30
101.90
10
Dik5.11
47.32 0.78 1.12 8.76
0.14
0.00 44.17
102.29
11
Dik5.12
54.17 0.87 0.07 0.10
0.00
0.00 43.57 98.78
12
Dik5.13
48.58 0.87 1.20 8.68
0.08
0.00 45.23
104.64
13
Dik5.14
50.12 0.98 0.84 6.56
0.03
0.00 44.99
103.51
14
Dik5.15
49.61 0.63 0.81 7.08
0.11
0.00 44.56
102.80
15
Dik5.16
53.72 1.09 0.09 0.24
0.13
0.00 43.61 98.88
16
Ba1.1
18.67 1.46 1.03 38.88
0.07
0.00 41.02
101.13
17
Ba1.2
6.46 0.46 0.57 53.74
0.00
0.00 39.27
100.50
18
Ba1.3
10.41 0.76 0.80 49.49
0.04
0.00 40.21
101.71
19
Ba1.4
30.42 1.63 0.40 26.26
0.13
0.00 42.24
101.08
20
Ba1-11
t
27.81 1.38 0.55 28.80
0.14
0.00 41.60
100.28
21
Ba1-12-s
9.58 0.68 0.86 49.61
0.05
0.04 39.60
100.42
22
Ba1-13-n
9.79 1.32 4.19 45.54
0.07
0.05 39.99
100.95
23
Ba1-14-n 30.90 21.65 0.23 0.72
0.11
0.00 48.53
102.14
24
Ba1-15-n 31.93 20.61 0.23 0.68
0.00
0.00 48.13
101.58
25
Ba1-16-s 14.50 1.08 0.75 42.75
0.00
0.00 39.54 98.62
26
Ba1-17-s 24.13 1.81 1.19 30.84
0.02
0.02 40.79 98.80
27
Ba1-18
p 27.11 3.35 6.74 20.12
0.19
0.04 41.64 99.19
28
Ba1-19-t
28.40 1.54 0.87 26.75
0.04
0.00 41.11 98.71
29
Ba1-20-s 19.61 1.25 0.87 36.78
0.00
0.01 40.11 98.63
30
Ba5.1
15.43 1.11 11.06 33.64 0.05 0.00 40.99 102.28
31
Ba5.2
8.02 0.58 16.06 40.39 0.04 0.00 41.83 106.91
32
Ba5.4
53.60 0.02 0.57 0.52
0.39
0.04 42.93 98.07
33
Ba5.5
6.80 1.49 10.33 44.08 0.00 0.02 40.65 103.38
34
Ba5.6
16.02 1.26 1.57 40.83
0.08
0.00 40.28
100.04
35
Ba6.1
49.55 0.45 2.15 7.49
0.35
0.01 45.49
105.48
36
Ba6.2
46.34 0.56 2.77 9.48
0.31
0.00 44.69
104.14
37
Ba6.3
50.10 0.56 2.56 9.03
0.32
0.00 47.24
109.81
38
Ba6.4
51.81 0.38 1.80 2.66
0.76
0.00 44.15
101.56
39
BaCDD1.1 55.85 0.36 0.00 0.00
0.00
0.00 44.22
100.43
40
BaCDD1.2 55.46 0.35 0.02 0.00
0.00
0.00 43.92 99.75
41
BaCDD5-1 55.30 0.46 0.00 0.11
0.05
0.00 43.99 99.91
42
BaCDD5-2 51.70 0.28 0.12 3.11
0.02
0.00 42.89 98.12
43
BaCDD5-3 54.34 0.31 0.00 3.33
0.00
0.00 45.05
103.03
44
BaCDD5-3 54.47 0.25 0.11 1.01
0.08
0.00 43.75 99.67
45
Ba-CDH14 28.26 5.17 11.69 11.86 0.15 0.00 42.41 99.54
46
BsCD-H14 21.78 2.99 6.43 26.25
0.08
0.00 40.62 98.15
47
BaHn1-5. 28.03 1.36 1.44 27.06
0.07
0.00 41.18 99.14
48
BaHN1-5. 7.29 0.79 0.75 50.90
0.09
0.00 38.66 98.48
49
BaHN1-5. 7.68 0.86 0.73 50.12
0.04
0.00 38.52 97.95
50
BaHn1-5. 19.91 1.24 0.75 35.99
0.04
0.00 39.78 97.71
51
BaHn1-5.
7.80 0.76 0.74 50.12
0.00
0.00 38.50 97.92
52
BaHn1-6a 20.09 1.25 0.87 36.61
0.05
0.01 40.40 99.27
53
BaHn1-6a 7.57 0.95 2.24 49.53
0.07
0.03 39.12 99.51
54
BaHn1-6a 8.82 1.00 6.81 43.41
0.03
0.00 39.13 99.20
55
BaHn1-6a 26.58 2.84 7.91 19.71
0.06
0.02 41.07 98.19
56
BaHn1-6a 20.91 1.14 1.04 34.38
0.00
0.00 39.62 97.09
57
BaHn1-6a 31.85 0.36 0.09 24.90
0.00
0.00 40.89 98.09
58
BaHn1-6a 17.96 1.63 2.18 35.98
0.01
0.00 39.54 97.29
59
BaHn1-6a 26.74 1.44 0.53 28.13
0.11
0.03 40.39 97.37
60
BaHn1-6a 18.48 1.08 0.72 38.45
0.05
0.00 40.00 98.78
61
BaHn1-6a 8.53 0.87 2.54 48.26
0.05
0.03 39.17 99.45
62
BaHN1-6a 22.31 1.43 1.55 32.49
0.12
0.04 40.24 98.18
63
BaSa2-2. 24.35 1.37 0.84 30.91
0.11
0.00 40.34 97.92
64
BaSa2-2. 54.73 0.00 0.23 0.53
0.38
0.00 43.58 99.45
65
LR1
51.92 0.00 0.70 1.71
0.00
0.00 42.24 96.57
66
LR2
55.61 0.00 0.00 0.00
0.00
0.00 43.64 99.25
67
LR3
33.23 17.86 0.77 1.36
0.00
0.00 46.90
100.12
68
LR3.1
25.41 1.38 0.50 31.00
0.05
0.01 41.01 99.36
69
LR3.2
23.60 1.26 0.82 32.91
0.07
0.06 40.87 99.60
70
LR3.3
51.60 1.06 2.41 5.38
0.99
0.00 46.89
108.34
ROJKOVIČ et al.: MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES;
ELECTRONIC SUPPLEMENT
E6
Table 2a: Continued. Part 2 from 3.
No. Sample
CaO
MgO
FeO
MnO
SrO
BaO
CO
2
Total
71
LR3.4
17.49 1.77 1.89 36.57
0.08
0.01 39.55 97.36
72
LR3.5
14.09 2.19 3.65 40.03
0.01
0.01 40.53
100.51
73
LR3.6
30.64 1.87 0.76 27.09
0.08
0.04 43.41
103.91
74
LR3.7
16.27 1.69 2.12 40.30
0.14
0.02 40.99
101.54
75
LR3.8
35.78 16.17 3.33 0.30
0.05
0.00 47.98
103.60
76
LR3.9
6.94 9.80 24.62 15.64 0.04 0.16 40.99 98.18
77
LR3.10
7.00 7.43 20.49 20.10 0.05 0.06 38.66 93.79
78
LR3.11
52.99 0.66 2.07 5.58
0.32
0.01 47.18
108.81
79
LR3.12
14.96 1.51 2.24 39.25
0.05
0.06 39.15 97.21
80
LR3.13
54.99 0.28 1.12 3.87
0.20
0.00 46.64
107.10
81
LR3.14
20.62 1.16 0.58 37.10
0.06
0.06 40.86
100.44
82
Za1zilka
50.05 0.40 0.96 5.37
0.00
0.00 43.63
100.41
83
Za1tmelt 48.99 0.54 0.40 5.74
0.00
0.00 42.84 98.51
84
Za 1 sve
31.29
4.66
5.41
12.59
0.00
0.00
40.77
94.72
85
Za1
svet
31.45 4.36 5.31 13.14
0.00
0.00 40.85 95.11
86
Za2.1
8.51 7.89 13.66 27.41 0.00 0.11 40.70 98.29
87
Za2.2
18.30 1.08 0.32 40.00
0.00
0.01 40.56
100.27
88
Za2.3
19.14 1.14 0.31 39.51
0.02
0.03 40.99
101.16
89
Za2.4
30.17 15.84 3.95 4.58
0.18
0.34 46.40
101.45
90
Za2.5
50.44 0.86 0.81 9.77
0.08
0.00 47.12
109.09
91
Za2.6
29.35 15.37 4.63 4.73
0.15
0.25 45.73
100.21
92
Za2.7
17.14 1.39 1.44 41.78
0.11
0.04 41.84
103.74
93
Za2.8
23.04 1.03 0.40 34.60
0.09
0.03 40.97
100.18
94
Za2.9
20.92 1.38 0.84 35.99
0.05
0.02 40.78 99.97
95
Za2.10
11.47 1.54 2.20 46.82
0.08
0.07 41.14
103.32
96
ZA5.1
47.25 0.77 0.65 7.37
0.11
0.00 42.94 99.09
97
Za5.2sv
31.42 4.03 5.36 16.34
0.02
0.00 42.49 99.66
98
Za5.3
tm 46.57 0.92 0.88 7.59
0.13
0.00 42.85 98.94
99
Za5.4
sv
19.30 1.05 0.37 38.35
0.00
0.04 40.32 99.43
100
Za5.5
sv
16.03 1.23 0.50 40.81
0.00
0.00 39.55 98.12
101
Za5.6
tm 18.34 1.34 0.55 38.13
0.00
0.01 39.85 98.22
102
Za5.7
sv
17.39 0.95 0.33 39.76
0.07
0.05 39.60 98.15
103
Za6
kt
23.10 1.79 0.81 30.18
0.00
0.00 39.30 95.18
104
Za6kt
19.77 1.20 0.56 36.42
0.04
0.00 39.78 97.77
105
Za6kt
23.32 1.62 1.00 30.17
0.06
0.00 39.43 95.60
106
Za6ka
52.48 1.41 0.35 3.04
0.19
0.00 44.91
102.38
107
Za6ka
46.53 0.69 0.71 10.35
0.25
0.00 44.23
102.76
108
Za6ka
49.89 0.49 0.81 5.53
0.24
0.00 43.72
100.68
109
Za6ka
51.44 0.82 0.73 8.82
0.00
0.00 47.18
108.99
110
ZaK9.1
19.74 2.16 0.38 34.19
0.05
0.00 39.32 95.84
111
Za11.1
59.42 0.78 0.60 1.29
0.10
0.00 48.69
110.88
112
Za12.1
s
8.73 3.02 10.67 35.71 0.06 0.04 38.88 97.11
113
Za12.2
t
26.77 1.44 1.07 28.14
0.06
0.00 40.72 98.20
114
Za12.3
n
32.08 18.89 0.39 3.76
0.51
0.00 48.59
104.22
115
Za12.4
n
48.23 1.36 3.56 4.85
0.60
0.00 44.78
103.38
116
Za12.5
n
30.35 18.57 0.73 3.55
0.04
0.00 46.76
100.00
117
Za12.6
s
10.11 4.09 13.67 30.81 0.00 0.07 39.91 98.66
118
Za12.7
s
54.28 0.12 0.87 0.53
0.10
0.00 43.63 99.53
119
Za12.8
s
11.85 1.41 1.96 43.99
0.02
0.01 39.34 98.58
120
Za12.9
s
9.42 5.20 19.27 24.76 0.03 0.09 40.27 99.04
121
Za12.10
28.63 1.68 1.56 25.75
0.11
0.00 41.28 99.01
122
Za15.1
52.43 0.49 0.95 3.30
0.03
0.00 44.32
101.52
123
Za15.2
54.21 0.68 0.25 0.91
0.06
0.00 44.03
100.14
124
Za17.1
t
51.60 3.41 0.09 0.06
0.20
0.00 44.40 99.76
125
Za17.2
s
49.10 0.60 1.30 4.21
0.00
0.00 42.60 97.81
126
Za17.3
s
51.66 0.71 0.69 2.54
0.36
0.00 43.47 99.43
127
Za17.4
t
55.61 0.28 0.00 0.05
0.03
0.02 44.00 99.99
128
Za17.5
t
54.77 0.01 0.18 0.16
0.15
0.00 43.27 98.54
129
Za17.6
s
14.77 0.97 0.22 43.87
0.01
0.03 40.02 99.89
130
Za17.7
s
11.79 1.72 0.69 44.14
0.12
0.00 38.99 97.45
131
Za17.8
s
14.18 0.88 0.33 44.57
0.00
0.00 39.94 99.90
132
Za17.9
s
22.78 1.33 0.36 31.99
0.06
0.12 39.46 96.10
133
Za17.10
21.09 1.31 0.32 34.60
0.07
0.11 39.70 97.20
134
Za17.11
54.03 0.02 0.30 0.04
0.27
0.00 42.75 97.41
135
Za17.12
27.80 1.86 0.37 28.51
0.10
0.00 41.80
100.44
136
ZaH19svf
5.09 6.88 27.46 17.19 0.00 0.00 38.99 95.61
137
ZaH19tm 29.95 1.48 0.64 25.76
0.21
0.00 41.58 99.62
138
ZaH19tm 32.01 1.32 0.83 22.29
0.06
0.00 40.92 97.43
139
ZaH19tm 28.59 1.33 1.38 25.88
0.13
0.00 40.85 98.16
140
ZaH19tm 28.14 1.73 1.39 25.62
0.09
0.00 40.76 97.73
ROJKOVIČ et al.: MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES;
ELECTRONIC SUPPLEMENT
E7
Table 2a: Continued. Part 3 from 3.
No. Sample
CaO
MgO
FeO
MnO
SrO
BaO
CO
2
Total
141
ZaH19pre 23.74 1.28 0.66 31.11
0.15
0.00 39.80 96.74
142
ZaH19sv 24.60 1.35 0.39 30.51
0.00
0.00 39.95 96.80
143
SJ2
3.52 1.89 20.90 33.34 0.00 0.00 38.31 97.96
144
SJ2
3.52 1.89 20.90 34.34 0.00 0.00 38.93 99.58
145
SJ9-19
0.55 2.01 32.79 23.42 0.00 0.00 37.24 96.01
146
SJ9-18
4.31 1.99 21.18 30.62 0.00 0.00 37.52 95.61
147
SJ16-11
2.15 2.04 28.48 24.57 0.00 0.00 36.61 93.86
148
SJ9
3.23 1.97 22.83 31.62 0.00 0.00 38.29 97.94
169
SJ10.1
4.63 2.04 23.05 30.95 0.01 0.00 39.19 99.87
150
SJ10.2
3.50 1.97 22.43 33.00 0.01 0.00 39.12 100.03
151
SJ16.1
10.20 1.93 2.16 43.13
0.01
0.00 38.20 95.63
152
SJ16.2
3.09 2.04 30.54 26.51 0.00 0.00 39.81 101.99
153
SJ16.3
6.67 2.00 13.12 37.75 0.02 0.00 38.88 98.44
154
SJ16.4
2.36 2.13 32.77 25.19 0.00 0.00 39.88 102.33
155
MaP1.5.1 51.68 0.53 0.78 0.28
2.51
0.00 42.85 98.63
156
MaP1.5.2 53.64 0.37 1.05 0.34
0.20
0.00 43.43 99.02
157
MaP1.5.3 53.69 0.34 1.14 0.34
0.09
0.00 43.45 99.05
158
MaP1.5.4 53.34 0.43 0.61 0.24
1.57
0.00 43.51 99.69
159
MaP1.5.5 53.90 0.26 0.96 0.47
0.14
0.00 43.52 99.24
160
MaP1.5.6 53.21 0.47 0.73 0.37
1.78
0.00 43.70
100.26
161
MaP1.5.7 53.21 0.42 0.65 0.17
1.83
0.00 43.51 99.80
162
MaP7b.8s 55.98 0.07 0.28 0.18
0.03
0.00 44.30
100.83
163
MaP7b.9s 53.14 1.51 0.16 0.00
0.03
0.00 43.47 98.31
164
MaP7b.10 54.14 0.54 0.61 0.13
0.17
0.00 43.60 99.19
CaO MgO FeO MnO SrO BaO CO
2
Total
Average
29.86 2.40 3.92 21.64
0.13
0.01 41.94 99.90
minimum
0.55 0.00 0.00 0.00
0.00
0.00 36.61
maximum
59.42 21.65 32.79 53.74 2.51 0.34 48.69
n
164
164
164
164
164
164
164
ROJKOVIČ et al.: MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES;
ELECTRONIC SUPPLEMENT
E8
Table 2b: Chemical composition of the Paleogene carbonates (WDX analyses in weight %).
Part 1 from 2.
No. Sample CaO MgO FeO MnO SrO BaO CO
2
Total
1
Ra2a.3
56.40 0.13 0.01 0.04
0.00
0.00 44.44
101.03
2
Ra1.2
56.00 0.33 0.02 0.01
0.00
0.00 44.32
100.68
3
Ho3.3
sv 13.11 1.27 0.31 44.98
0.00
0.00 39.77 99.44
4
Ho3.5
sv 11.40 1.81 0.98 43.83
0.00
0.00 38.72 96.74
5
Ho3.8 tm
30.54
22.10
0.13
0.63
0.00
0.00
48.57
101.97
6
MnKis1/1 29.47 2.16 0.00 23.38
0.00
0.00 39.99 95.00
7
MnKis1/3 25.64 1.71 0.00 28.42
0.00
0.00 39.62 95.39
8
MnKis1/5 24.54 1.96 0.59 29.97
0.00
0.00 40.35 97.41
9
Sv7sv
10.97 1.09 0.57 45.06
0.00
0.00 38.10 95.79
10
Sv8.2
sv
6.41 0.99 0.65 51.88
0.00
0.05 38.71 98.69
11
Sv8.5
tm
30.50 20.45 0.18
1.17 0.00 0.00 47.10 99.40
12
Sv8.6
st
31.73 1.83 0.19 22.46
0.00
0.10 40.98 97.29
13
Sv8.7 tm
30.58
21.49
0.12
0.37
0.00
0.02
47.77
100.35
14
Sv8.9
sv
9.04 1.73 0.83 46.53
0.00
0.00 38.36 96.49
15
Ko2-klas
31.76 20.28 0.00
0.00 0.00 0.00 47.07 99.11
16
Ko2-karb 48.04 0.48 3.24 3.15
0.00
0.00 42.16 97.07
17
Ko3-1
54.14 0.82 0.07 0.03
0.00
0.00 43.44 98.50
18
Ko3-2
53.96 0.38 1.37 0.62
0.00
0.00 43.99
100.32
19
Mich11bt 45.14 1.95 2.45 8.18
0.00
0.00 44.13
101.85
20
Mich11bs
6.58 1.14 1.47 48.73
0.00
0.00 37.54 95.46
21
Mich11b 46.77 1.69 2.02 8.05
0.00
0.00 44.78
103.31
22
Mich11b 46.30 1.97 2.20 8.35
0.00
0.00 45.01
103.83
23
ByP9.5b
55.95 0.35 0.33 0.09
0.00
0.00 44.55
101.26
24
ByP9.5b
55.65 0.33 0.14 0.03
0.00
0.00 44.14
100.29
25
P11R1
16.02 1.61 2.31 38.44
0.00
0.00 39.59 97.96
26
P11R1
21.14 1.62 2.47 33.18
0.00
0.00 40.46 98.87
27
ByP9.5c
55.20 0.41 0.16 0.05
0.00
0.00 43.89 99.70
28
ByP5.7
56.12 0.24 0.10 0.06
0.01
0.00 44.41
100.93
29
Ho3.6
sv 11.87 1.52 1.03 44.92
0.02
0.01 39.49 98.86
30
Kis2-105 11.38 1.84 1.07 43.46
0.02
0.01 38.57 96.35
31
Kis10.9
20.08 1.66 0.36 35.58
0.02
0.00 39.87 97.57
32
P11R1
18.52 2.13 5.02 32.07
0.02
0.01 39.84 97.61
33
ByP9.5c
50.58 0.63 1.24 2.01
0.03
0.01 42.40 96.89
34
ByP5.5a
53.65 0.71 0.71 0.11
0.03
0.00 43.40 98.61
35
Ra2a.2
54.25 0.78 0.95 0.12
0.03
0.00 44.10
100.23
36
Kis2-105 14.38 1.66 0.41 41.10
0.03
0.03 38.87 96.48
37
Sv8.10
s
15.49 1.54 0.64 40.32
0.03
0.00 39.26 97.28
38
Sv8.11
s
5.68 0.96 0.53 53.68
0.03
0.02 39.15
100.05
39
Ko3-3
54.36 0.38 1.27 0.70
0.03
0.00 44.30
101.04
40
By3
55.55 0.46 0.78 0.11
0.03
0.00 44.66
101.59
41
By3
44.76 0.72 3.85 2.02
0.03
0.02 39.54 90.94
42
P11R1
19.49 1.81 4.99 32.61
0.03
0.01 40.58 99.52
43
ByP5.1
8.87 0.56 1.44 49.67
0.03
0.11 39.31
100.00
44
Ra2a.4
54.19 0.17 0.22 0.08
0.04
0.01 42.91 97.62
45
Sv8.8sv
9.21 1.31 0.40 48.56
0.04
0.00 39.05 98.57
46
Mich11bs
6.07 1.71 3.04 46.55
0.04
0.00 37.39 94.80
47
Ra2a.5
54.21 0.73 0.48 0.51
0.05
0.00 43.96 99.93
48
Ho1tm
43.49 2.07 2.40 10.44
0.05
0.00 44.36
102.81
49
Kis2-105 41.63 1.56 1.80 10.36
0.05
0.00 41.93 97.33
50
Sv7tm
42.66 2.82 1.88 10.76
0.05
0.00 44.41
102.58
51
Mich11b
6.24 1.16 1.65 48.97
0.05
0.00 37.58 95.65
52
By3
55.24 0.75 0.06 0.02
0.05
0.00 44.24
100.36
53
Ra1.1
54.88 0.84 0.10 0.09
0.06
0.00 44.13
100.11
54
Ho3.7
st
29.29 2.17 0.13 25.50
0.07
0.00 41.29 98.45
55
Kis10.2
40.06 2.65 2.46 11.15
0.07
0.00 42.79 99.18
56
P11R1
25.74 1.44 3.00 28.42
0.07
0.00 41.27 99.94
57
Ho3.4
st
26.23 1.67 0.32 29.74
0.08
0.00 41.09 99.13
58
Kis2-105 40.49 1.78 2.14 9.55
0.08
0.02 40.99 95.05
59
Kis10.8
19.56 1.93 0.37 35.27
0.08
0.00 39.60 96.81
60
P11R1
47.92 1.74 3.82 5.27
0.08
0.02 45.16
104.01
61
Ho3.1
tm 44.55 1.31 1.48 7.12
0.09
0.00 41.75 96.30
62
Kis2-105 26.51 2.03 0.11 27.53
0.09
0.00 40.21 96.48
63
Kis10.5
38.91 1.92 0.12 14.26
0.09
0.00 41.59 96.89
64
Sv8.12
s
6.79 0.57 0.48 54.59
0.09
0.02 40.16
102.70
65
Ra1.3
54.47 0.88 0.20 0.09
0.09
0.00 43.93 99.66
66
Sv7tm
32.55 1.65 0.14 23.20
0.10
0.00 41.87 99.51
67
Sv8.3
st
26.58 1.68 0.31 28.60
0.10
0.00 40.67 97.94
68
ByP5.5
53.35 1.25 0.42 0.29
0.11
0.00 43.72 99.14
69
Kis2-120 52.73 0.26 0.30 0.00
0.11
0.00 41.90 95.30
70
Kis10.1
39.59 2.75 2.47 11.17
0.11
0.00 42.56 98.65
ROJKOVIČ et al.: MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES;
ELECTRONIC SUPPLEMENT
E9
Table 2b: Continued. Part 2 from 2.
No. Sample CaO MgO FeO MnO SrO BaO CO
2
Total
71
Sv8.4 tm
30.72
21.08
0.08
2.27
0.11
0.00
48.63
102.89
72
Ra2a.1
49.76 0.23 4.88 0.41
0.12
0.00 42.59 97.99
73
Kis10.3
50.47 2.04 1.17 4.91
0.12
0.00 45.65
104.36
74
Mich4-1
47.28 0.14 6.46 0.58
0.12
0.00 41.63 96.21
75
By3
52.03 0.37 0.87 2.75
0.12
0.00 43.53 99.67
76
Sv7tm
15.33 2.34 0.79 37.59
0.13
0.00 38.45 94.63
77
Sv8.1
st
32.49 2.02 0.17 21.72
0.13
0.00 41.34 97.87
78
Ho1sv
13.72 1.53 0.52 42.18
0.14
0.00 38.98 97.07
79
Ho3.9
st
30.59 2.17 0.19 23.45
0.14
0.00 41.10 97.64
80
Michh11b 49.19 1.40 1.91 8.21
0.14
0.00 46.45
107.30
81
By3
51.92 0.36 1.03 2.88
0.14
0.00 43.62 99.95
82
ByP5.4
54.40 0.15 0.47 0.45
0.15
0.02 43.49 99.12
83
Kis2-105
9.86 1.22 0.24 46.31
0.15
0.01 38.01 95.80
84
By1c
54.58 1.02 0.12 0.00
0.15
0.00 44.08 99.95
85
Kis10.4
48.23 1.61 1.05 4.37
0.16
0.00 43.03 98.45
86
Kis10.10 20.96 1.56 0.41 38.06
0.16
0.00 42.08
103.23
87
Sv7tm
35.53 2.10 0.09 18.85
0.16
0.00 41.99 98.72
88
Ho3.2
tm 45.98 1.43 1.87 7.25
0.17
0.00 43.36
100.06
89
Sv7sv
10.85 0.98 0.56 47.45
0.18
0.00 39.44 99.46
90
Mich4-2
54.10 0.35 0.88 0.32
0.18
0.01 43.66 99.50
91
Ho1tm
43.30 2.34 2.83 11.28
0.20
0.00 45.35
105.30
92
Kis10.7
38.82 1.73 0.16 14.57
0.21
0.03 41.59 97.11
93
Ho1sv
12.72 1.84 1.27 40.85
0.22
0.00 38.21 95.11
94
Kis10.6
39.04 1.82 0.12 13.66
0.24
0.00 41.28 96.16
95
ByP9.5c
50.92 0.54 1.70 3.12
0.24
0.02 43.63
100.17
96
Kis2-105 54.70 0.11 0.12 0.46
0.25
0.01 43.52 99.17
97
ByP9.5c
51.47 1.28 0.58 2.57
0.25
0.00 43.85
100.00
98
P11R1
50.99 0.41 1.28 3.43
0.29
0.00 43.50 99.90
99
Ho1tm
41.73 2.20 2.51 10.83
0.31
0.00 43.54
101.12
100
ByP5.9
50.58 0.26 0.70 3.32
0.33
0.06 42.63 97.88
101
ByP5.11
51.58 0.38 1.08 1.94
0.56
0.00 42.99 98.53
102
ByP5.6
51.47 0.40 0.94 2.35
0.56
0.00 43.10 98.82
103
ByP5.10
51.47 0.36 1.08 2.58
0.59
0.00 43.30 99.38
104
ByP5.8
51.20 0.41 1.03 2.37
0.70
0.00 43.01 98.71
3769.12 228.63 116.65 1777.61 10.21 0.63 4386.38
CaO MgO FeO MnO SrO
BaO CO
2
Total
Average
36.24
2.20
1.12
17.09
0.098
0.006
42.17
98.92
minimum
5.68
0.11
0.00
0.00 0.00 0.00
37.39
maximum
56.40
22.10
6.46
54.59 0.70 0.11
48.63
n
104
ROJKOVIČ et al.: MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES;
ELECTRONIC SUPPLEMENT
E10
Table 3a: Chemical composition of rancieite (weight %). Part 1 from 2.
No. Sample MnO
2
CaO Fe
2
O
3
MgO SiO
2
K
2
O BaO Al
2
O
3
SrO P
2
O
5
Na
2
O Total
1
Dik7.3
83.60 4.39 0.75 1.32 0.07 0.27 0.01 0.51 0.17 0.00 0.13 91.22
2
Dik7.5
81.40 4.28 3.49 1.23 0.13 0.21 0.00 0.34 0.05 0.04 0.19 91.35
3
Dik7.6
85.02 4.64 0.52 1.26 0.02 0.23 0.00 0.19 0.06 0.04 0.18 92.16
4
Dik7.7
84.56 4.68 0.88 1.24 0.06 0.25 0.00 0.13 0.08 0.00 0.22 92.10
5
Dik7.8
83.66 4.61 1.12 1.25 0.26 0.24 0.00 0.22 0.07 0.00 0.17 91.59
6
Dik6b.1
82.29 4.33 1.20 1.86 0.03 0.47 0.00 0.18 0.00 0.01 0.20 90.57
7
Dik6b.2
83.37 2.68 0.80 3.16 0.29 0.50 0.03 0.24 0.05 0.03 0.33 91.48
8
Dik6b.3
83.60 6.82 1.04 1.47 1.23 0.38 0.00 0.67 0.01 0.02 0.03 95.28
9
Dik6b.4
83.15 7.17 1.47 1.44 0.59 0.21 0.00 0.35 0.06 0.04 0.01 94.50
10
Dik6b.5
79.98 6.25 0.63 1.36 3.36 0.25 0.01 1.28 0.00 0.02 0.02 93.16
11
Dik5.10
82.91 4.21 0.33 1.70 0.06 0.67 0.19 0.18 0.25 0.00 0.22 90.72
12
Ba-6b
ana1
sv
82.05 5.26 0.66 1.37 0.02 0.19 0.01 0.02
0.00 89.58
13
Ba-6b
ana3 81.20 5.04 1.24 1.23 0.03 0.18 0.00 0.06
0.00 88.98
14
Ba-6b
ana4 82.48 5.20 0.65 1.20 0.01 0.17 0.00 0.02
0.00 89.73
15
Ba-6b
ana5 84.26 5.31 0.61 1.10 0.03 0.19 0.00 0.01
0.00 91.51
16
Ba-6b
ana6 83.96 5.15 0.61 1.11 0.00 0.17 0.00 0.02
0.00 91.02
17
Ba-6b
ana7 74.23 4.72 8.39 1.01 0.37 0.14 0.02 0.25
0.00 89.13
18
CD-D7
an1 77.07 7.57 0.45 0.78 0.10 0.52 0.09 0.05
0.00 86.63
19
CD-D7
an2 77.35 7.74 0.40 0.69 0.23 0.54 0.01 0.04
0.00 87.00
20
CD-D7
an3 77.67 7.12 0.57 0.83 0.23 0.48 0.13 0.03
0.00 87.06
21
CD-D7
an4 78.15 7.67 0.46 0.72 0.08 0.51 0.07 0.05
0.00 87.71
22
CD-D7
an5 80.80 6.96 0.42 0.94 0.08 0.76 0.07 0.00
0.00 90.03
23
CD-D7
an6 79.26 7.01 0.55 1.01 0.36 0.64 0.14 0.06
0.00 89.03
24
CD-D7
an7 79.95 6.93 0.41 1.02 0.67 0.49 0.15 0.43
0.00 90.05
25
CD-D7
an8 76.24 8.57 2.16 0.51 0.27 0.52 0.03 0.10
0.00 88.40
26
CD-D7
an9 72.93 6.30 5.94 0.99 0.63 0.53 0.08 0.24
0.00 87.64
27
CD-D7
an10
78.42 7.55 0.60 0.79 0.15 0.53 0.08 0.06
0.00 88.18
28
CD-D7
an11
80.29 5.24 0.83 1.31 0.17 1.02 0.22 0.00
5.00 94.08
29
CD-D7
an12
81.01 5.15 0.82 1.40 0.12 1.13 0.15 0.00
0.00 89.78
30
CD-D7
an13
80.52 5.62 1.01 1.27 0.15 0.99 0.19 0.08
0.00 89.83
31
CD-D7
an14
78.02 8.42 0.83 0.60 0.16 0.67 0.02 0.04
0.00 88.76
32
CD-D7
an15
78.50 8.24 0.95 0.59 0.11 0.46 0.05 0.02
0.00 88.92
33
CD-D7
an16
72.38 5.96 8.45 1.00 1.01 0.45 0.09 0.28
0.00 89.62
34
CD-D7
an17
80.33 4.78 3.64 1.44 0.30 0.98 0.03 0.03
0.00 91.53
35
CD-D7
an18
81.68 4.39 0.98 1.61 0.14 1.08 0.07 0.02
0.00 89.97
36
CD-D7
an19
79.79 4.71 2.18 1.50 0.29 1.05 0.08 0.03
0.00 89.63
37
CD-H1
an1 83.80 3.32 0.65 0.90 0.10 0.60 0.00 0.41
0.00 89.78
38
CD-H1
an2 88.50 3.23 0.20 0.63 0.06 0.53 0.00 0.04
0.00 93.19
39
CD-H1
an3 84.19 3.63 0.49 0.97 0.04 0.46 0.01 0.17
0.00 89.96
40
CD-H1
an4 85.18 3.55 0.62 0.93 0.06 0.57 0.00 0.55
0.00 91.46
41
CD-H1
an5 86.72 3.62 0.22 0.57 0.06 0.57 0.00 0.03
0.00 91.79
42
CD-H1
an6 85.69 3.28 0.25 0.72 0.06 0.63 0.00 0.35
0.00 90.98
43
CD-H1
an7 80.26 3.18 3.92 0.87 0.27 0.58 0.00 0.82
0.00 89.90
44
CD-H1
an8 83.39 3.27 0.59 1.15 0.06 0.74 0.00 0.16
0.00 89.36
45
CD-H1
an9 82.61 3.63 1.22 0.97 0.37 0.71 0.00 0.47
0.00 89.98
46
ČD-H1
84.98 3.58 0.42 0.00 0.02 0.53 0.00 0.34
0.00 89.87
47
ČD-H1
85.31 3.54 0.38 0.00 0.00 0.56 0.04 0.09
0.00 89.92
48
ČD-D7
80.56 4.73 3.14 0.00 0.18 0.90 0.07 0.07
0.00 89.65
49
ČD-D7
77.68 7.74 0.56 0.00 0.02 0.48 0.07 0.07
0.00 86.62
50
CDD7.1
78.08 7.60 0.44 0.80 0.11 0.55 0.08 0.06
0.03 87.75
51
CDD7.2
75.80 7.53 0.69 0.81 0.17 0.51 0.08 0.08
0.03 85.70
52
CDD7.3
78.70 7.26 0.41 0.93 0.09 0.76 0.06 0.06
0.05 88.32
53
CDD7.4
74.11 8.42 2.75 0.56 0.39 0.46 0.04 0.13
0.07 86.93
54
CDD7.5
76.70 8.76 0.76 0.51 0.17 0.45 0.02 0.06
0.11 87.54
55
CDD7.6
75.96 8.68 0.46 0.46 0.24 0.45 0.00 0.09
0.04 86.38
56
CDD7.7
78.14 9.18 0.92 0.48 0.15 0.46 0.02 0.26
0.04 89.65
57
CDD7.8
71.76 9.58 2.06 0.40 0.28 0.42 0.00 0.30
0.11 84.91
58
CDH1.2
79.88 3.62 2.56 0.86 0.24 0.43 0.00 0.85
0.11 88.55
59
CDH1.3
81.99 3.13 2.77 0.98 0.15 0.71 0.00 0.25
0.39 90.37
60
CDH1.4
79.41 3.41 3.92 0.91 0.34 0.48 0.06 0.76
0.38 89.67
61
CDH1.5
84.55 3.36 0.43 0.71 0.09 0.66 0.00 0.38
0.70 90.88
62
CDH1.6
85.31 3.54 0.93 0.56 0.02 0.54 0.00 0.09
0.94 91.93
63
CDH1.7
84.01 3.57 0.47 0.83 0.09 0.59 0.00 0.45
0.71 90.72
64
LR2.1
80.02 8.40 0.00 0.00 0.18 0.35 0.00 0.00
0.00 88.95
65
LR2.1svf 81.08 6.39 1.91 0.00 0.33 0.55 0.30 0.00
0.00 90.56
66
LR2.3
80.53 10.10 0.00 0.00 0.00 0.23 0.00 0.00
0.00 90.86
67
LR2.4
78.56 6.00 1.88 0.00 0.20 0.58 0.00 0.00
0.00 87.22
68
LR1
81.02 5.03 0.89 0.43 0.20 0.94 0.13 0.00
0.00 88.64
69
By1a
80.23 5.93 0.87 0.88 0.02 0.53 0.00 0.01 0.21
0.16 88.85
70
By1a
79.36 6.00 0.53 0.81 0.04 0.47 0.00 0.00 0.21
0.15 87.58
ROJKOVIČ et al.: MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES;
ELECTRONIC SUPPLEMENT
E11
Table 3a: Continued. Part 2 from 2.
No. Sample MnO
2
CaO Fe
2
O
3
MgO SiO
2
K
2
O BaO Al
2
O
3
SrO P
2
O
5
Na
2
O Total
71
By1a
80.74 6.39 0.31 0.71 0.00 0.46 0.00 0.00 0.14
0.12 88.88
72
By1a
81.01 7.21 0.81 0.65 0.00 0.40 0.00 0.02 0.19
0.11 90.39
73
By1a
78.96 10.14 1.04 0.27 0.02 0.20 0.00 0.32 0.01
0.07 91.04
74
By1c
80.50 8.86 0.29 0.36 0.02 0.18 0.06 0.06 0.11
0.04 90.47
75
By1c
79.44 8.90 0.74 0.23 0.04 0.11 0.04 0.13 0.02
0.03 89.69
76
By1c
79.23 9.16 0.51 0.33 0.04 0.16 0.00 0.11 0.00
0.05 89.61
77
By2a
69.42 4.94 11.14 1.00 0.49 0.61 0.25 0.26 0.08
0.08 88.27
78
By2a
81.15 5.96 1.02 1.03 0.02 0.77 0.35 0.02 0.04
0.09 90.44
79
By2a
82.49 5.93 1.26 1.04 0.00 0.73 0.36 0.02 0.07
0.15 92.06
80
By2b
67.00 5.51 11.21 0.50 0.75 0.33 0.06 0.23 0.26
0.04 85.88
81
By2b
78.33 5.50 5.55 1.03 0.30 0.00 0.06 0.19 0.18
0.07 91.19
82
By2b
78.57 5.86 6.82 0.93 0.30 0.47 0.01 0.21 0.30
0.04 93.50
83
ByP9.5b 80.92 5.50 0.60 1.06 0.04 0.72 0.11 0.00 0.26 0.00 0.12 89.33
84
ByP9.5b 80.80 5.49 0.34 1.16 0.02 0.75 0.10 0.00 0.30 0.00 0.10 89.08
85
ByP9.5b 79.12 5.95 0.45 0.96 0.01 0.66 0.12 0.01 0.24 0.01 0.09 87.61
86
ByP9.5b 81.50 5.18 0.52 1.18 0.01 0.76 0.12 0.01 0.30 0.01 0.11 89.69
87
ByP9.5b 81.01 5.87 1.13 0.98 0.02 0.50 0.01 0.00 0.22 0.00 0.10 89.85
88
ByP9.5b 64.89 7.21 13.13 0.45 0.49 0.17 0.01 0.59 0.17 0.59 0.06 87.18
89
ByP9.5b 70.51 7.41 6.62 0.53 0.24 0.26 0.01 0.25 0.16 0.25 0.07 86.07
90
ByP9.5b 78.95 7.46 0.36 0.72 0.04 0.40 0.02 0.04 0.20 0.04 0.10 88.29
91
ByP9.5a 80.22 7.81 0.36 0.67 0.03 0.42 0.02 0.05 0.18 0.05 0.13 89.90
92
ByP11a.2 81.15 5.98 0.54 0.91 0.24 0.60 0.24 0.09 0.16 0.09 0.17 90.13
93
ByP11a.2 79.16 5.77 0.64 0.87 0.15 0.60 0.26 0.19 0.18 0.19 0.15 88.01
94
ByP11a.2 79.43 7.01 0.43 0.61 0.00 0.50 0.15 0.07 0.23 0.07 0.10 88.53
95
ByP11a.2 79.51 7.27 0.32 0.57 0.01 0.47 0.02 0.02 0.18 0.02 0.18 88.57
96
ByP11a.3 80.62 5.99 0.51 0.85 0.04 0.63 0.10 0.05 0.28 0.05 0.17 89.25
97
ByP9c.31 75.69 8.08 0.48 0.61 2.05 0.49 0.10 1.83 0.09 1.83 0.05 89.48
98
ByP9.5c 73.87 7.76 0.47 0.75 1.39 0.32 0.05 0.96 0.12 0.96 0.07 85.78
99
ByP9.5c 78.91 8.19 0.61 0.46 0.01 0.17 0.01 0.12 0.06 0.12 0.01 88.56
100
ByP5.2
72.37 10.57 0.98 0.61 0.89 0.13 0.11 2.29 0.06 2.29 0.00 88.02
101
St5.2
84.80 7.64 1.03 0.54 0.24 0.40 0.03 0.19 0.07 0.05 0.06 95.05
102
St5.3
78.62 8.61 1.30 0.35 0.32 0.15 0.00 0.13 0.21 0.29 0.06 90.03
103
St5.4
76.44 8.76 2.65 0.42 1.15 0.19 0.05 0.59 0.13 0.29 0.04 90.71
104
St5.5
80.42 9.86 0.76 0.61 1.51 0.31 0.03 0.83 0.10 0.05 0.13 94.62
105
Ra2b.1
76.59 10.72 0.75 0.12 0.10 0.18 0.06 0.27 0.03 0.03 0.09 88.95
106
Ra2b.2
77.77 10.59 0.60 0.13 0.06 0.20 0.06 0.22 0.02 0.04 0.04 89.73
107
Ra2b.3
78.55 9.48 0.80 0.15 0.04 0.08 0.38 0.01 0.09 0.01 0.08 89.66
108
Ra2b.4
81.67 11.18 0.55 0.10 0.10 0.07 0.05 0.20 0.01 0.01 0.05 94.05
109
Ra2b.5
73.32 9.20 6.67 0.22 0.49 0.09 0.59 0.54 0.05 0.20 0.08 91.44
110
Ra2b.6
75.69 11.40 1.44 0.15 0.21 0.27 0.49 0.21 0.07 0.22 0.04 90.02
111
Kis16–12 79.72 9.35 0.55 0.45 0.75 0.31 0.02
91.11
112
Kis16–12 78.49 9.18 0.46 0.51 0.98 0.69 0.00
89.93
113
Kis16–12 70.61 5.90 4.22 1.16 4.09 0.62 0.08
86.75
114
Kis16–12 82.28 5.55 0.65 1.40 0.06 0.74 0.03
90.59
115
Kis16–12 82.49 5.89 0.28 1.40 0.59 0.58 0.00
91.39
116
kis16–12 82.03 6.42 0.34 1.16 0.02 1.10 0.00
90.55
117
Mich9b-1 88.35 1.29 0.47 0.21 0.43 0.48 0.00
91.85
118
Mich9b-1 89.45 1.99 0.89 0.25 0.26 0.44 0.05
93.37
119
Mich9b-1 90.32 1.77 2.19 0.23 0.43 0.41 0.07
95.45
120
Mich9b-1 90.31 1.17 0.80 0.37 0.85 0.55 0.05
93.96
121
Mich9b-1 77.99 8.17 0.90 0.62 0.59 0.44 0.00
88.82
123
Mich9b-1 77.57 8.23 0.59 0.62 0.67 0.33 0.03
88.15
124
Mich9b-1 80.17 8.71 0.45 0.71 0.20 0.49 0.02
90.59
125
Mich9b-1 77.60 8.67 0.60 0.63 0.50 0.17 0.02
88.51
126
Mich9a-1 80.44 9.09 0.37 0.62 0.00 0.40 0.00
90.69
127
Ko1-106 83.74 6.31 0.47 0.53 0.08 0.36 0.00
91.53
128
Ko1-106 83.01 6.21 0.47 0.53 0.65 0.38 0.06
91.29
129
Ko1-124 82.76 4.37 0.24 0.89 0.02 0.38 0.01
88.67
ROJKOVIČ et al.: MANGANESE MINERALIZATION IN THE PALEOGENE AND JURASSIC SHALES;
ELECTRONIC SUPPLEMENT
E12
Table 3b: Chemical composition of pyrolusite (weight %).
No. Sample MnO
2
Fe
2
O
3
SiO
2
Al
2
O
3
MgO CaO BaO K
2
O Total
1
Ba-1
98.04 0.18 0.28 0.00 0.02 0.14 0.00 0.02 98.69
2
Ba-1
98.88 0.18 0.17 0.02 0.02 0.27 0.00 0.01 99.55
3
Ba-1
99.70 0.20 0.14 0.00 0.01 0.17 0.00 0.00 100.23
4
Ba-1 100.07 0.19 0.09 0.02 0.01 0.19 0.00 0.01 100.58
5
Ba-1
98.97 0.16 0.17 0.08 0.02 0.41 0.00 0.01 99.82
6
Ba-1
98.81 0.15 0.44 0.00 0.02 0.01 0.00 0.00 99.42
7
Ba-1
98.56 0.16 0.33 0.00 0.03 0.13 0.00 0.00 99.22
8
Ba-1 100.34 0.21 0.11 0.00 0.02 0.10 0.00 0.01 100.80
9
Ba-1 100.42 0.22 0.07 0.00 0.01 0.08 0.00 0.01 100.80
10
Ba-1
99.79 0.18 0.09 0.01 0.00 0.04 0.00 0.01 100.12
11
Ba-1
98.25 0.20 0.26 0.04 0.02 0.18 0.00 0.00 98.95
12
Ba-1
98.16 0.25 0.27 0.00 0.00 0.20 0.00 0.00 98.88
13
Ba-1 100.50 0.18 0.12 0.00 0.02 0.05 0.00 0.01 100.89
14
Ba-1
98.22 0.17 0.24 0.03 0.01 0.17 0.00 0.00 98.84
15
Ba-5
98.65 0.15 0.31 0.07 0.00 0.00 0.00 0.00 99.18
16
Ba-5
98.64 0.16 0.21 0.02 0.02 0.03 0.00 0.00 99.07
17
Ba-5
99.02 0.21 0.46 0.05 0.00 0.04 0.00 0.00 99.78
18
Ba-5
96.15 0.16 0.84 0.21 0.02 0.11 0.00 0.00 97.49
19
Ba-5
95.91 0.22 0.79 0.10 0.03 0.25 0.00 0.00 97.31
20
Ba-5
96.98 0.22 0.70 0.08 0.03 0.24 0.01 0.02 98.28
21
Ba-5
98.46 0.23 0.29 0.03 0.02 0.09 0.00 0.00 99.11
22
Ba-5 100.07 0.18 0.26 0.04 0.01 0.03 0.00 0.00 100.58
23
Ba-5
98.18 0.21 0.29 0.01 0.00 0.12 0.00 0.01 98.81
24
Ba-5
98.54 0.19 0.34 0.06 0.02 0.05 0.00 0.00 99.21
25
Ba-6b 96.34 1.14 0.15 0.16 0.29 1.70 0.00 0.03 99.81
26
CD-H1 97.15 0.23 0.53 0.23 0.01 0.34 0.00 0.01 98.51
27
CD-H1 96.69 0.21 0.41 0.24 0.03 0.44 0.00 0.03 98.04
28
CD-H1 94.72 0.14 0.92 0.39 0.02 0.41 0.00 0.02 96.63
29
CD-H1 97.24 0.19 0.43 0.27 0.01 0.48 0.00 0.02 98.63
30
CD-H1 97.15 0.16 0.57 0.22 0.01 0.41 0.00 0.01 98.54
31
CD-H1 95.13 0.17 0.75 0.26 0.02 0.49 0.00 0.01 96.82
32
CD-H1 97.38 0.22 0.32 0.16 0.03 0.39 0.00 0.01 98.50
33
CD-H1 97.65 0.22 0.47 0.30 0.02 0.43 0.00 0.02 99.11
34
CD-D1 98.23 0.49 0.72 0.38 0.02 0.61 0.01 0.02 100.48
35
CD-D1 98.11 0.52 0.68 0.39 0.04 0.61 0.00 0.01 100.36
36
CD-D1 99.11 0.28 0.41 0.13 0.03 0.84 0.00 0.01 100.81
37
CD-D1 98.56 0.23 0.35 0.07 0.03 0.45 0.00 0.01 99.71
38
CD-D1 99.61 0.30 0.31 0.14 0.03 0.80 0.00 0.01 101.20
39
CD-D1 98.68 0.98 0.65 0.38 0.02 0.63 0.00 0.01 101.35
40
CD-D1 97.31 1.73 0.48 0.29 0.01 0.71 0.00 0.02 100.55
41
CD-D1 96.92 0.97 0.59 0.22 0.02 0.55 0.00 0.00 99.28
42
CD-D1 93.93 3.09 0.68 0.41 0.05 0.63 0.00 0.02 98.80
43
CD-D1 99.34 0.24 0.25 0.12 0.01 0.69 0.00 0.01 100.66
44
CD-D1 98.33 0.34 0.45 0.11 0.05 0.73 0.00 0.01 100.02
Table 3c: Chemical composition of manganite (weight %)
.
No. Sample Mn
2
O
3
Fe
2
O
3
SiO
2
Al
2
O
3
MgO CaO BaO K
2
O Total
1
Ba-5-1 89.58 0.15 0.31 0.07 0.00 0.00 0.00 0.00 90.11
2
Ba-5-2 89.56 0.16 0.21 0.02 0.02 0.03 0.00 0.00 90.00
3
Ba-5-3 89.91 0.21 0.46 0.05 0.00 0.04 0.00 0.00 90.67
4
Ba-5-4 87.30 0.16 0.84 0.21 0.02 0.11 0.00 0.00 88.64
5
Ba-5-5 87.09 0.22 0.79 0.10 0.03 0.25 0.00 0.00 88.49
6
Ba-5-6 88.06 0.22 0.70 0.08 0.03 0.24 0.01 0.02 89.35
7
Ba-5-7 89.40 0.23 0.29 0.03 0.02 0.09 0.00 0.00 90.05
8
Ba-5-8 89.14 0.21 0.29 0.01 0.00 0.12 0.00 0.01 89.78
9
Ba-5-9 89.48 0.19 0.34 0.06 0.02 0.05 0.00 0.00 90.15
ROJKOVI
Č
et al
.: MANGA
N
ESE
MINERA
LI
ZA
TION IN
THE PALEOGE
NE AND J
U
RASSIC SHALES;
EL
ECT
R
ONIC
SUPP
LEME
NT
E13
Ta
ble 4
a:
C
hemical co
m
po
sitio
n
of th
e Jurassic sh
ale
with
man
ga
ne
se
m
in
eralizatio
n (ox
id
es in
weigh
t %,
elem
en
ts i
n
pp
m
)
.
Part
1 fr
om
2.
No.
1
2 3 4
5 6 7
8 9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
Sa
m
p
le
Ba 1
Ba 4
Ba 5
Ba 6a
Ba
Č
D-
H
14
BaH
N
1-
6A
BaL-4
BaMA-
11
BaMA-
12
BaSA-
4
Dik 1
Dik 2
Dik 3
Dik 4
Dik 5
Dik 6
Dik 7
LR 2
LR 3
Ma-
P
-0
m
Ma-
P
-1
m
M
a-P-1
.5
–
1.
6m
M
a-P-2
m
SiO
2
7.
74
16.
55
25.
31
37.
99
23.
56
15.
22
37.
13
39.
24
38.
10
29.
50
22.
03
31.
30
39
.24
25.
20
9.
20
46.
00
11.
68
13.
95
8.
35
41.
78
39.
16
23.
21
29.
14
TiO
2
0
.2
2
0
.2
1
0
.4
3
0
.2
0
0
.3
7
0
.1
9
0
.1
5
0
.6
1
0
.5
3
0
.4
1
0
.0
57
0.
069
0.
253
0.
093
0.
389
0.
194
0.
191
0.
34
0.
10
0.
688
0.
546
0.
181
0.
320
Al
2
O
3
2.
47
3.
02
6.
03
3.
87
7.
25
3.
22
5.
39
12.
62
11.
86
9.
10
1.
41
1.
45
4.
95
1.
81
4.
41
5.
50
4.
96
5.
06
1.
23
14.
07
11.
65
4.
50
7.
00
FeO
1
.1
4
6
.7
3
Fe
2
O
3
7
.5
8
3
.2
1
Fe
2
O
3
to
ta
l
8.
85
16.
18
11.
22
10.
68
7.
60
14.
38
9.
94
4.
95
5.
16
9.
38
0.
98
2.
35
3
.2
8
1
.9
0
1
1.
29
6
.9
4
1
3.
09
1
5.
23
2
.9
1
5
.6
1
5
.0
0
2
.9
7
3
.7
9
MnO
22.
84
24.
66
21.
14
3.
66
13.
81
20.
94
2.
62
0.
21
0.
18
15.
24
2.
054
2.
299
1.
870
2.
305
33.
22
15.
70
31.
12
34.
06
3.
08
0.
160
0.
170
0.
283
0.
234
MgO
3
.7
5
1
.8
7
1
.7
6
5
.2
6
3
.0
9
1
.8
7
6
.3
7
3
.0
7
2
.4
3
1
.9
7
1
.0
7
0
.6
7
2
.0
6
0
.9
2
2
.3
9
1
.9
3
2
.5
3
0
.9
6
9
.7
9
3
.0
6
2
.7
0
1
.4
5
2.
03
CaO
22.
95
15.
93
9.
06
16.
01
16.
40
14.
85
16.
52
17.
79
19.
76
10.
85
40.
22
34.
14
25
.27
37.
21
10.
52
7.
57
12.
31
5.
76
37.
49
15.
04
18.
98
36.
07
29.
62
Na
2
O
0
.0
2
0
.5
3
0
.6
8
0
.0
9
0
.6
9
0
.6
4
0
.9
2
1
.3
8
1
.2
9
1
.2
1
0
.0
7
0
.0
5
0
.0
4
0
.0
6
0
.0
8
0
.6
4
0
.0
8
0
.2
4
0
.5
9
0
.6
4
0
.6
3
0
.3
5
0.
59
K
2
O
0
.4
0
1
.1
1
2
.0
0
0
.2
0
0
.8
7
0
.4
4
0
.1
4
2
.4
8
2
.3
0
0
.8
2
0
.2
4
0
.3
2
1
.2
5
0
.4
8
1
.1
3
1
.0
3
0
.9
1
1
.0
0
0
.6
4
2
.4
5
1
.9
2
0
.7
6
1.
11
P
2
O
5
0
.6
1
0
.4
2
0
.2
1
0
.2
2
0
.1
3
0
.3
9
0
.5
3
0
.1
0
0
.1
0
0
.3
2
0
.0
8
0
.2
0
0
.2
0
0
.1
2
0
.7
3
0
.5
8
0
.9
2
0
.2
4
0
.1
6
0
.1
7
0
.1
0
0
.1
3
H
2
O-
0
.6
5
1
.8
5
0
.9
0
0
.3
4
0
.1
8
0
.3
4
0
.0
8
0
.0
7
0
.0
3
0
.4
6
0
.2
5
0
.3
5
0
.3
6
0
.2
9
2
.2
3
1
.8
4
3
.6
8
8
.5
0
0
.0
7
0
.5
1
0
.4
3
0
.2
9
0.
33
*LO
I
29.
72
17.
30
20.
92
19.
68
25.
73
27.
14
19.
84
17.
07
17.
90
20.
34
31.
67
27.
08
21.
38
29.
75
26.
44
13.
71
22.
06
14.
51
35.
66
16.
12
18.
78
29.
80
25.
74
B
164
48
118
16
33
38
<10
91
71
107
57
39
Ba
245
<30
<30
66
102
53
<30
148
127
165
62
69
266
95
382
256
242
598
2119
308
256
101
152
Co
18
95
191
27
62
48
18
12
10
122
4
14
13
12
78
64
119
93
3
2
1
2
2
1
0
1
9
Cr
2
5
5
4
5
5
2
2
3
7
3
3
3
2
4
9
4
7
4
7
8
1
5
3
4
1
6
3
0
8
1
6
6
0
1
0
8
5
7
1
3
0
3
6
Cu
2
9
1
5
3
9
3
7
3
6
2
6
3
0
4
3
4
5
6
9
4
1
2
2
4
1
4
4
4
2
6
6
3
4
5
1
3
4
5
3
9
2
0
3
2
La
1
3
1
3
2
5
2
6
1
6
7
2
4
1
7
0
2
3
2
6
1
6
1
6
Mo
3
3
3
3
3
3
3
6
1
1
2
2
2
2
Ni
19
23
92
40
48
21
20
39
38
102
13
19
28
14
60
46
73
25
1
1
6
9
5
4
2
8
4
3
Pb
2
5
1
9
3
3
1
6
2
4
4
2
1
7
2
2
2
5
7
5
6
1
2
1
3
1
2
2
6
2
3
2
6
5
1
8
2
9
2
7
2
2
3
5
Sr
480
406
175
525
239
211
401
330
312
223
500
348
226
384
318
182
271
1000
500
1258
1484
2202
2254
V
28
34
41
38
87
70
75
117
103
104
11
20
43
39
82
63
71
83
63
121
77
61
45
Y
4
9
4
1
1
8
3
5
3
4
3
5
3
3
2
5
3
5
1
0
2
1
1
7
1
5
5
5
3
0
5
9
1
9
2
1
2
1
1
5
2
1
Zr
274
290
62
69
160
82
37
41
137
10
18
50
19
109
44
71
97
114
9
3
3
8
6
8
Th
1
1
1
3
9
1
0
4
1
0
9
1
2
3
4
5
3
1
4
7
1
4
4
1
0
8
7
1
0
U
3
3
3
2
3
2
2
3
2
2
2
2
4
2
6
2
3
3
3
3
TC%
8
.5
5
7
.6
5
5
.8
2
5
.9
3
8
.8
6
8
.7
6
6
.5
5
4
.5
2
4
.4
5
.3
5
7
.3
5
6
.2
7
5
.0
3
7
.0
2
6
.1
2
3
.6
1
4
.8
0
.3
2
1
1.
05
4
.0
2
4
.9
5
8
.3
7
6
.9
TO
C%
0
.9
7
1
.6
2
1
.2
4
1
.1
7
2
.6
5
3
.2
1
.7
0
.9
6
0
.6
7
2
.6
8
0
.2
1
0
.1
0
.1
2
0
.1
8
2
.2
6
1
.0
8
1
.6
8
0
.2
4
1
.8
2
0
.4
2
0
.3
1
0
.3
0
.4
2
TIC%
6
.5
8
6
.0
3
4
.5
8
4
.7
6
6
.2
1
5
.5
6
4
.8
5
3
.5
6
3
.7
3
2
.6
7
7
.1
4
6
.1
7
4
.9
1
6
.8
4
3
.8
6
2
.5
3
3
.1
2
0
.0
8
9
.2
3
3
.6
4
.6
4
8
.0
7
6
.48
CO
2
carb.
22.
07
16.
76
17.
422
22.
73
20.
35
17.
75
13.
03
13.
652
9.
77
26.
132
22.
582
17.
971
25
.034
14.
127
9.
26
13.
18
16.
98
29.
54
23.
72
ROJKOVI
Č
et al
.: MANGA
N
ESE
MINERA
LI
ZA
TION IN
THE PALEOGE
NE AND J
U
RASSIC SHALES;
EL
ECT
R
ONIC
SUPP
LEME
NT
E14
T
able
4a:
C
ont
in
ue
d. Part
2 fr
om
2.
No.
24
25
26
27
28
29
30
31
32
33
34 35 36 37 38 39 40 41
42
43
44
45
46
Sa
m
p
le M
a-P-3
m
M
a-P-3
.4
–
3.
43m
M
a-P-4
m
M
a-P-5
m
M
a-P-6
m
M
a-
P-7
m
M
a-P-8
m
M
a-P-8
.1
0–
8.
16m
Ma-
P
-9
m
M
a-
P
-9.
5m
ŠJ 1
ŠJ 9
ŠJ-
16
Z
a 1
Z
a 2
Z
a 6
Z
a 7
Z
aK 9
Z
aH-
11
Z
aH-
19
Z
aH-
20
Z
aH-
21
Z
aK-
22
SiO
2
38.
16
27.
22
38.
17
36.
88
34.
64
39.
08
43.
69
23.
21
38.
72
31.
31
33.
12
27.
94
32.
87
4.
55
10.
43
35.
05
19.
82
33.
15
49.
12
34.
5
15.
44
39.
21
7.
23
TiO
2
0.
566
0.
144
0.
528
0.
519
0.
568
0.
539
0.
730
0.
137
0.
566
0.
372
0.
18
0.
13
0.
12
0.
04
0.
04
0.
19
0.
18
0.
25
0.
41
0.
15
0.
174
0.
286
0.
128
Al
2
O
3
12.
24
3.
54
11.
01
11.
17
12.
97
11.
43
15.
73
3.
45
12.
01
8.
14
8
.4
1
2
.7
2
2
.0
1
0
.6
0
0
.7
5
3
.2
3
2
.6
2
4
.1
2
1
1.5
6
2
.8
1
2
.6
2
6
.5
7
2
.8
7
FeO
2
.5
6
2
.1
8
7
.7
8
Fe
2
O
3
2
.3
8
3
.4
9
3
.2
82
Fe
2
O
3
to
ta
l
4
.7
7
2
.3
4
4
.7
8
4
.6
7
4
.9
9
4
.1
5
4
.6
2
2
.6
0
5
.1
0
5
.07
5.
22
23.
29
20.
08
5.
00
5.
91
9.
96
35.
67
14.
81
8.
34
11.
93
2.
85
16.
67
14.
23
MnO
0.
176
0.
255
0.
181
0.
190
0.
174
0.
166
0.
132
0.
271
0.
163
0.
209
18.
27
20.
59
29.
72
9.
11
8.
03
13.
17
9.
16
11.
69
0.
68
14.
20
2.
49
8
6.
069
24.
66
MgO
3
.0
0
3
.2
1
2
.4
6
2
.6
7
3
.0
4
2
.5
9
2
.9
1
1
.1
3
2
.6
7
1
.9
7
0
.9
4
1
.5
1
0
.1
5
9
.6
9
8
.3
2
2
.5
5
1
.7
5
2
.3
6
1
.7
4
2
.5
9
8
.7
5
3.
04
4.
61
CaO
18.
97
32.
80
20.
77
21.
24
20.
49
19.
91
13.
39
37.
77
19.
28
27.
52
19.
11
1.
89
1.
31
31.
65
29.
34
20.
64
11.
16
17.
91
10.
68
9.
25
30.
82
8.
22
11.
85
Na
2
O
0
.6
6
0
.4
2
0
.6
4
0
.6
5
0
.8
6
0
.7
3
0
.8
7
0
.3
7
0
.7
2
0
.5
6
0
.0
2
0
.8
8
0
.8
6
0
.1
1
0
.2
9
0
.1
0
0
.3
4
0
.1
0
0
.7
4
0
.1
8
0
.2
4
0.
32
0.
11
K
2
O
2
.0
6
0
.5
8
1
.9
2
1
.8
0
2
.0
9
1
.9
8
2
.7
6
0
.5
1
1
.9
8
1
.3
4
0
.0
3
0
.8
1
0
.8
0
0
.0
7
0
.0
8
1
.3
3
1
.0
6
1
.7
2
5
.5
2
0
.5
3
0
.3
6
1.
06
0.
42
P
2
O
5
0
.1
8
0
.0
7
0
.1
5
0
.1
6
0
.1
6
0
.1
6
0
.2
2
0
.0
7
0
.1
8
0
.1
1
2
.5
6
0
.0
3
0
.0
4
0
.1
0
0
.5
1
0
.2
8
0
.1
6
0
.3
8
0
.8
9
1
.0
9
H
2
O-
0
.3
2
0
.2
6
0
.3
5
0
.3
4
0
.3
3
0
.3
8
0
.4
9
0
.3
0
0
.4
1
0
.2
9
0
.0
1
0
.5
1
2
.0
9
0
.1
0
0
.0
3
0
.0
5
0
.1
9
0
.1
5
0
.3
0
0
.5
6
0
.3
6
1.
31
0.
75
*LO
I
18.
93
29.
20
19.
17
19.
84
19.
77
18.
99
14.
74
30.
21
18.
36
23.
02
14.
56
19.
30
9.
52
38.
67
36.
72
13.
39
17.
61
13.
47
10.
17
21.
05
35.
60
17.
39
32.
68
B
2
357
41
36
38
52
42
151
113
82
Ba
276
81
237
235
268
255
350
75
252
187
15
127
42
1100
1286
20
20
63
119
398
1133
220
839
Co
19
7
19
15
19
27
19
7
18
19
106
30
21
6
1
4
2
1
6
5
1
9
3
1
4
5
9
3
4
6
8
Cr
6
7
2
7
6
8
6
9
7
2
6
8
9
3
3
0
7
0
5
0
2
4
2
3
5
9
7
4
3
5
1
5
4
6
5
8
2
6
2
4
1
7
3
Cu
4
5
1
6
4
1
4
4
4
9
4
5
5
6
2
1
5
1
3
4
2
1
7
3
1
1
2
7
3
2
4
7
6
2
8
4
3
0
2
6
5
1
2
5
La
30
12
27
18
26
32
27
9
28
22
61
186
82
151
2
4
1
4
4
9
4
5
Mo
2
2
2
2
2
2
2
2
2
2
1
3
4
4
6
–
3
7
3
3
Ni
7
2
1
9
4
5
5
4
5
8
4
5
6
0
2
4
5
6
5
1
5
8
4
8
2
0
4
5
19
108
31
42
34
25
44
36
Pb
3
8
1
9
2
4
2
9
2
4
2
3
2
4
1
9
2
5
3
0
3
8
2
1
4
5
7
1
1
1
4
8
2
2
4
1
2
6
1
1
2
7
1
4
Sr
1426
2750
1392
1542
1449
1240
863
2384
1339
1665
227
192
>500
500
416
316
136
427
291
600
930
508
586
V
94
38
84
87
92
91
120
35
95
64
50
17
20
3
1
1
47
12
59
221
53
253
77
45
Y
1
9
1
8
2
0
1
9
1
6
1
8
2
1
1
5
2
4
2
1
1
8
3
7
3
1
7
9
2
2
9
8
4
6
2
2
1
6
6
6
4
4
Zr
93
33
89
90
93
93
116
27
90
70
58
220
184
42
86
8
1
7
3
3
7
4
1
6
3
3
5
Th
1
0
6
9
1
0
1
0
9
1
2
7
1
0
1
0
1
1
1
1
2
2
4
8
3
7
1
1
U
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
TC%
4
.9
8
8
.5
5
5
.0
5
5
.2
6
5
.3
8
5
.4
2
4
.5
8
.2
7
4
.8
6
.5
4
4
.5
6
5
.1
1
0
.1
2
1
1.
62
1
1.
02
6
.8
8
3
.2
3
6
.4
2
6
.1
8
6
.6
1
9
.3
0
4
.87
8.
68
TO
C%
0
.4
7
0
.2
8
0
.4
6
0
.4
7
0
.4
0
.5
8
0
.5
6
0
.5
2
0
.5
7
0
.3
8
0
.1
0
.2
0
.1
2
0
.5
0
.4
4
1
.2
0
.5
7
1
.7
4
3
.5
6
4
.4
2
1
.7
3
2.
78
2.
92
TIC%
4
.5
1
8
.2
7
4
.5
9
4
.7
9
4
.9
8
4
.8
4
3
.9
4
7
.7
5
4
.2
3
6
.16
4.
46
4.
91
st.
11.
12
10.
58
5.
68
2.
66
4.
68
2.
62
2.
19
7.
57
2.
09
5
.7
6
CO
2
carb.
16.
51
30.
27
16.
80
17.
53
18.
23
17.
71
14.
42
28.
37
15.
48
22.
55
17
.9
7
st.
9
.5
8
8.
015
27.
706
7.
649
21.
08
ROJKOVI
Č
et al
.: MANGA
N
ESE
MINERA
LI
ZA
TION IN
THE PALEOGE
NE AND J
U
RASSIC SHALES;
EL
ECT
R
ONIC
SUPP
LEME
NT
E15
Ta
ble 4
b
:
C
he
m
ical
co
m
posi
tion
of
th
e Pal
eoge
ne
shal
e
wi
th
m
angane
se
m
ineral
izat
ion
(o
xi
des
in
wei
ght
%, el
em
ent
s i
n
pp
m
)
.
Part
1
fr
om
2.
No.
1
2
3
4
5
6
7
8
9
10
11
12
13 14
15 16
17
18
19 20 21 22 23 24
25 26 27 28 29 30
31
Sa
m
p
le
By
-1
By
-2
By
-3
By
-P-0
By
-P-1
By
-P-2
By
-P-3
By
-P-4
By
-P-5
By
-P-6
By
-P-7
By
-P-8
By
-P-9
By-P-
9.
40
By-P-
9.
50
By-P-
10
By
-P-1
1
By-P-
11.
10
By-P-
12
By-P-
13
By-P-
14
By-P-
15
By-P-
16
By-P-
17
By-P-
18
By-P-
19
Ho
1
Ho
3
Kis
1
Kis
2
Kiš
1
2
SiO
2
28.
05
25.
08
32.
87
36.
68
31.
19
30.
06
25.
28
38.
53
29.
81
35.
79
36.
02
17.
91
41.
43
42.
84
24.
48
34.
49
23.
99
36.
02
38.
76
40.
65
34.
51
44.
92
36.
25
45.
62
43.
66
39.
05
3.
42
3.
66
12.
11
2
2.
27
3
0.6
9
TiO
2
0
.2
5
0
.1
4
0
.4
3
0
.5
3
0
.3
9
0
.3
6
0
.3
4
0
.5
6
0
.3
0
0
.5
3
0
.5
6
0
.1
6
0.
55
0.
63
0.
13
0.
45
0.
26
0.
50
0.
52
0.
63
0.
43
0.
60
0.
48
0.
70
0.
70
0.
52
0
.1
3
0
.0
7
0
.1
9
0
.3
1
0
.3
4
Al
2
O
3
7.
63
5.
85
8.
90
11.
24
8.
35
8.
31
9.
60
11.
52
4.
97
10.
91
11.
53
2.
81
11.
85
14.
14
4.
27
9.
17
7.
04
10.
59
11.
25
13.
77
8.
55
12.
33
10.
94
15.
14
14.
22
10.
59
1.
88
1
.5
7
2
.7
2
4
.6
7
5
.1
2
FeO
0
.7
3
0
.8
7
1
.5
3
2
.1
8
Fe
2
O
3
1
.6
9
1
.4
8
1
.7
7
1
.6
9
Fe
2
O
3
to
ta
l
1
8.
15
2
5.
27
6
.8
4
5
.1
2
6
.1
9
5
.7
0
1
9.
59
9
.4
3
4
.5
9
5
.9
5
6
.1
6
3
.6
8
9
.01
10.
83
25.
28
8.
92
11.
93
7.
56
8.
74
10.
09
7.
97
7.
09
12.
40
6.
15
5.
57
11.
61
4.
11
2
.5
0
2
.4
5
3
.4
7
4
.1
1
MnO
1
6.
05
1
3.
13
1
.1
0
0
.5
0
1
.0
0
1
.2
9
1
1.
59
1
.2
2
1
.2
8
0
.5
3
0
.5
1
1
.3
1
0
.65
2.
40
14.
09
1.
77
29.
68
0.
65
0.
74
1.
29
0.
94
0.
41
0.
49
0.
50
0.
45
1.
33
29.
15
28.
04
29.
88
14.
04
15.
96
MgO
1
.7
1
1
.9
0
1
.4
5
1
.7
9
1
.3
8
1
.3
3
2
.3
4
2
.2
7
1
.1
3
1
.6
7
1
.7
8
1
.0
8
1.
95
2.
46
1.
34
1.
83
1.
60
1.
68
1.
71
2.
31
1.
45
1.
93
1.
80
2.
13
1.
91
1.
62
2
.6
5
2
.9
6
5
.2
6
3
.5
1
3
.2
5
CaO
10.
40
11.
04
23.
61
20.
78
24.
98
25.
96
12.
20
16.
11
30.
10
21.
56
20.
36
39.
66
14.
96
9.
64
11.
91
20.
45
8.
19
19.
93
16.
98
12.
49
22.
36
14.
09
16.
37
11.
75
14.
11
15.
53
23.
42
26.
40
15.
20
2
3.
66
1
5.0
6
Na
2
O
0
.2
1
0
.0
9
0
.5
4
0
.5
1
0
.3
9
0
.3
9
0
.2
2
0
.5
3
0
.6
6
0
.5
2
0
.5
2
0
.2
8
0.
55
0.
55
0.
07
0.
47
0.
18
0.
51
0.
55
0.
62
0.
55
0.
64
0.
40
0.
63
0.
66
0.
53
0
.0
8
0
.1
0
0
.0
7
0
.3
3
0
.6
0
K
2
O
0
.7
9
0
.2
8
1
.6
2
2
.2
3
1
.6
5
1
.6
7
1
.0
1
1
.9
1
0
.8
3
2
.1
5
2
.2
7
0
.4
7
2.
02
2.
43
0.
29
1.
45
0.
84
2.
08
2.
09
2.
29
1.
61
2.
23
1.
98
3.
13
3.
02
1.
91
0
.5
7
0
.4
1
0
.4
9
0
.9
3
0
.9
2
P
2
O
5
1
.0
0
1
.3
1
0
.1
8
0
.2
3
0
.1
9
0
.1
5
2
.5
6
0
.2
0
0
.1
6
0
.1
5
0
.1
5
0
.3
6
0.
27
0.
14
1.
16
0.
23
0.
39
0.
20
0.
16
0.
18
0.
33
0.
21
0.
18
0.
22
0.
17
0.
24
0
.1
1
0
.1
7
0
.1
8
0
.1
9
0
.2
0
H2
O-
4
.8
6
4
.3
6
1
.6
1
1
.3
2
1
.2
3
1
.2
1
4
.1
6
1
.9
2
0
.7
5
1
.5
1
1
.5
9
0
.6
2
2.
07
2.
99
3.
98
1.
92
5.
51
1.
57
1.
76
2.
57
1.
42
1.
77
2.
02
1.
58
1.
62
2.
00
0
.0
8
0
.4
3
0
.3
2
0
.1
6
0
.5
3
LO
I
15.
05
15.
44
22.
19
20.
03
23.
94
24.
42
14.
96
17.
53
25.
91
20.
07
19.
95
31.
96
16.
56
13.
70
16.
74
20.
47
15.
50
19.
99
18.
32
15.
45
21.
08
15.
30
18.
40
13.
77
15.
28
16.
83
34.
05
33.
06
31.
03
2
6.
43
2
2.7
4
B
120
77.
00
245
231
75
Ba
1354
600
276
263
251
327
750
339
250
285
290
153
299
386
432
308
1304
284
392
483
307
349
326
4
58
426
491
245
199
150
265
241
Co
5
8
6
5
3
0
8
2
0
2
1
8
8
5
6
9
1
9
1
9
1
2
2
8
6
8
5
6
3
2
3
5
3
3
2
2
3
9
2
5
2
6
7
1
1
9
1
5
3
4
7
3
4
.0
0
1
2
7
Cr
85
59
79
97
90
94
91
113
51
112
116
30
122
134
61
88
110
121
107
123
9
2
107
155
116
105
130
28
35
71
73
41
Cu
5
0
3
2
4
7
3
6
6
3
5
6
4
7
5
5
1
5
4
8
5
7
1
1
5
7
8
2
3
0
5
4
4
7
5
7
5
7
7
1
5
9
5
5
7
2
4
3
4
1
6
3
2
0
1
2
2
2
3
4
1
2
La
2
9
3
2
2
8
2
4
2
2
2
2
6
5
3
4
1
8
2
6
2
8
1
3
3
3
3
0
3
0
2
7
2
9
2
9
2
9
3
4
2
8
3
0
3
3
3
0
3
0
3
3
9
1
6
Mo
1
0
7
3
2
2
5
5
2
2
2
2
2
2
2
2
2
1
9
2
2
2
4
2
3
2
2
4
1
5
–
3
Ni
92
90
60
51
62
64
148
123
38
63
66
34
87
156
81
106
83
95
76
118
69
90
136
76
62
113
29
13
21
41
30
Pb
1
0
3
1
8
2
5
2
0
2
1
1
6
3
2
1
7
2
0
2
0
1
1
2
4
3
1
3
1
9
1
0
2
4
1
8
2
6
2
1
2
6
3
8
2
8
2
7
2
7
2
8
7
2
7
1
8
1
2
Sr
1000
701
879
708
1139
1147
897
690
1112
789
770
1069
664
437
723
987
1051
807
669
510
796
513
760
446
524
611
457
733
316
450
363
V
112
85
114
143
163
132
176
164
48
149
167
34
159
234
76
155
147
198
182
194
165
154
274
180
168
192
36
42
77
62
52
Y
3
1
3
5
2
3
2
5
2
0
1
9
7
8
2
7
1
8
2
4
2
7
1
1
3
6
2
5
3
9
3
0
3
6
2
9
3
0
3
0
3
4
3
0
3
3
2
7
2
8
3
1
8
1
5
Zr
57
38
87
100
72
66
77
133
101
111
108
39
117
122
32
101
46
100
103
132
106
133
89
133
135
116
19
103
Th
8
1
0
8
1
0
8
9
9
1
1
5
9
9
4
1
1
1
3
8
8
1
0
9
1
0
1
0
9
9
8
1
2
1
0
1
0
5
7
U
4
2
5
3
8
5
5
3
5
3
3
3
6
3
3
3
3
5
7
3
5
5
3
5
5
3
2
2
TC%
1
.5
6
1
.9
2
6
.1
4
.9
3
7
.4
7
5
.9
3
1
.7
1
4
.4
3
7
.0
4
5
.1
4
.9
4
8
.6
1
3.
68
2.
62
1.
75
4.
8
1.
05
5.
45
4.
89
3.
51
5.
31
3.
7
4.
62
3.
17
3.
52
3.
71
1
0.
52
1
0.7
8
9
.0
3
7
.9
2
6
.8
3
TO
C%
0
.3
7
0
.3
9
0
.9
7
0
.6
2
1
.2
5
0
.9
6
0
.4
8
1
.0
8
0
.4
2
0
.5
6
0
.6
3
0
.2
0.
85
1.
04
0.
53
0.
94
0.
58
0.
93
1.
07
1.
1
0.
75
0.
84
1.
14
0.
59
0.
67
0.
73
0
.4
2
.1
2
0
.5
5
0
.5
3
2
.6
5
TIC%
1
.1
9
1
.5
3
5
.1
3
4
.3
1
6
.2
2
4
.9
7
1
.2
3
3
.3
5
6
.6
2
4
.5
4
4
.3
1
8
.4
1
2.
83
1.
58
1.
22
3.
86
0.
47
4.
52
3.
82
2.
41
4.
56
2.
86
3.
48
2.
58
2.
85
2.
98
1
0.
12
8
.6
6
8
.4
8
7
.3
9
4
.1
8
CO
2
carb
.
4.
36
5.
60
18.
78
15.
78
22.
77
18.
19
4.
50
12.
26
24.
23
16.
62
15.
78
30.
78
10.
36
5.
78
4.
47
14.
13
1.
72
16.
54
13.
98
8.
82
16.
69
10.
47
12.
74
9.
44
10.
43
10.
91
31.
70
15
.3
0
*LO
I — loss of ignition.
ROJKOVI
Č
et al
.: MANGA
N
ESE
MINERA
LI
ZA
TION IN
THE PALEOGE
NE AND J
U
RASSIC SHALES;
EL
ECT
R
ONIC
SUPP
LEME
NT
E1
6
Ta
ble 4
b
:
C
on
tinued
. Pa
rt
2 f
rom
2.
No.
32 33 34
35
36
37
38
39
40
41 42
43 44
45 46
47 48
49 50
51 52
53 54
55 56
57
58
59 60
61
62
Sa
m
p
le
K
iš 15
K
iš 16
K
o 1
Mich 8
Mich 9
Mich
11
O
B
P
-1
O
BP
-2
P
-1 P
-2
P
-3 P
-4
P
-5 P
-6
P
-7 P
-8
P
-9
P
-10
P
-11
P
-12
P
-13
P
u
11-
R1
P
u
11-
R2
P
11-
6
P
11-
7
R
a-
2
St
-1
St
-5
Šv 2
Šv 7
Šv 8
SiO
2
9.
84
12.
27
23.
19
8.
42
12.
04
8.
09
8.
86
14.
10
34.
34
34.
35
27.
41
31.
93
32.
49
39.
53
49.
99
36.
16
36.
07
34.
17
35.
52
35.
20
40.
19
13.
18
37.
25
27.
47
25.
89
35.
82
49.
22
13.
19
4.
19
9.
34
20.
37
TiO
2
0.
08
0.
31
0.
51
0.
39
0.
34
0.
09
0.
156
0.
245
0.
44
0.
43
0.
38
0.
45
0.
45
0.
54
0.
67
0.
51
0.
51
0.
46
0.
53
0.
47
0.
63
0.
12
0.
49
0.
32
0.
20
0.
482
0
.4
0
0
.2
0
0
.1
0
0
.0
8
0
.2
5
Al
2
O
3
1.
74
6.
76
8.
71
4.
53
4.
33
1.
97
3.
07
4.
55
9.
70
9.
47
8.
50
9.
05
10.
13
11.
44
17.
12
11.
15
11.
24
10.
33
10.
44
10.
43
12.
97
3.
37
10.
06
7.
35
4.
25
10.
14
7.
89
5.
03
1.
58
1.
74
4.
90
FeO
0.
87
0.
00
0.
69
2.
98
0.
22
2.
25
Fe
2
O
3
1.
75
7.
15
8.
09
3.
23
2.
638
1.
61
Fe
2
O
3
to
ta
l
2.
72
7.
15
8.
86
5.
42
9.
36
6.
54
2.
90
3.
25
3.
82
3.
90
3.
27
3.
61
3.
79
4.
61
5.
68
4.
42
5.
05
3.
93
5.
11
7.
80
6.
17
21.
94
8.
77
12.
55
2.
66
10.
28
2.
16
20.
74
2.
20
2.
88
4.
10
MnO
33.
01
39.
74
34.
30
43.
23
33.
97
30.
54
0.
19
0.
37
0.
06
0.
05
0.
08
0.
04
0.
06
0.
20
0.
19
0.
39
0.
31
0.
74
0.
86
1.
21
0.
21
8.
52
1.
63
4.
44
1.
27
5.
95
0.
96
25.
70
21.
65
32.
57
22.
38
MgO
2.
05
1.
55
0.
55
1.
85
1.
50
3.
61
14.
91
11.
78
1.
90
1.
98
2.
10
2.
98
2.
59
1.
76
2.
22
1.
67
1.
72
1.
52
1.
68
2.
39
1.
73
5.
67
2.
46
2.
97
2.
56
1.
38
1.
04
1.
35
3.
66
2.
20
4.
08
CaO
17.
84
12.
37
2.
29
8.
81
9.
63
15.
76
28.
56
28.
16
24.
68
24.
92
29.
64
25.
30
24.
63
19.
84
9.
02
21.
03
21.
73
24.
11
21.
77
19.
75
16.
74
15.
48
17.
89
19.
64
33.
16
16.
03
17.
11
12.
87
30.
41
18.
02
14.
87
Na
2
O
0.
08
0.
17
0.
57
0.
10
0.
12
0.
13
0.
14
0.
19
0.
62
0.
62
0.
43
0.
56
0.
53
0.
68
0.
79
0.
68
0.
67
0.
73
0.
57
0.
68
0.
64
0.
09
0.
77
0.
38
0.
88
0.
51
2
.3
7
0
.1
0
0
.4
8
0
.0
6
0
.0
9
K
2
O
0.
33
1.
12
1.
68
3.
30
3.
11
0.
48
0.
64
0.
95
1.
93
1.
84
1.
77
1.
85
2.
04
2.
11
2.
92
2.
08
2.
00
1.
84
2.
16
1.
84
2.
56
0.
22
1.
47
1.
04
0.
48
1.
54
1
.2
2
0
.7
5
0
.5
4
0
.3
6
1
.0
8
P
2
O
5
0.
15
0.
35
0.
17
0.
10
0.
24
0.
31
0.
11
0.
11
0.
06
0.
09
0.
07
0.
08
0.
06
0.
10
0.
14
0.
11
0.
11
0.
14
0.
12
0.
17
0.
12
0.
76
0.
16
0.
25
0.
10
0.
24
0
.1
4
1
.2
2
0
.0
8
0
.1
4
0
.1
6
H2
O-
0.
40
6.
15
4.
03
5.
77
7.
81
0.
77
0.
64
0.
90
1.
45
0.
15
1.
36
1.
36
1.
51
1.
83
3.
03
1.
80
1.
71
1.
84
1.
47
1.
58
1.
31
0.
73
2.
01
1.
30
0.
47
3.
59
0
.1
4
5
.2
6
0
.1
0
0
.4
8
0
.8
6
LO
I
30.
81
17.
82
14.
89
17.
62
17.
20
32.
14
40.
28
36.
15
22.
20
22.
19
26.
30
23.
96
23.
03
18.
86
1
1.
18
21.
68
20.
42
21.
74
20.
93
19.
82
17.
87
30.
34
18.
37
23.
43
28.
44
17.
39
16.
95
18.
73
34.
70
30.
95
27.
08
B
114
37
26
10
19
52
19
139
90
125
Ba
190
271
30
<30
<30
215
336
202
279
321
254
823
309
291
284
260
246
300
406
275
483
222
266
178
74
1073
229
411
241
211
160
Co
4
1
3
3
4
3
4
2
2
5
2
5
7
9
4
5
1
4
1
0
1
2
1
1
1
6
7
1
6
2
6
1
5
4
6
5
1
4
2
4
2
6
5
4
9
8
1
2
1
6
Cr
46
61
144
74
60
22
33
48
52
42
42
45
49
63
75
62
57
59
77
63
7
6
40
64
31
24
93
24
94
28
47
115
Cu
1
8
2
0
5
9
1
4
1
0
6
1
1
1
4
3
4
3
2
3
6
2
4
3
6
3
8
5
8
4
0
4
0
3
8
4
4
4
0
35
14
43
35
10
36
17
33
21
14
43
La
9
2
5
8
3
1
3
9
1
4
2
5
2
6
2
4
2
4
2
5
2
7
3
9
2
7
2
6
2
5
2
5
2
6
2
7
2
0
28
23
10
24
25
10
17
Mo
1
0
–
3
8
1
–
3
2
2
2
2
3
3
6
2
5
2
–
3
Ni
35
71
186
44
18
14
16
29
28
26
20
26
36
48
46
47
50
27
56
55
5
7
81
94
102
22
70
8
98
18
73
67
Pb
5
1
9
3
6
4
3
3
9
8
9
1
0
–
5
6
6
3
1
2
1
2
1
6
8
1
0
6
1
2
3
2
0
3
1
9
1
5
1
0
2
1
1
0
7
2
5
1
4
1
4
Sr
621
836
338
>500
>500
329
396
286
625
643
625
603
558
576
330
663
665
754
787
701
465
709
634
612
695
649
218
637
383
482
420
V
55
100
177
61
30
27
35
74
79
65
60
73
80
89
118
92
86
87
123
98
103
66
103
85
36
119
49
118
36
62
146
Y
7
2
7
3
7
1
9
1
8
1
3
8
1
4
1
8
2
0
1
8
1
9
1
8
2
0
2
4
2
0
1
9
1
9
1
9
2
0
2
1
1
9
2
2
1
8
8
2
2
2
1
3
2
8
1
5
Zr
18
61
114
114
299
22
34
64
90
83
64
81
82
101
140
96
88
79
89
80
121
26
104
58
45
97
72
40
18
49
Th
1
4
1
7
2
4
7
9
6
3
9
8
1
2
4
U
2
3
3
3
2
4
2
2
3
2
9
2
TC%
9.
57
1.
71
0.
24
0.
12
0.
51
9.
72
11.
13
9.
78
8.
96
4.
12
5.
38
6.
96
3.
03
4.
27
1.
74
10.
78
9.
55
7.
8
TO
C%
3.
34
1.
25
0.
24
0.
005
0.
1
4.
65
0.
2
0.
27
5.
27
0.
92
1.
36
0
.1
7
0
.5
2
0
.6
3
0
.4
5
0
.4
2
2
.9
3
2
.0
6
TIC%
6.
23
0.
46
0
0.
12
0.
41
5.
07
10.
93
9.
51
3.
69
3.
2
4.
02
6
.7
9
2
.5
1
3
.6
4
1
.2
9
1
0.
36
6
.6
2
5
.7
4
CO
2
carb
.
22.
80
1.
68
0.
44
1.
50
18.
56
40.
00
34.
81
13.
51
11.
71
14.
71
25.
47
9.
19
13.
32
4.
72
24.
23
21.
01
*LO
I — loss of ignition.