SEDIMENT-HOSTED MINERAL DEPOSITS

Sediment-Hosted Mineral Deposits

Proceedings of a symposium held in

Beijing, People's Republic of China, 30 July-4 August 1988

Edited by John Parnell, Ye Lianjun and

Chen Changming

Symposium sponsored by

the International Association of Sedimentologists,

the National Natural Science Foundation of China,
IGCP project 219 (Comparative Lacustrine Sedimentology
in Space and Time),

IGCP project 226 (Correlation of Manganese

Sedimentation to palaeoenvironments), and

I GCP project 254 (Metalliferous Black Shales)

SPECIAL PUBLICATION NUMBER 11 OF THE

INTERNATIONAL ASSOCIATION OF SED I MENTOLOGISTS

PUBLISHED BY BLACKWELL SCIENTIFIC PUBLICATIONS

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Cataloguing in Publication Data

Sediment-hosted mineral deposits.

1. Sedimentary rocks. Mineral de po sits
I. Parnell, John II. Ye, Lianjun )[(. Chen, Changming
IV. I ntern a t ional Association of Sedimentologists
V. Series
553
ISBN 0-632-02881-5

Library of Congress
Cataloguing-in-Publication Data
Sediment-hosted mineral deposits: proceedings of a
symposium held in
Beijing, People's Republic of China, 30 July-4 August
1988/edited by John Parnell, Ye Lianjun, and Chen
Changming; sponsored by the International Association of
Sedimentologists ... ret a/.].
p. em. (Special publication number J 1 of the
-

International Association of Sedimentologists)

Includes bibliographical references and index.
ISB 0-632-02881-5
I. Ore deposits-Congresses. 2. Metallogeny­
Congresses. I. Parnell, John. 11. Yeh, Lien-
chOn. TIL Chen, Changming. IV. International
Association of Sedimcntologists. V. Series: Special
pu bli ca tion ... of the International Association of
Sedimentologists; no. ll.
QE390.S43 1.990
553-dc20 90-674
CIP
 Contents

vii Preface

Manganese and Iron Deposits

3 Groote Eylandt manganese norm: a new application of m�neral normalization

techniques on supergene alteration products
B. Pracejus

17 Palaeogeographic setting of late Jurassic manganese mineralization in the Molango

district, Mexico
J.B. Maynard, P.M. Okita, E.D. May and A. Martinez-Vera

31 Manganese and iron facies in hydrolithic sediments

G.A. Gross

39 Manganese deposits of the Proterozoic Datangpo Formation, South China: genesis and
palaeogeography
X. Xu, H. Huang and 8. Liu

51 Manganese enrichment in a Triassic aulacogen graben in the Lijiang Basin, Yunnan

Province, China
H.Liu

57 Processes of formation of iron-manganese oxyhydroxides in the Atlantis-ll and Thetis

Deeps of the Red Sea
G. Yu. Butuzova, V.A. Drits, A.A. Morozov and A. I. Gorschkov

73 Mineoka Umber: a submarine hydrothermal deposit on an Eocene arc volcanic ridge in

central Japan
A. Iijima, Y. Watanabe, S. Ogihara and K. Yamazaki

89 Mineralogy, geochemistry and genesis of manganese-iron crusts on the Bezymiannaya

Seamount 640, Cape Verde Plate, Atlantic
l.M. Varentsov, V.A. Drits and A./. Gorschkov

109 Microbiota from middle and late Proterozoic iron and manganese ore deposits in
China
L. Yin

v
vi Co111e111s

119 Metal precipitation related to Lower Ordovician oceanic changes: geochemical evidence
from deep-water sedimentary sequences in western Newfoundland
J. W. Borsford and D. F. Sangsrer

139 Origin of iron carbonate layers in Tertiary coastal sediments of Central Kalimantan
Pro vi nee (Borneo), Indonesia
G. R. Sieffermann

147 Mineral deposits in Miocene lacustrine and Devonian shallow-marine facies in

Yugoslavia
J. Obradovic and N. Vasic

Copper Deposits

159 Syngenetic and paleokarstic copper mineralization in the Palaeozoic platform sediments
of West Central Sinai, Egypt
M.A. £1 Sharkawi, M.M. £1 Aref and A. Abdel Motelib

173 Geochemical data for the Dongchuan- Yimen strata-bound copper deposits, China
C. Ran

Metal Enrichments Associated with Organic Matter

183 Metal enrichments in organic materials as a guide to ore mineralization

J. Parnell

193 Relationships between organic matter and metalliferous deposits in Lower Palaeozoic
carbonate formations in China
R. Jia, D. Liu and.!. Fu

203 Comparative geochemistry of metals and rare earth ekments from the Cambrian alum
shale and kolm of Sweden
J. Leventhal

217 Uranium enrichment in the Permian organic-rich Walchia shale, Intra-Sudetic

Depression, southwestern Poland
S. Wo/kowicz

225 Index
 Preface
This special publication consists of papers delivered
at an International Symposium of the International
Association of Sedimentologists, held in Beijing,
People's Republic of China, from 30 July to 4 August
L988. The theme of the symposium was Sedimen­
tology Related to Mineral Deposits and incorpo­
rated meetings of three International Geological
Correlation Programme (IGCP) projects; IGCP 219
on Comparative Lacustrine Sedimentology in Space
and Time, IGCP 226 on Correlation of Manganese
Sedimentation to Palaeoenvironments, and IGCP
254 on Metalliferous Black Shales. Each of these
projects has been very successful and enhanced our
knowledge of economic resources in sedimentary
rocks. The papers arc included for convenience
under the headings of (1) manganese and iron
deposits, (2) copper deposits, and (3) metal enrich­
ments associated with organic matter. However,
there is considerable overlap between these themes,
and in particular several accounts of manganese
deposits involve ores hosted in black shale. The
papers include five contributions from Chinese
workers. The interpretation of many of the exciting
ore deposits in China is still at an early stage but we
have taken this opportunity to present what data are
available for some of them.
Accounts of manganese mineraljzation include
two papers on Recent manganese and iron deposits
in the Red Sea (Butuzova et at.) and the Atlantic
(Yarentsov et at.) which emphasize the roles of
Auctuating redox conditions and hydrothermal ac­
tivity respectively. The redox theme is taken up for
ancient manganese enrichments in the Jurassic of
Mexico (Maynard er at.) and the Ordovician of
Newfoundland (Botsford & Sangster), while fossil
hydrothermal activity is invoked in the Proterozoic
VII
of China (Xu er at.), the Triassic of China (Liu) and
the Tertiary of Japan (lijima er at.). A more
specialized aspect of the Proterozoic deposits in
China, the evidence for a microbial role in manga­
nese precipitation, is discussed by Leiming. Super­
gene manganese mineralization, and in particular
the use of a normalization technique to express it, is
described by Pracejus. A review of manganese­
bearing facies in iron formations is provided by
Gross, and the diversity of iron-bearing deposits is
represented by papers on Tertiary siderite formation
in Indonesia (Sieffermann) and Devonian oolitic
ironstones in Yugoslavia (Obradovi6 & Yasic).
Two accounts of copper mineralization emphasize
the role of organic matter in a Proterozoic deposit in
China (Chongying) and pedogenic processes in
Palaeozoic deposits in Egypt (EI Sharkawi er at.).
The significance of organic matter in metal con­
centration is further discussed in accounts of the
Cambrian alum shales in Sweden (Leventhal) and
Permian shales in Poland (Wolkowicz). Character­
ization of the organic matter in some Palaeozoic­
hosted deposits in China is used to infer conditions
of ore deposition (Jia et at.), and metal enrichments
in organic materials arc considered as an ore pro­
specting guide (Parnell).
The Beijing symposium was equally successful in
attracting workers who would not normally contri­
bute to lAS activities, and in emphasizing to sedi­
mentologists the economic importance of their
subject. lt is to be hoped that the common ground
between Sedimentology and Metallogeny will be
further explored.
JoHN PARNELL, DepartmenrofGeofogy,
The Queen's University of Bela
f st,
Belfast BT7 INN. UK
Manganese and Iron Deposits
Spec. Pubis int. Ass. Sediment. (1990) 11, 3-16

Groote Eylandt manganese norm:

a new application of mineral normalization techniques
on supergene alteration products

B . P R A C EJU S
Department of Geology and Geophysics, University of Adelaide, Adelaide, PO Box 498, Australia 5001

ABSTRACT

The method described assists in the quantification of oxidic manganese minerals and associated
materials from the Groote Eylandt manganese deposits (Northern Territory, Australia) which have
been influenced by supergene processes. These ores are commonly composed of very fine grained
minerals, intergrown with lateritic components like kaolinitic clays and iron oxyhydroxides. Additionally,
many manganese phases are poorly-ordered structures which are difficult to identify. Although Fourier
transform infrared (FTIR) spectroscopy has produced dependable data for a limited range of processed
ores, it failed with rocks that contained a mixture of ore minerals and various gangue phases, as was the
case with other analytical techniques (microscopic studies, XRD, IR, etc.). The normalization is based
on the same principles as other mineral norms (e.g. CIPW-Norm) and the norm minerals themselves
were developed according to the mineralogical conditions in the supergene manganese deposits of
Groote Eylandt in the Northern Territory of Australia. Nevertheless, the list of minerals can easily be
extended and adjusted to slightly different environments (e.g. bauxites). The following minerals can be
obtained from this normalization technique: romanechite, todorokite, cryptomelane, pyrolusite, anatase,
quartz, kaolinite, gibbsite, goethite for hematite-free and hematite-containing samples, hematite, and
excess water.

INTRODUCTION

Until recently, many researchers examining manga­
nese oxides have had to overcome a number of
problems when a quantitative mineralogical analysis
of their samples was required for scientific or techni­
cal application. Very commonly manganese ores are
extremely fine grained and their manganese minerals
possess low crystallinities and are intergrown with
other minerals. The crystal structures are not well
defined, or hybrid structures exist. This makes
quantification and even identification very difficult,
because traditional mineralogical techniques, such
as ore microscopy, X-ray diffraction (XRD), and
the more advanced Fourier transform infrared
(FTIR) analysis fail, when confronted with such
complex matter. Therefore, a method has been
developed which approaches the problem from a
theoretical viewpoint (Pracejus et al., 1988a). Indi­
cations for an attempted development of a norm for
manganese minerals can be found in a paper by
Babenko et al. (1983), who quoted calculated min­
eral compositions (partly different from those of this
discussion) of manganese ores from Nikopol. Unfor­
tunately, they do not specify the method for their
calculations, nor do they state whether or not this is
only an approximation.
It is not intended here to replace sophisticated
analytical techniques, such as FTIR (including com­
puterized infrared characterization of materials:
CIRCOM) or differential thermal analysis (DTA),
because this would go far beyond the capability of
the proposed method. However, the norm provides
a tool to process quickly large sample sets, once the
calculation procedure has been established in a com­
puter program. The obtained data can then be cor­
related with results from other analyses.
The necessary background information for the

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun 3

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
4 B. Pracejus
normalization technique has been obtained from
Ostwald (1980, 1988) and Pracejus et al. (1988b),
who examined the mineralogy and geochemistry of
supergene manganese ores from Groote Eylandt in
the Northern Territory of Australia. The deposit
shows an extensive supergene alteration of the pri­
mary sedimentary sequence, which is mainly com­
prised of oolitic and pisolitic manganese oxides.
Because the secondary manganese minerals were
precipitated in a number of host lithologies (e.g.
manganese ores, sands and sandstones, clays
and claystones, iron oxides and oxyhydroxides),
they have created a large range of assemblages
which obscure the 'real picture' of the quantitative
relationships.
The deposits of Groote Eylandt contain pyrolusite,
cryptomelane, romanechite and todorokite as the
main ore constituents. Manganite, vernadite, bir­
nessite, and a number of other manganese oxides
can also be identified, but they appear in much
smaller quantities (Ostwald, 1988) and are therefore
neglected in this theoretical approach. The dominant
gangue minerals are quartz, kaolinite, goethite (plus
other iron oxyhydroxides) and hematite. These
minerals set the frame for the norm model and sensu
stricto can only be applied to conditions similar to
those of Groote Eylandt (tropical/subtropical
supergene alteration of manganiferous protores),
but the setup of the norm can easily be adjusted to
comparable geological environments (e.g. bauxites).
At the moment it is difficult to assess how far this
method can be used for manganese minerals of
other origins (e.g. deep-sea nodules), but it may
prove to be helpful for the understanding of other
deposits.
METHODOLOGY
When the first mineral norm (CIPW; Cross et al.,
1902) was developed, the complex structure of sili­
cates and many other minerals was not yet known.
The chemical composition of minerals was generally
described by molecules and the molecular weights of
oxides. This idealized approach provides a relatively
easy way for a theoretical assessment of mineral
quantities in very fine grained rocks or even glass,
but it has serious disadvantages when minerals occur
in higher amounts in the natural sample which are
not covered by the calculation. Nevertheless, de­
posits which are comparable to Groote Eylandt
should present no problem for the normalization
procedure. Additional norm minerals such as rhodo­
chrosite (MnC03) or alabandite (MnS) can also be
incorporated without difficulty, provided that the
necessary carbonate and sulphide analyses are avail­
able. However, the latter compounds can only be
found in trace element quantities in Groote Eylandt
and thus they only serve as examples for possible
extensions of the norm.
Often it has not been possible to incorporate
specific elements such as potassium, magnesium,
aluminium, iron or barium in more than one norm
mineral because of strong element variations in a
number of host minerals (for instance barium in
cryptomelane). The minerals also rely on at least
one element for their calculation, and this element is
subsequently 'consumed' for the formation of the
respective norm mineral. Potassium for instance can
be found in cryptomelane, romanechite, todorokite,
and also kaolinite, but the normalization uses po­
tassium only for cryptomelane and kaolinite, and all
other phases are calculated on a potassium-free basis.
This means that relatively small errors are automati­
cally introduced for the remaining minerals which
also accommodate potassium. For the same reasons,
intergrowths of different manganese oxides had
to be neglected (e.g. romanechite-todorokite or
romanechite-hollandite; Turner & Buseck, 1979).
In the following sections, the various minerals are
discussed in the same order in which they should be
calculated, because a number of phases depend on
preceding minerals for their own calculations. The
numbers in parenthesis next to the formulae cor­
respond to the steps shown in Figs 1(a)-(d). To
simplify the understanding of the norm, two example
calculations are shown in Table 1 (manganese ore)
and Table 2 (iron ore).
The norm calculation commences with the division
of the weight percentage of the analysed elements
by their molecular weight. The result will be called
mol equivalent (ME). As the ME is represented
by fairly small numbers, it is multiplied by 1000
(ME 1000). The latter step is not necessary, but it
makes handling easier for separate calculations
which are not done by the computer. The next step
distributes the ME 1000 product to the various norm
minerals. The consumption of the appropriate el­
ements must be calculated after each step. The
addition of each oxide that is needed to produce one
mineral is followed by a division of the sum of all
ME 1000 products of the total of the analysis, and a
multiplication by 100 to produce the final mineral
percentages.
 Groote Eylandt manganese norm 5

3
(a)

(4)

Print gb = 0%

Fig. l(a). Flow diagrams of mineral normalization,

calculated from chemical analyses. For explanatioll of
abbreviations see text.

Fig. l(b).

(11)
Fig. l(c). Normalization flow (continued).
As every chemical analysis contains an analytical
error, the reliability on the final results may not
exceed one decimal place or even less. Despite these
limitations it is advisable to calculate the norm to
two decimal places, as this improves the quality of
diagrams which otherwise might be distorted. Errors
that could develop from the necessary simplifications
for some of the minerals are in most cases negligible,
especially when ores of the same type are being
compared, because the errors will also be compar-
no
able. The basis on which each mineral is calculated
is printed in bold. The nomenclature of this norm
has been chosen in such a way that mineral abbrevi­
ations of already existing norms are not duplicated
where possible.
Anatase (an): Ti02 (1)
The mineral anatase is used instead of rutile (also
Ti02), because it is the main constituent in bauxitic
and lateritic soils (Bardossy, 1982). At present,
 Groote Eylandt manganese norm 7

no

Print: check for

additional minerals
and correct input

( ) Input, Output

Decision

D (1) Calculation, Step

yes

/ 7 Print � Flow Direction

J_ Joint

Fig. l(d). Normalization flow (continued) and legend for Fig. l(a to d).

Quartz (q): Si02 (2)

Ti02 is calculated as a separate phase. However, A decision has to be made as to whether or not there
later developments of this normalization might lead is excessive quartz. This will also be the basis for the
to an incorporation of Ti02 into kaolinite, because it determination of kaolinite and gibbsite. In the system
has an excellent correlation with the latter mineral. quartz (q) - kaolinite (ka) -gibbsite (gb) no more
 00

Table l. Normalization procedure for manganese oxide orcs

Mn-Orc Wt'Y., At. wt ME 1000 an 6 q /"-, ka /"-, gb /"-, gt (I) /"-, he /"-, gt (II) /"-,

Mn02 72-3 86·936 831·6

Fc203 1·5 159·692 9·4 4·2 5·2 5·2 0·0 0·0 0·0 0·0
Si02 5-4 60·084 89·9 0·0 89·9 89·9 0·0
AI20, 4·7 101·961 46·1 44·9 1·2 1·2 0·0
P20o 0·07 141·944 0-49
KzO 1·29 94·203 13·7 0·4 13·3
CaO 0·05 56·079 0·9
SrO 0·21 103·619 2·0
BaO 2-46 153·339 16·0
Ti02 0·15 79·898 1·9 1·9 0·0
Na20 0·20 61·979 3·2
MgO 0·5 40·304 12-4
LOI 11·2 18·015 621·7 89·9 531·8 3·5 530·2 5·2 525·1
L 100·0 1649·4 1·9 0·0 229·3 4·6 10-4
Norm 0·1 0·0 13-9 0·3 0·6 bJ
'"i:l
Wt% At. wt ME 1000 em /"-, rm /"-, to /"-, pr /"-, P20s /"-, w /"-, L ;:;
'"'
�
54·9 ;::
Mn02 72-3 86·936 831·6 248·3 583·3 105·6 477-7 422·8 422·8 0·0 "'
Fez03 1·5 159·692 9·4
Si02 5-4 60·084 89·9
Alz03 4·7 101·961 46·1
Pz Os 0·07 141·944 0-49 0·49 0·0
K20 1·29 94·203 13·7 13·3 0·0
CaO 0·05 56·079 0·9 0·9 0·0
SrO 0·21 103·619 2·0 2·0 0·0
BaO 2-46 153·339 16·0 16·0 0·0
Ti02 0·15 79·898 1·9
Na20 0·20 61·979 3·2 3·2 0·0
MgO 0·5 40·304 12-4 12-4 0·0
LOI 11·2 18·015 621·7 32·0 493·1 49·5 443-6 211-4 232·2 232·2 0·0

L 100·0 1649·3 263-6 153·6 120·9 634·2 0·49 232·2

Norm 16·0 9·3 7·3 38·5 0·03 14·1 100·1
Table 2. Normalization procedure for iron oxyhydroxide ores

Fe-Ore Wt% At. wt ME 1000 an 6. q 6. ka 6. gb 6. gt (I) 6. he 6. gt (II) 6.

Mn02 1-4 86·936 16·1

F�03 73·7 159·692 461·5 3·5 458·0 458.0 0·0 51·8 406·2 406·2 0·0
Si02 4·9 60·084 81·6 0·0 81·6 81·6 0·0
AI203 7·7 101·961 75·5 40·8 34·7 34·7 0·0
P20s 1·17 141·944 8·2
K20 0·08 94·203 0·8 0·3 0·5
CaO 0·01 56·079 0·2
SrO 0·01 103·619 0·1
BaO 0·01 153·339 0·1
Ti02 0·36 79·898 4·5 4·5 0·0 C)
...,
Na20 0·01 61·979 0·2 C)
C)
MgO 0·01 40·304 0·2
�
LOI 10·7 18·015 593·9 81·6 512·4 104·2 408.2 458·0 -49·8
W Corr. 593·9 81·6 512·4 104·2 408.2 406·2 2·0 �
El
L 100·0 1243·0 4·5 0·0 207·7 139·0 916·0 51·8 812·4 ;:;

Norm 0·4 0·0 16·7 11·2 4·2 65·4 �

2l
1:>
Wt% At. wt ME 1000 em 6. rm 6. to 6. pr 6. P20s 6. w 6. L ;:;
C1Q
1:>
;:;
Mn02 1·4 86·936 16·1 15·3 0·8 0-4 0·3 2·0 -1·6 0·0 0·0 "'
"'
"'
F�03 73·7 159·692 461·5
;:;
Ah03 7·7 101·961 75·5 C)
...,
P20s 1·17 141·944 8·2 8·2 0·0 �
K20 0·08 94·203 0·8 0·8 0·0
CaO 0·01 56·079 0·2 0·2 0·0
SrO 0·01 103·619 0·1 0·1 0·0
BaO 0·01 153·339 0·1 0·1 0·0
Na20 0·01 61·979 0·2 0·2 0·0
MgO 0·01 40·304 0·2 0·2 0·0
LOI 10·7 18·015 593·9 0·2 -50·0 1·8 -51·8 0·0 -51·8 -51·8
W Corr. 593·9 0·2 1·8 1·8 0·0 0·0 0·0 0·0 0·0
L 100·0 1242·9 16·3 0·7 4·3 0·0 8·2 0·0
Norm 1·3 0·1 0·3 0·0 0·7 0·0 100·2

'D
lO B. Pracejus
than two minerals can be in equilibrium at one time
(Kittrick, 1969). In aqueous systems kaolinite will
form at the expense of either gb or q. This means
that q � 0 when gb = 0 or q = 0 when gb � 0 in
the present calculation. Under natural conditions
this thermodynamic rule can be broken because of
the slow reaction kinetics of the involved mineral
species. Nevertheless, the final stage will lead to a
two mineral configuration which will be accounted
for in this calculation. The decision mentioned above
depends on a preliminary calculation of kaolinite
(only step 3a!). The result will indicate excess quartz
(remaining Si02) or an overestimated consump­
tion which will lead to no quartz, but also to the
calculation of gibbsite (4).
Kaolinite (ka): AhSi205(0H)4
::::} Al203 + 2Si0z + 2Hz0 (3a)
::::} Si02 + 1/2Al203 + H20 (3b)
Depending on the result of the previous decision,
kaolinite will either be determined �rom (3a) or
(3b). If there is excessive quartz, then kaolinite is
calculated on the basis of the available alumina. In
the case of a quartz deficiency, the mineral relies on
the total silica content of the sample and there will
be free alumina for the formation of gibbsite as an
additional phase (4). Analyses of reasonably pure
clay samples have shown that the kaolinite from
Groote Eylandt contains �1·7% FeO and �0·17%
K20. These values are incorporated in the final
result of the kaolinite calculation. The latter two
steps should be investigated for materials from other
deposits and adjusted accordingly. Because these
compounds are relatively low in their concentration,
they could also be omitted from this part of the
norm.
Gibbsite (gb): 2Al(OH)3::::} Alz03 + 3H20 (4)
The conditions for the stability of gibbsite have
already been discussed in context with quartz (2)
and kaolinite (3). Although this mineral has been
described as an accessory from the deposits on
Groote Eylandt, it has to remain a theoretical phase
under the present normalization program, because it
is not known to what extent the excess alumina is
incorporated in minerals like goethite or hematite.
If excess quartz has been determined, then gibbsite
does not exist.
Cryptomelane (em): Ks1Mn801r, ::::} K20 + MnO
+ 15Mn02
Correlations with SrO strongly suggest that stron-
tium is incorporated in the lattice of the cryptome­
lane, and the size of its ionic radius (within a range
of ± 15% ) implies that strontium can substitute for
potassium. This is also in accordance with Post et a!.
(1982), who discussed a cryptomelane with the fol­
lowing formula: (K0.9 Nao.zsSro.nBao.t) (Mn, Fe,
4
Al)8(0, OH)16. Because cryptomelane at Groote
Eylandt varies in its barium content, and also because
barium is needed for the calculation of romanechite,
this element will not be used here. The same applies
for sodium which is taken for the development of
todorokite. The following oxide formula will be
used:
(K20 + SrO) + MnO + 15 Mn02 (5)
A small amount of potassium has been used in the
kaolinite calculation. Therefore it may happen that
manganese samples with a very low cryptomelane
content will give a result of em = 0. Theoretically,
such a sample could be calculated on the basis of the
strontium content, if present, but the normalization
procedure neglects cryptomelane if there is no po­
tassium. Separate strontium minerals such as celestite
have not been detected in the deposit. MnO is
calculated from the total Mn02 analysis, because it
had not been determined for the Groote Eylandt
2
samples. However, if an analysis of Mn + is avail­
able, it should preferably be used.
Romanechite (rm): Baz[Mnl+ Mn114+030]·4H20
::::} BaO + Mn203 + 5·5Mn02 + 2H20 (6)
The barium content of the sample is taken as the
basis for the romanechite calculation (Burns &
Burns, 1977; Giovanoli & Balmer, 1983; Burns et a!.
1985). Mn203 is calculated from the total Mn02
content, as is the case for the previous mineral for
MnO. The strongly varying K20 contents of ro­
manechite in Groote Eylandt (Ba0/K20 ratios of
1·8-34·7; Ostwald, 1988) have been neglected in
favour of cryptomelane, because no consistent values
could be obtained.
Todorokite (to)
This mineral seems to be fairly complicated, having
different compositions in different deposits. A num­
ber of formulae have been proposed by various
authors:
2 2
(Ca, Na, K, Mn +)(Mn4+, Mn +, Mg0)r,01z·3Hz0
after Straczek et a!. (1960);
2
(Ca, Na, K, Ba, Mn +)Mn5012·3H20 after Burns
& Burns (1977);
 Groote Eylandt manganese norm
2
(Mn +, Zn, Mg, Ba, Sr, Ca, Na2, K2, Cu,
PbhMn104+023·9H20 after Larson (1962).
Calculations of analytical results from Groote
Eylandt ores demonstrate that a high number of
rock samples show a very limited interval of the
ratio between calcium, sodium and magnesium
(Ca + Na20)/Mg0 = 0·30-0·34. This indicates a
strong structural association of these three elements,
which most probably is due to a concentration in one
single mineral. Although some samples contain ex­
cess MgO when compared with the ratio mentioned
above, no correlation to any other mineral has been
found for this element. Therefore calcium, sodium
and all the magnesium will be taken as the basis for
the todorokite calculation. The error is fairly small,
which is introduced knowingly by the incorporation
of all the magnesium into todorokite, and it saves
the normalization from further complications.
Fronde! et al. (1960) and Straczek et a!. (1960)
reported significant amounts of magnesium in
todorokites. The author favours the composition
quoted by Larson (1962) because it contains all the
elements that are believed to play an important role
in the todorokite under investigation. This formula
will be shortened and adjusted in the following way:
(Mg, Ca, NazhMn104+0z3'9HzO =?
(MgO, CaO, Na20) + 3·33Mn0z + 3Hz0 (7)
Pyrolusite (pr): Mn02 =? MnOz + xHzO
(x = 0-0·5) (8)
Pyrolusite, the last manganese phase, is calculated
from the remaining manganese which has not been
consumed by the previous minerals (em, rm, to).
Correlation plots between pyrolusite and excess
water also led to the additional incorporation of up
to 50% water, although water does not take part in
the structure of pyrolusite. However, this finding is
in accordance with analytical results from Gryaznov
& Danilov (1980) and Ostwald (1988). It is assumed
that the pyrolusite lattice contains micro-inclusions
of <XMnOOH or yMnOOH, which thus result in a
larger loss on ignition (LOT) than expected.
As indicated by x = 0-0·5 for the water portion
of the norm mineral, the water content of pyrolusite
can be variable. Normally the excess water of the
sample will be larger than 50% of the remaining
manganese (after the calculation of the previous
manganese minerals) and therefore, the 'inclusion
water' can easily be accommodated, where a small
amount of water is left. In a few cases however, less
water is available at this stage of the calculation, and
11
all remaining water is then added to the manganese
component of the formula above.
Goethite (gt) (1): 2FeOOH =? Fe203 + H20 (9)
Goethite is calculated from the remaining iron (a
small amount has been used for kaolinite) and its
equivalent to water. As there are many samples
which have undergone oxidation, it is necessary to
adjust the goethite content in a later step (11). The
decision for this correction is based on step (10). If
an adjustment has to be made, then it will result in
the production of hematite.
Structural water (xw):
XW =? LOI - HzO[ka. gb, gt, rm, to] (10)
The LOI and most of the previous water-containing
phases are used for a first approximation of the
remaining structural water in goethite. The only
exception in this calculation is pyrolusite, because
of its variable water content. If the value of the
calculation becomes negative at this stage, it is an
indication for the formation of hematite in iron-rich
samples. Therefore this operation is essential for the
adjustment of goethite in step (11) and for the
establishment of hematite (12). The LOI of the
Groote Eylandt ores relates entirely to water-bearing
phases, because other compounds such as carbon­
ates are absent in the deposit or exist only as traces.
Goethite (gt) (II):
2Fe00H =? Fe203 + HzO - 21 xw I (11)
If hematite replaced goethite, then the amount of
goethite must be corrected. This is done by a correc­
tion with the help of negative structural water.
Hematite (he): Fe203 =? I xw I (12)
In the case of oxidized goethitic rocks where hematite
has formed, the amount of Fe203 is equivalent to
overestimated structural water from step (10).
Phosphorus: PzOs (13)
All P205 is normalized only, and it is not put into a
mineral. The most appropriate phosphate mineral
which has been described from Groote Eylandt is
vivianite (hydrated iron phosphate), but it is very
rare and it will not be calculated as a separate phase.
Further treatment will have to rely on correlations
with other minerals where it may be incorporated.
This phase is not essential for the normalization and
can be omitted in most cases as long as the amount
in the sample is negligible.
 12 B. Pracejus

1.2
�· Excess water: w :::} LOI - HzO [ka, gb, gt, rm, to, prJ
..
' �. ..
. .. (14)
1.0
· \, ..
'· . The final determination of excess (free ) water is
� 0.8
.
.
based on the LOI and all water-containing phases.
. . .
� 0.6
. .

.s · ...
,
Final sum: L :::} L (norm minerals) (15)
"' . : ... :
"
0.4 � · ·' . .
...:
I.. •.
. .
t,"
· · Normally it is not necessary to calculate the sum of
the normalized minerals, because the result should
,-y·
0.2
be very near to 100% , if existing and normative
0.0 minerals coincide. Deviations of more than ±2%
0 20 40 60 80 100
Kaolinite[%] are considered to be indicative of analytical mistakes,
erroneous input, or additional minerals that contain
Fig. 2. Correlation between norm minerals kaolinite and elements which have not been accounted for in the
anatase (n = 364). normalization (e.g. organic remains) . The latter case
might be camouflaged by a larger LOI and could

20 40 4 8 20 40 60 1 2 3 4 0.4 0.8
ka [%] gb [%] gt[%] he [%1 P205 [%]

Fig. 3. Vertical geological cross­

section from Groote Eylandt
showing the distribution of
10 20 1 2 1 2 3 25 50 75 10 20 30 normalized gangue and ore
em[%] rm[%] to[%] pr [%] w[%] minerals.
 Groote Eylandt manganese norm
probably go undetected. Nevertheless, it is a quick
way of checking the correctness of the norm result
(statistics of a large batch of samples: n = 364, 0 =
99·82, max = 102·24, min = 98·7, SD= 0·529).
Rhodochrosite and alabandite are examples of
additional manganese minerals which could easily
be incorporated into the previous calculation flow
before pyrolusite (step 8). These minerals do not
exist in Groote Eylandt, but are mentioned as
examples for the development of additional norma­
tive phases. Such minerals may be required for the
examination of other deposits. Other more complex
manganese phases require an exact knowledge about
the element(s) that can be taken as the calculation
basis.
Rhodochrosite (rh): MnC03 =? MnO + C02 (7b)
Alabandite (ad): MnS =? Mn + S (7c)
EXAMPLES
The previous sections have demonstrated the nor­
malization procedures in detail. A few possible ap­
plications are shown below. The first one is a simple
correlation plot between kaolinite and anatase
(Fig. 2). A similar plot can be obtained by correlating
Fig. 4. Ternary plot of manganese
oxide norm minerals for some
manganese ore types from Groote
Eylandt. pr
13
Ti02 (not normalized) with Al203, but silica, which
is also part of the kaolinite, will produce ambiguous
results (both a positive and a negative trend) when
correlated with Ti02. The normalization however is
able to split the silica in the calculation and produce
free quartz which can later be related to other
minerals, for instance to heavy minerals in the sand
fraction. The quartz content may also be used to
detect and estimate trace element contaminations
that derive from grinding procedures (e.g. tungsten
from a tungsten-carbide mill). Other analysed el­
ements, such as trace elements and rare earths,
allow a detailed insight into the relationships be­
tween the various minerals and elements.
The next example shows a vertical geological
profile and the distribution of norm minerals (Fig. 3).
The samples were taken from a section on Groote
Eylandt and they represent a sandwich-like structure
of manganese ores that are replaced by iron on top
and at the bottom of the unit. Easily detectable is a
separation of minerals and a preferential develop­
ment of specific phases at different horizons. Dia­
grams like this can provide genetic information, for
instance for overprinting supergene processes.
A third way of using the norm is its application on
ternary diagrams (Fig. 4). Here the ore or gangue
minerals can be plotted for rock types, and fields for
2.5 rm
em+ to
14
30 .-------�
• 12th week
o 17th week
•
s 20 •
•
Q, • ••
..:::
•
+
N
•
c 0
:::; 10
o +-----�----�--4
0 10
Norm Mineral [%]
individual rocks can be produced. Such diagrams
can also provide valuable ideas about formation
conditions for minerals.
In the last example the norm was used to monitor
the successive time-related breakdown of manganese
phases during microbiological leaching tests (Fig. 5;
after Pracejus et al., 1989). It can be observed that
the thermodynamically least stable manganese
oxides are also the first to become unstable during
the leaching procedure, that time gaps exist between
the breakdown of the individual minerals, and that
pyrolusite (not plotted here), the most stable phase
of the examined system, seems to resist the microbial
reduction.
DISCUSSION
Above, the development of a number of normative
manganese phases and associated gangue minerals
has been discussed using the example of supergene
manganese oxide ores from Groote Eylandt. The
method has been applied with success to over 600
partially very complex ore/rock samples ( =20 differ­
ent types), and the results of this normalization
procedure are promising. However only further work
on materials from other deposits can test the wider
applicability of this technique. The examples that
were given above demonstrate the practical use of
the method, but it must be added that a mineral
norm should only be an aid in cases where other
methods of quantification have failed, are very diffi­
cult to obtain or are too expensive. Such a theoretical
technique must always go hand in hand with studies
B. Pracejus
•
Fig. 5. Time-related breakdown of
two manganese oxides (norm
minerals) from Groote Eylandt,
exposed by dissolved manganese
20 30 during microbiological leaching
tests. (After Pracejus et al., 1990.)
of the relevant deposits and should come as close as
possible to the natural conditions of the rocks/ores,
otherwise the results are superficial and of no use.
ACKNOWLEDGEMENTS
This paper is a contribution to IGCP project 226.
The Australian UNESCO Committee has provided
financial assistance through Grant-in-aid 1988, which
is gratefully acknowledged. I am thinkful to Dr R.
Burns (Massachusetts Institute of Technology) and
to Dr A. Kleyensttiber (Mintek, South Africa) for
their helpful comments on the manuscript.
REFERENCES
BABENKO, Y.S., DOLGIKH, L.M. & SEREBRYANAYA, M.Z.
(1983) Characteristics of the bacterial breakdown of
primarily oxidized manganese ores from the Nikopol
deposit. Mikrobiologiya, 5215, 851-856.
BARDOSSY, G. (1982) Karst Bauxites: Bauxite Deposits on
Carbonate Rocks, p. 441. Akademiai Kiad6, Budapest.
BURNS, R.G. & BURNS, V.M. (1977) Mineralogy of manga­
nese nodules. In: Marine Manganese Deposits (Ed. by
G.P. Glasby), pp. 185-248. Elsevier, Amsterdam.
BURNS, R.G., BURNS, V.M. & STOCKMAN, H.W. (1985)
Tl.e todorokite-buserite problem: Further consider­
ations. Am. Mineralogist 70, 205-208.
CROSS, W., IDDINGS, P.J., PIRSSON, L.V. & WASHINGTON,
H.S. (1902) Quantitative Classification of Igneous Rocks,
pp. 286. Chicago University Press, Chicago.
FRONDEL, C., MARVIN, U .B. & ITo, J. (1960) New occur­
rences of todorokite. Am. Mineralogist 45, 1167-1173.
GIOVANOLI, R. & BALMER, B. (1983) Darstellung und
Reaktionen von Psilomelan (Romanechit). Chimia
37(11), 424-442.
 Groote Eylandt manganese norm
GRYAZNOV, V.I. & DANI LOV , I.S. (1980) Oxidized manga­
nese ores of the Nikopol manganese deposit, Ukranian
SSSR. In: Geology and Geochemistry of Manganese
(Ed. by l.M. Varentsov & G. Grassely), Vol. 2,
pp. 403-416. E. Schweizerbartsche Verlagsbuchhand­
lung (Nagele & Obermiller), Stuttgart.
KITTRICK, J .A. (1969) Soil minerals in the Al203- Si02-
H20 system and a theory of their formation. Clay and
Clay Minerals 17, 157-160.
LARSON, L.T. (1962) Zinc-bearing todorokite from Philips­
burg, Montana. Am. Mineralogist 47, 59-66.
OsTWALD, J. (1980) Aspects of the mineralogy, petrology
and genesis of the Groote Eylandt manganese ores.
In: Geology and Geochemistry of Manganese (Ed. by
I.M. Varentsov & G. Grassely), Vol. 2, pp. 149-58.
E. Schweizerbartsche Verlagsbuchhandlung (Nagele &
Obermiller), Stuttgart.
OSTWALD, J. (1988) Mineralogy of the Groote Eylandt
manganese oxides: A review. Ore Geol. Rev. 4, 3-45.
PosT, J.E., VoN DREELE, R.B. & BusEcK, P.R. (1982)
Symmetry and cation displacements in hollandites: Struc­
ture refinements of hollandite, cryptomelane and pride-
15
rite. Acta crystallog. 38, 1056-1065.
PRACEJUS, B., BOLTON, B.R. & FRAKES, L . A. (1988a)
Mineral normalization for supergene Mn-oxides and
associated rocks on ores from Groote Eylandt, NT,
Australia. !AS Symposium on Sedimentology Related to
Mineral Deposits 1988 (Abstract), p. 202. Beijing,
China.
PRACEJUS, B., BOLTON, B.R. & FRAKES, L.A. (1988b)
Nature and development of supergene manganese de­
posits, Groote Eylandt, Northern Territory, Australia.
Ore Geol. Rev. 4, 71-98.
PRACEJUS, B., VARGA, R.A., MADGWICK, J.L., FRAKES,
L . A. & BoLTON, B.R. (1990) Effects of mineral com­
position on microbiological reductive leaching of man­
ganese oxides. Chern. Geol (under review).
STRACZECK, J.A., HOREN, A., Ross, M. & WARSAW,
C.M. (1960) Studies of the manganese oxides- IV,
Todorokite. Am. Mineralogist 45, 1174-1184.
TuRNER, S. & BuSECK, P.R. (1979) Manganese oxide
tunnel structures and their intergrowths. Science 203,
256-458.
Spec. Pubis inr. Ass. Sediment. ( 1990) 11, 17 -30

Palaeogeographic setting of late Jurassic manganese mineralization

in the Molango district, Mexico

J . B . M A YNA R D*, P . M. O K I T A*, E . D . MA yt and A. MA R T I N EZ- V E RA *

*"�"Department of Geology, University ofCincinnati 13, Cincinnati, OH 45221, USA;
*Cia. Minera Aut/an, S.A. de C. V., Mariano Escobedo 456, Mexico, DF 11590

ABSTRACT

A large sedimentary deposit of manganese carbonate formed during the late Jurassic in eastern Mexico.
Throughout the Mesozoic, deposition in this area was in fault-bounded basins with considerable relief.
Both clastic and carbonate sediment was derived from adjacent highs. The manganese ores were
deposited in the slope facies of a shelf-basin transition in water deeper than storm wave base. Rocks
below the ore were deposited in a euxinic basin; rocks above the ore in a more oxidizing, but still suboxic
basin. Manganese was mobilized in deeper, low-oxygen water, then precipitated as manganese oxide on
contact with shallower , oxygen-rich water. Manganese carbonate formed diagenetically from the
manganese oxide via reduction by organic matter and iron sulphide. Because organic matter was in
excess, no primary manganese oxide survived early diagenesis.

INTRODUCTION

Upper Jura s sic rock s of ea st-central Mexico are ho st
to several sedimentary mangane se ore depo sit s that
compri se the Molango di strict. Centred on the town
of Molango, the di strict produce s mangane se car­
bonate ore from one mine at the village of Tetzintla
and supergene oxide ore from several smaller oper­
ation s. The di strict cover s an area of about 25 x
50 km (Fig. 1) and ha s been in production since
1968, with Compania Minera Autlan the major
operator. DeYoung et a/. (1984) e stimated the total
re source to be 1·5 billion metric ton s of mangane se.
In 1982, 183 000 ton s were mined, making Mexico
the world's eighth large st producer of mangane se.
Carbonate ore s make up the bulk of the production,
700 000 ton s of ore compared with 34 000 ton s of
oxide s in 1987 ( Jone s, 1986), but the supergene
oxide s are a much more valuable product becau se of
their suitability for u se in dry-cell batterie s.
* Present address: MS 954, National Center, US Geo­
logical Survey, Reston, VA 22092, USA.
t Present address: Chevron USA, PO Box 6056, New
Orleans, LA 70174, USA.
The predominance of carbonate ore in the
Molango di strict i s in contra st to better-known giant
mangane se depo sit s such a s Chiatura and Groote
Eylandt where mo st production i s from primary
oxide s (Force & Cannon, 1988). Recent model s for
the gene si s of the se large depo sit s have empha sized
the importance of geometry and degree of oxygen­
ation of the ba sin for concentrating large volume s
of mangane se (Cannon & Force, 1983; Frake s &
Bolton, 1984; Bolton & Frake s, 1985; Force &
Cannon, 1988). Becau se mangane se i s soluble a s
2
Mn + under reducing condition s but in soluble a s a
solid such a s Mn02 under oxidizing condition s
( Maynard, 1983), a euxinic marine ba sin such a s
the Black Sea can accumulate large amount s of
mangane se in solution in deep water, mangane se
that i s available for precipitation at the interface
between oxygen-bearing surface water and H2S­
bearing deep water. Wherever thi s anoxic-oxic
boundary inter sect s the edge of the ba sin, there i s
a potential for mangane se enrichment in the
sediment s.
In thi s paper we will examine the stratigraphic and

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun 17

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
18 J. B. Maynard et a!.

·o
.'g 'g ....... 0 •
0 0
Ol
Ol
"'
Ol
� � T ampico
(
.::c --"-0-
r:2:.2-=00 · --- · C iudad
Valles
�·�--------1-----,�-��
,�I
;...
"'J
p, "'q:/,
.,�
3i
-4.
21° 30' \--t--- ----'<1''-\+-------+-------\--l
(j)'i\
(i1 �.
>J �\.. Taman (
�';I ./"\
o•
• L.
"-· ......._ . ..-
.\ \. __.. .
. _, . �a.J 1
;./l .
�
,.. I
* Tetzint l a ---J;·,_
21°00'
)_-+------1
�
I s.
1--;-
"�( Mola ngo ('-\�
•

I ,.Y/1
(_.!:.

,...
0 Km 50

Pachuca Fig. 1. Location of principal sites

•
mentioned in text. Tetzintla is the
largest mine .

palaeogeographic setting for mangane se mineral­ that follow s i s ba sed on thi s literature plu s our field
ization in the Molango di strict. We will attempt to ob servation s in the area between the town s of Taman
recon struct the depo sitional hi story of the area and and Molango (Fig. 1).
compare and contra st that hi story to the model s
developed for oxide facie s mangane se depo sit s.
Pre-Jurassic rocks

Precambrian metamorphic rock s of the Huiznopala

STRATIGRAPHY
Carrillo- B. (1965) and Cantu-C. (1971) have de­
scribed the Jura s sic bio stratigraphy of ea stern
Mexico and Hermo sa de a I Torre & Martinez- P.
(1972), Aguilera- H. (1972), Aguayo-C. (1977) and
Pedrazzini & Ba sanez (1978) have di scu s sed a spect s
of the sedimentology of the region. A de scription of
the geology near the Tetzintla mine i s available in
Alexandri- R. & Martinez-Y. (1988). The di scu s sion
Gnei s s form the ba sement for the di strict (Frie s &
Rincon-0., 1965). Garnet gnei s s and metaquartzite
are the dominant lithologie s, and garnet s yield Sm/
Nd age s of 0·9 Ga ( Ruiz et at., 1988). The se Pre­
cambrian rock s crop out in two place s in the vicinity
of the Tetzintla mine, the fir st in the Arroyo Pilapa
below the mine village of Otongo, about 4·5 km
southwe st of the mine. Here the Precambrian i s
overlain by a serie s of pre- Upper Jura s sic strata,
including the Guacamaya, Huayacocotla and
 Manganese mineralization, Mexico 19

Cahuasas Formations. The second locality studied
lies below the processing plant at Ayotetla, about
2 ·5 km west of the mine, where the Upper Jurassic
rests unconformably on the Precambrian. The con­
tact is marked by a basal conglomerate made up of
fragments of the basement lithologies,and the Upper
Jurassic section is attenuated. The contrast between
this and the first section suggests considerable
topographic relief in the area during the Jurassic.
The oldest sedimentary rocks in the area are
Permian marine strata of the Guacamaya Formation,
which is up to 2000 m thick (Fig. 2). It consists of
rhythmic alternations of dark grey to black shale and
sandstone or conglomerate.
Red beds of the Huizachal Formation overlie the
Guacamaya Formation with angular unconformity.
The Huizachal Formation contains plant fossils that
indicate a Triassic age (Carrillo-B., 1965). In the
immediate vicinity of Molango, the Huizachal
Formation is about 1300 m thick and consists of
yellow to light grey sandstone and conglomerate. In
several areas to the north,including the type locality
at Huizachal near Ciudad Victoria in Tamaulipas,
volcanic rocks of andesitic to rhyolitic composition
are prominent (Lopez-!., 198 6). Deposition appears
to have occurred in fault-bounded troughs similar to
the Newark Basin of the eastern USA (Lopez-!.,
198 6).
Jurassic rocks
Jurassic deposition began with the Huayacocotla
Formation, a dominantly marine unit of highly vari­
able thickness. At the type section in Veracruz,
north of the Molango area,it consists of about 3 00 m
of dark grey shale with some sandstone (Carrillo-B.,
19 65); near Molango, it thickens to nearly 900 m
comprising a basal conglomerate of 20 m, followed
by 50 m of sandy limestone and then by 8 00 m or
more of interbedded black shale and dark grey
sandstone. The early Jurassic ammonite Arnioceras
is common in the sandy limestones. 7 0 km farther
south, near Tenango de Doria, the marine Lower
Jurassic thickens to more than 1500 m of section that

Tertiary Volcanics 170

160
Pimienta Formation
150

Chipoco Facies ] Taman

Fm.
Covered and Faulted
Manganese Horizon 120
Santiago Formation
110
Tepexic Formation
100 --l='=='::i Dark gray to black

Cahuasas Formation
90
----j:::I;:::I::;.\ interbedded micrite and
argillaceous limestone
"' 80
.,
0 70
"'
Huayacocotla 0
60
Formation 0
0 50
c.
"" 40
(..)
30
Huizachal Formation 20
10
0
----jr.=;.-==1 Ore Zone
10 �} Thin- to medium-bedded
�
thinly laminated dark gr y

p Guacamaya Formation .0 "

0 -10
� ------ to black limestone

Cl ·-
.,_
·- "'
� ------
o .
Hi gh·grade ore

� E
"' �
-20
-�
en o
Basement Rocks
.

Fig. 2. Generalized stratigraphic column. Left: complete section. Because of the angular unconformities, the section at a
given locality may be less complete. Right: detailed section across the ore zone at the Tetzintla mine showing the position of
various lithologies discussed in metres above and below the Chipoco -Santiago contact.
20 1. B. Maynard et a/.
Schmidt-Effing (1980) assigned to the Huayacocotla
Group. He interpreted these rocks to be products of
an aulacogen that trended to the northwest and was
an arm of the newly opening Gulf of Mexico.
The cycle: angular unconformity-red beds­
marine strata, began again in the Middle Jurassic
with the deposition of the red beds of the Cahuasas
Formation unconformably on the Huayacocotla
Formation. Thicknesses of the Cahuasas Formation
are variable. It thins southeastwards from about
1 200 m at its type locality near Taman to about
250 m near Tetzintla to as little as 40 m near Mol ango
(Carrillo-B., 1965). It lacks fossils and so may
belong to either the Lower or Middle Jurassic.
Lopez-1. ( 1986) interpreted similar rocks of the
Nazas Formation in San Luis Potosi as having been
deposited in the Middle Jurassic in local basins
developed in a transgressive tectonic setting during
opening of the Gulf of Mexico.
The onset of marine deposition is marked by the
calcarenites of the Tepexic Formation, which
Cantu-C. ( 19 7 1) assigned to the Middle Callovian.
In different localities this unit can be found resting
discordantly on each of the older stratigraphic units.
Its thickness ranges from about 20 to about 1 25 m.
Aguilera-H. ( 19 7 2) interpreted its environment of
deposition as shallow lagoonal, with a soft mud
substrate and perhaps higher than normal salinity.
In the mine area, the Tepexic Formation is domi­
nated by two lithologies: a micritized ooid grainstone
and an oncolitic wackestone,both rich in echinoderm
fragments, which suggests deposition under con­
ditions of normal marine salinity. In the subsurface,
the Tepexic interval is locally marked by a sandstone
or conglomerate. For example in the well Pilcuatla
No. 1, 16 km east of the Tetzintla mine, the Tepexic
Formation is represented by a fining-upwards sand­
stone that has a litharenitic composition at the base,
but becomes more feldspathic and less lithic-rich
upwards ( Pedrazzini & Basanez, 19 78).
The Tepexic Formation passes upwards gra­
dationally into a more argillaceous unit that
Cantu-C. ( 19 7 1) defined as the Santiago Formation.
Unfortunately this name had already been used in
Mexico,for a Palaeozoic stratigraphic unit (Hermoso
de a I Torre & Martinez- P., 19 7 2; Longoria, 1984)
and so should be replaced with another name. How­
ever the application of the term Santiago to the
argillaceous beds above the Tepexic Formation has
become well established (e.g. Imlay, 1980; Enos,
1983; Salvador, 198 7; Winker & Buffier, 1988) and
is used in mapping by the mine geologists for Cia.
Minera Autlan. Accordingly the unit will be referred
to here as the 'Santiago' Formation of Cantu-C.
( 19 7 1), recognizing that a revised terminology that
accords with the code of stratigraphic nomenclature
is needed. The 'Santiago' Formation is a calcareous
shale, rich in organic matter and pyrite, with a well­
laminated appearance that suggests deposition below
wave base in a euxinic basin. Benthic fauna are
absent, except in the top 5- 10 m where Bositra
and Ostrea are found, but ammonites are found in
abundance on a few bedding planes. Rocks of the
bulk of the 'Santiago' Formation correspond to the
barren laminite category of Hallam ( 198 7),indicating
oxygen contents in the bottom water of less than
0· 1 ml/1, whereas the top few metres of the unit
have features typical of the shelly laminite category
of Hallam, indicating oxygen contents that at least
transiently reached levels of 0· 1-0·5 ml/1. Re­
gionally, ammonites indicate ages ranging from late
Callovian to late Oxfordian (Cantu-C., 19 7 1) for the
'Santiago' Formation, but in the vicinity of the
mines we have been unable to find any genera
younger than Callovian,and Reineckiaoccurs within
10 m of the upper contact. The thickness of the
'Santiago' Formation in the mine district is usually
about 300 m, but at the village of Huitepec, about
9 km north of the Tetzintla mine, the S ' antiago'
Formation occupies only 20 m of section, and in
the Pilcuatla No. 1 well to the east it is absent
( Pedrazzini & Basanez, 19 78, fig. 3). These vari­
ations in age and thickness confirm the suggestion of
considerable topographic relief during deposition of
the Upper Jurassic units. Some sections may be
missing by erosion, but the transitional contacts
between units and the generaLly deep-water setting
suggest that slower deposition on local submarine
highs could also be responsible for the variation in
sediment thickness.
The S
' antiago'Formation is overlain by the Taman
Formation, which is of Kimmeridgian age (Cantu­
C., 19 7 1). At the type locality, near the village of
Taman in San Luis Potosi (Fig. 1), the unit consists
of a rhythmic alternation of limestones and shales
that show fining-upwards texture in the limestone
beds, suggesting deposition as turbidites in a basinal
environment. The rocks in this area contain no
enrichment of manganese.
Farther east, in the mining district, the rocks
above the 'Santiago' Formation have been referred
to as the Chipoco Formation (Aguayo-C., 19 7 7;
Alexandri- R. & Martinez- V., 1988), but the name
never seems to have been formally applied. We will
 Manganese mineralization, Mexico
refer to these rocks using the informal designation of
Chipoco facies of the Taman Formation and to the
strata at the type section as the basinal facies of the
Taman Formation. The Chipoco facies contains a
mixture of lithologies (the rocks are referred to as
the ' Taman Mixto' in older reports), dominantly
fine-grained limestone alternating with shale, but
with prominent beds of calcarenite and sandstone in
the upper part of the unit. Horizons rich in a single
bivalve genus, usually Astarte (Force & Cannon,
1988) but sometimes Bositraor Aulacomyella, occur
in places, indicating that the water in the basin at
the time of deposition contained some oxygen.
Posidoniad bivalves like Bositra and Aulacomyella
may have been nektoplanktonic, living attached to
floating wood or seaweed (Stanley, 197 2; Duff,
19 75), but the Astartids were undoubtedly infaunal
( Duff, 19 78). However, the scarcity of other biota
and the general absence of bioturbation place these
rocks in the shelly laminite category of Hallam
( 198 7), implying low oxygen in the bottom water.
Throughout this area, the basal 50- 100 m of the
Chipoco facies is enriched in manganese, most
strongly in the lower 3- 5 m, decreasing upwards.
Farther eastward, the Taman Formation consists
of calcarenites of shallow-water aspect (Aguayo-C.,
19 7 7)that are referred to as the San Andres Member.
These rocks, like the basinal facies of the Taman
Formation, lack manganese enrichment. Because of
folding, the stratigraphic thicknesses of the Taman
Formation in these three areas are difficult to esti­
mate. Aguayo-C. (1977) estimated 500 m for the
western, basinal facies, and we measured 300 m of
continuous section at the type locality followed by
several hundred metres of strata repeated by folding.
At the Tetzintla mine, Aguayo-C. (19 7 7) estimated
2 75 m, but there is a fault here below the calcarenite
beds that cuts out a considerable amount of section.
Thickness of the San Andres Member is between 60
and 1 2 0 m (Aguayo-C., 19 7 7).
Jurassic deposition ended with the Pimienta
Table 1. Framework composition of sandstones of the Molango district
Formation Quartz, M
Guacamaya 89
Huayacocotla
Base 57
Top 62
Cahuasas 81
Chi poco 45
M = monocrystalline; P = polycrystalline.
21
Formation. It is the most widely distributed of all
the units discussed, covering even those palaeohighs
where the Taman and 'Santiago' Formations are
absent ( Pedrazzini & Basanez, 19 78, fig. 3). The
Pimienta Formation overlies the Taman Formation
with a transitional contact, and is distinguished by its
lighter colour, thinner and more even bedding, and
the presence of abundant layers and lenses of black
chert. The basal part of the unit is Tithonian in
age, while the upper part is Lower Cretaceous
(Cantu-C., 19 7 1). Aguilera- H. ( 19 7 2) assigned it to
a basinal environment with normal seawater salinity.
PETROGRAPHY
Thin section study of samples from the older clastic
units shows them to be generally quartzose ( Table 1)
and fine grained with abundant matrix. The terres­
trial units ( Guacamaya and Cahuasas Formations)
show early hematite rims on the framework grains,
whereas the marine units ( Huayacocotla Formation)
have less matrix and abundant quartz overgrowths.
Rock fragments, when present, are internally fine
grained and are generally so altered as to be un­
identifiable. The sandstone beds from the Chipoco
facies differ from those of older rocks in having
a much higher ratio of polycrystalline to mono­
crystalline quartz and in having numerous volcanic
rock fragments with plagioclase microphenocrysts.
Limestone and shale dominate the Upper Jurassic
strata. The Tepexic Formation is a coarse-grained
limestone. A typical lithology is micritized ooid
grainstone. These grainstones consist entirely of
coated grains in a sparry cement. Most grains are
completely micritized, but of those with identifiable
nuclei, echinoderm and bivalve fragments are about
equal in abundance. Another common lithology is
oncolitic wackestone. The oncolites float in a mud
matrix with scattered bioclasts, almost all of which
are echinoderm fragments. The Tepexic Formation
Quartz, P Feldspar Rock fragments
11 0 0
18 11 14
17 14 6
12 0 7
31 8 16
22 J. B. Maynard eta!.
increases in clastic content upwards and becomes
finer grained. The upper contact is placed where
shale becomes dominant over limestone.
The overlying 'Santiago' Formation is a well­
laminated, pyritic, black shale. In thin section, it
consists of 20- 25% silt-sized quartz and 1 0- 25%
calcite,with the balance being mostly clay with some
organic matter and pyrite. The formation becomes
more calcareous upwards, developing calcite con­
cretions near its upper contact. The uppermost beds
are argillaceous pelletal wackestones with many
allochems. The most common are platypelecypod
and echinoderm fragments, peloids, and coated
grains that appear to be micritized ooliths. At
Tetzintla,the top surface of the 'Santiago'Formation
is marked by abundant oysters, wood fragments and
fish scales.
The Taman Formation displays considerably more
variation in lithologic character, both horizontally
and vertically. The basinal facies, as seen in the Rio
Moctezuma at the town of Taman, comprises three
repeated lithotypes: massive wackestones, finely
laminated wackestones and black, finely laminated
shales. The massive wackestones have about 75%
carbonate mud in which are suspended about
20% bioclasts, mostly recrystallized radiolaria, and
5% silt-sized quartz. Laminated wackestones have
more carbonate mud, about 90%, and quartz silt is
more abundant, 5- 1 0%. Bioclasts are rare, never
more than 5%. Shales are similar to those of the
'Santiago' Formation. These three lithotypes are
monotonously repeated in limestone-shale couplets
about 0·5 m thick.
In the mining area, at Tetzintla and at the nearby
village of Acoxcatlan where several test adits have
been driven, the Chipoco facies of the Taman
Formation consists of three distinct lithologies
(rhodochrosite ore, limestone and calcareous shale)
with several prominent fossil-rich horizons. The base
of the stratigraphic unit is marked by the rhodo­
chrosite ore bed, 2-10 m thick, which is very fine
grained with crystallites about 10 to 15 f.tm in dia­
meter. In hand sample the ore looks well laminated,
but in thin section these laminae are wavy and
discontinuous. At Tetzintla, clotted texture is
ubiquitous, and peloids and coated grains are
abundant, up to 3 0% of the rock. The ore at
Acoxcatlan, by contrast, is generally lacking in
peloids and presents a more homogeneous, fine­
grained texture (Force & Cannon, 1988, fig. 1 7).
Laminae are defined by an alternation of lighter­
coloured rhodochrosite-rich material with darker
layers rich in clay and organic material. The-bedding
couple is about 2 mm thick. Chlorite is seen as a
late-stage mineral in many samples.
Above the ore, the Chipoco facies consists of
peloidal wackestones and packstones interbedded
with mudstones and shales. The coarser lithology
contains micritized pellets and ooliths with some
bioclasts, most commonly bivalve fragments. The
finer lithology is well laminated and dark coloured
with about 8 0% carbonate mud and 20% clay and
silt-sized quartz. Three horizons rich in sponge
spicules interrupt this sequence. All three are less
than 1 m thick, and are characterized by abundant
monaxon spicules (now mostly calcite) cemented by
ferroan calcite. Calcite concretions about 20 em
across are common in these beds. Also present in
the Chipoco facies are several bivalve-rich horizons.
The most prominent, about 50 m above the base,
contains 20% whole shells of Bositra, 15% bioclastic
material and 65% mud.
At a level of 1 00 m (at Acoxcatlan) to 160 m (at
Tetzintla) above the base of the Chipoco facies, the
lithology changes abruptly to a mixed sandstone­
calcarenite. Beds are about 1 m thick and show
normal grading, often with granule-sized quartz at
the base. The proportion of calcareous and silici­
clastic framework grains varies greatly. Siliciclastics
range from 30 to 90% with the Acoxcatlan section
having the higher values. Calcareous components
are mostly peloids and micritized ooliths, about 8 0%
of the grains, with subordinate bioclasts, 1 0-15%,
and rare intraclasts. The bioclasts are predominantly
fragments of red algae. Calcite cement makes up
1 0-30% of the rock. The calcarenite interval is 20-
4 0 m thick, followed by about 50 m of section similar
in lithology to that below the calcarenites and then
by the Pimienta Formation, which we did not study
petrographically.
The San Andres Member of the Taman Formation
is poorly exposed in the study area. We collected a
set of samples from a remote locality at Totonicapa,
8 km east of the Tetzintla mine. Of eight samples
studied, six were pelletal wackestones, heavily
micritized with some silt-sized quartz and calci­
spheres. One sample was a bivalve packstone,
another a fine ooid grainstone.
MINERALOGY AND GEOCHEMISTRY
We have examined the Santiago-Chipoco interval
at the Tetzintla mine using X-ray diffraction,electron
 Manganese mineralization, Mexico
probe microanalysis, stable isotope geochemistry,
and measurement of carbon/sulphur ratios. X-ray
diffraction ( Okita, 198 7) shows that the 'Santiago'
Formation contains mostly illite and quartz with
some chlorite, an assemblage common in pre­
Cretaceous shales ( Potter et at., 1980). Calcite is
also common, but no other carbonate phases were
identified. The Chipoco facies contains the same
silicates in smaller amounts. The carbonate fraction
is almost entirely rhodochrosite in the ore bed,
becoming manganese calcite at about 8 m above
the base, then gradually decreasing in manganese
content upwards until the carbonates are again
entirely calcite by about 60 m. Kutnahorite and dolo­
mite are present but in minor amounts. Also found
were abundant magnetite and maghemite, which
make up 5- 1 0% of the ore. These minerals impart a
magnetism to the ore that is detectable in the field.
Electron probe microanalysis ( Okita, 198 7) con­
firms rhodochrosite as the only manganese-bearing
mineral in the ore zone. The average composition is
Mno·66 Mgo.tsCao.uFeo.08, but there is a wide vari­
ation owing to substitution of magnesium for man­
ganese. Calcium and iron are essentially constant.
Carbonates from the low-grade interval above the
ore are manganese calcites, averaging Mn0.18 Mg0.03
Cao.74 Feo.os ·
Stable isotope geochemistry of the rocks exposed
at the Tetzintla mine provides insight into depo­
sitional and diagenetic conditions ( Okita & Shanks,
198 7; Okita et al., 1988). Carbon isotopes of car­
bonate minerals show a strong negative excursion
through the ore zone. Rocks below the ore, in the
3
'Santiago'Formation have b1 C values close to zero,
typical of primary marine carbonates ( Table 2). Ore
zone rhodochrosite is much more negative, as light
as - 16%o, whereas manganese calcites from above
the ore zone have intermediate values, from -5 to
O%o. The light carbon in the ore is suggestive of
derivation of carbonate in part from oxidation of
organic matter. Based on a typical organic matter
value of -3 0%o, the rhodochrosite reflects equal
parts organic- and inorganic-derived carbon ( Okita
et al., 1988). The association of light carbon with
manganese mineralization could arise from a dia-
Table 2. Carbon and sulphur isotopes of carbonate minerals and pyrite from the Tetzintla mine (Okita & Shanks, 1 988)
Host rock
0 to +2·5
-35·5 to -24·0
23
genetic reaction, mediated by bacteria, tietween
manganese oxides and organic matter, as described
by Aller & Rude ( 1988) from experiments:
2
2 Mn0z + Corg + 3C Oz + 2 Hz0� 2 Mn + + 4 HC03-
A similar reaction may lead to the removal of re­
duced sulphur from manganese-rich sediments:
2
4·5 Mn0z + FeS + 7C02 + 4 H2�4·5 Mn +
+ soi- + 7 HC03- + Fe O O H
In both cases the increase in alkalinity should lead to
the precipitation of MnC03:
2
2 HC03- + Mn +� MnC03 +C02 + H20
Thus the isotopic data is consistent with the forma­
tion of rhodochrosite by diagenetic replacement of
manganese oxide rather than by direct precipitation
from the water column or by replacement of pre­
existing carbonate minerals, as had been suggested
from textural evidence by Force & Cannon ( 1988).
Sulphur isotopes, like those of carbon, show an
anomaly in the ore zone ( Okita & Shanks, 1988).
3
Pyrite from above and below the ore has light b 4S
values, about -30%o, typical of open system re­
duction of sulphate by bacteria ( Table 2). Within the
3
ore zone, b 4S values are heavy, about +8%o. Okita
& Shanks ( 1988) attributed heavy sulphur in the
manganese ores of the Molango district and in a
similar deposit in China to sulphate reduction in
a nearly closed system. A closed system favours
heavier sulphide because nearly all of the sulphate
in the system is reduced, leading to values that
approach that of seawater, whereas in an open
system only the lightest sulphate is reduced and the
resulting sulphide is very negative ( Hoefs, 1980).
One mechanism for a closed system is a basin with
limited connection to open seawater, as has been
proposed for the Selwyn Basin of Canada ( Good­
fellow & Jonasson, 1984; Shanks et al., 198 7).
Alternatively a closed system could result from
pyrite formation within the sediment at a depth
below that for effective transport from seawater by
diffusion. If the oxidation of FeS by Mn02 hypo­
thesized by Aller & Rude ( 1988) applies, then
pyrite formation would be delayed until all Mn02
High-grade ore Low-grade ore
-16-4 to -11-5 -5·2 to 0
+4·6 to +11-3 +4·3 to + 12·5.
24 1.8. Maynard et a!.

was converted to MnC03, far enough below the
sediment-water interface that exchange of pore
water sulphur species with overlying seawater would
be limited.
As first described by Leventhal (1983) and elab­
orated by Raiswell & Berner (1985),the relationship
between organic carbon and sulphide sulphur in
sediments can be used to decipher depositional con­
ditions, especially the degree of anoxia in the basin.
Liu (1990) has found that the Molango district was
characterized by euxinic conditions in the basin
prior to the onset of ore deposition, followed by
more oxidizing conditions in the mine area during
and after deposition of the ore. The 'Santiago' For-
SANTIAGO FORMATION
10
•
• under more oxidizing conditions, but still somewhat
* 8
:;:
::::> 6 Chipoco facies has the most oxidizing chemical
�
mation shows a typical euxmtc pattern (Fig. 3): a
high sulphide sulphur content, 2-10%, and a posi­
tive correlation between sulphur and carbon with an
intercept on the sulphur axis. The degree of pyrit­
ization (the proportion of available iron incorporated
in pyrite) is high,averaging about 75%. The Chipoco
facies by contrast contains less sulphur, 1-3% in
shales and usually less than 0·5% in the rhodochro­
site ore, and the sulphur vs carbon plot has an
intercept near zero on the sulphur axis. The degree
of pyritization is quite variable in the Chipoco facies,
ranging from near zero in the ore to about 60% for
shales and limestones above the ore. Liu (1990) has
interpreted these patterns as indicating deposition of
the 'Santiago'Formation in a restricted basin having
a stratified water column with hydrogen sulphide in
the bottom water. The Chipoco facies was deposited
depleted in oxygen; the suboxic facies of Froelich
et al. (1979). The ore zone at the base of the

::::> signature of all rocks in the sequence, but this aspect

"'
Q) 4 may well be a result of the oxidation of FeS by
"0
Mn02 rather than a result of abundant free oxygen
::::> in the bottom water. The scarcity of benthos, the
(/) 2
general lack of bioturbation, and the presence of
0 low-diversity assemblages of opportunistic genera
0 such as Aulacomyella confirm the Chipoco facies as
Organic carbon wt. %
a product of deposition under low-oxygen but not
euxinic conditions. We have been unable to perform
CHIPOCO FACIES
10 a comparable geochemical evaluation of the basinal
facies of the Taman Formation because the exposed
* 8 rocks are too weathered for sulphide sulphur ana­
:;:
lysis, but the lack of benthos and bioturbation sug­
�
::::> gest euxinic conditions.
6 ..
Chipoco
::::>
<f) ..
Q) 4
"0

�
to PALAEOGEOGRAPHY
-
::::> to ·
(/) 2
• to The sedimentological and geochemical data summar­
� to
.. to
ized above suggest a depositional model for the
0 ;;$�!...
0 1 2 3 4 5 6 7 8 9 10 Molango ore (Fig. 4) in which the ore was deposited
Organic carbon wt. % on the slope in a shelf-basin transition. The San
Andres Member is representative of the shallow
• Black shale "'Rhodochrosite to Limestone
shelf, the Chipoco facies represents the slope, and
Fig. 3. Relationship of sulphide sulphur to organic carbon the Taman Formation at the town of Taman is
in ore and host rocks. The positive intercept on the sulphur representative of the deepest part of the basin in the
axis for samples from the 'Santiago' Formation implies Kimmeridgian. The rapid facies transitions and
deposition under euxinic conditions; the lower sulphur abundance of clastic material suggest a rimmed shelf
concentrations and intercept of the sulphur/carbon
correlation line near the origin for Chipoco facies samples
rather than a carbonate ramp, following the classi fi­
implies less reducing, probably suboxic conditions. cation scheme of Read (1985). The ideal facies
.
Redrawn from Liu ( 1990). sequence for this setting is tidal flat/lagoon-rim
 Manganese mineralization, Mexico 25

Sections studied
1. Nonoalco
2. Te tz:i ntl a
3. Acoxcatlan
4. Totonicapa
5. Taman
6. Huitepec

Fig. 4. Depositional model for the Molango area. Ore deposition occurred on the slope on the west side of a chain of
islands. The other slope facies shown on the diagram are not exposed and are only inferred from the shelf facies at Amixco
reported by Aguayo-C. (1977).

shoal-escarpment-talus-mud blanket with dominant feature in similar deposits of the Alps

gullies-proximal turbidites-distal turbidites­
pelagics. The San Andres Member contains lith­
ologies typical of the first two facies, the Chipoco
facies represents the mud blanket environment with
packages of proximal turbidites, and the rocks at the
town of Taman are the distal turbidites. The base­
of-scarp talus is conspicuously lacking, but it is a
( Eberli, 198 7). The Alpine sequence seems to have
formed in a similar tectonic setting to that of eastern
Mexico, is of early Jurassic age, and contains
manganese enrichments ( Germann, 19 73; Jenkyns
1988). The southern part of the Gulf of Mexico
seems to have lacked biohermal accumulations in
shallow-water facies in the Jurassic, unlike the Alpine
26 J. B. Maynard et a!.

sequences ( Wilson, 1975; Crevello & Harris, 1984).
This absence of frame builders perhaps accounts for
the absence of base-of-escarpment talus in the
Molango district. Deeper-water sponge reefs are
common in the Jurassic, and may have been the
upslope source of the prominent spiculite horizons
seen at the Tetzintla mine.
Changes in lithology with time in the Molango
district can be attributed to a nearly continuous
rise in sea level. Worldwide, sea level was rising
throughout the middle and late Jurassic (Vail et at.,
1984, fig. 2; Hallam, 1989, fig. 10). The total rise
over this time interval was about 50-100 m. Super­
imposed on this trend of rising sea level are several
shorter regressive episodes. Hallam (1989)identi fied
a regression at the end of the Callovian and two
in the Oxfordian, with a pronounced transgressive
event in the middle Oxfordian. The Vail et al. (1984)
curve only identifies a late Callovian unconformity,
followed by a smooth rise of sea level into the late
Kimmeridgian (see Hallam & Maynard, 1987, for a
further discussion of the differences in these two
sea-level curves for the mid to late Jurassic). In the
Molango district, the Tepexic Formation is the
shallowest marine facies, and indicates the onset of
the Callovian transgression. The Tepexic Formation
passes upwards gradually into the deeper-water
sediments of the 'Santiago' Formation, but the
change from dominantly carbonate to dominantly
clastic sediments suggests that there was tectonic
movement, accentuating the relief between adjacent
highs and lows,and that the highs provided abundant
fine clastics. Most of the 'Santiago' deposition in the
study area occurred during the Callovian. A brief
regressive episode, correlative with one of Hallam's
(1989) Oxfordian regressions, may have occurred at
the top of the 'Santiago', where grain size becomes
coarser, a shelly fauna appears, and wood fragments
are common. This event may correspond to the
Buckner red bed-anhydrite sequence intercalated in

--s- Tithonian
Sea Level

Kimmeridgian
Sea Level

0 50
Km

PRE-JURASSIC BASEMENT

Fig. 5. Generalized palaeogeographic model for eastern Mexico during the late Jurassic showing progressive flooding. Ore
deposition began abruptly at the beginning of the Kimmeridgian, perhaps reflecting access of the basin to an external
supply of manganese such as the spreading centre in the newly opened Gulf of Mexico. (Based on Padilla y Sanchez, 1982,
fig. V7, and Aguilera-H, 1972, fig. 1.)
 Manganese mineralization, Mexico
the underlying Smackover ( Oxfordian) and overlying
Haynesville ( Oxfordian- Kimmeridgian) Lime­
stones of the northern Gulf region (Faucette &Ahr,
1984, fig. 3). The return to carbonate deposition in
the Taman-Chipoco-San Andres interval can be
attributed to sea level rising to the point that most
highs were covered by seawater and began exporting
carbonate debris to deeper water, in the same way
as the Bahamas do today. As reconstructed by
Boardman & Neumann (1984) and by Boardman et
al. (1986), the Bahama Banks act as a carbonate
factory when bank tops are flooded during high
stands of sea level, exporting fine carbonate mud,
largely aragonite, to the deep water between the
banks. During low stands, the bank tops are subject
to karstic erosion, little material is washed over the
rim into deep water, and only a pelagic calcite
component is seen in the sediments adjacent to the
banks. For eastern Mexico, the low stand time
would have seen abundant clastics produced by
weathering of the exposed basement and pre-Jurassic
clastic deposits, a supply that was mostly shut off in
the Kimmeridgian. The Pimienta Formation reflects
the continuation of this process to maximum flooding
of the bank tops (Fig. 5).
IMPLICATIONS FOR
METALLOGENESIS
Manganese mineralization in the Molango district is
con fined to the slope facies of a shelf-basin tran­
sition. Neither the shelf nor the basin facies show
manganese enrichment, and the mineralization is
continuous along the exposed trend of the slope
facies. Vertically, manganese appears abruptly at
the transition from a euxinic black shale to a suboxic
shale-limestone sequence at a time of rising sea
level. These patterns are consistent with the strati fied
basin model of manganese deposition described by
Force & Cannon (1988): manganese was soluble
in deep water, precipitated at the oxic-anoxic
boundary, and settled back through the water
column as manganese oxide particles. Over most of
the basin, these particles redissolved, but in shal­
lower water on the basin slope they reached the
bottom sediment, de fining a manganese oxide com­
pensation depth. In a refinement of the Force &
Cannon model, Okita et at. (1988) proposed that
reaction with organic matter during early diagenesis
converted the manganese oxides to manganese
carbonates.
27
At Molango, in contrast with other large deposits,
all the manganese oxide was converted to carbonate.
Perhaps the proximal oxide facies has been lost by
subsequent erosion, but one would expect some
remnant over such a large district. The balance
between manganese oxide and manganese carbonate
in a deposit is most likely controlled by the rate of
supply of Mn02compared with the rate of supply of
organic matter at the time of deposition. If available
carbon exceeds one-half the (molar) amount of
manganese, then all oxide will be converted to
carbonate. Mineralization at Molango appears to
have occurred on a steeper palaeoslope in deeper
water than in the deposits at either Chiatura or
Groote Eylandt (Force & Cannon, 1988). Molango
was entirely below normal wave base, whereas other
deposits show abundant evidence of wave activity
(Bolton et at., 1988). Consequently, organic matter
preservation should have been better at Molango
than at the other deposits, an idea supported by
residual Corg values between 0·5 and 1·0% (Liu,
1990).
The sudden appearance of manganese and its
gradual disappearance also needs explanation. If
the progressive flooding model presented above is
correct,the basin should have experienced increasing
communication with adjacent basins through time in
the late Jurassic. The vertical sequence suggests that
at the beginning of the Kimmeridgian, the depth of
water in the basin exceeded a sill depth that allowed
communication with an external source of manga­
nese. One possible source would be a spreading
centre in the Gulf of Mexico ( Pindell, 1985). In­
creasing water depth then led to a gradual improve­
ment in the ventilation of deep water in the basins
and a consequent decrease in the amount of
manganese in solution.
ACKNOWLEDGEMENTS
Special thanks are due to E. Force, who first sugges­
ted this project to us, and to R. Alexandri, who
made the field work possible. R. Imlay identified an
early collection of bivalves, and we are grateful for
being able to bene fit from his years of experience
with the Jurassic of Mexico. J. Calloman was kind
enough to identify our collection of ammonites, and
T. Hallam joined us in the field to help with
fossil identi fications and with environmental re­
constructions. We are particularly appreciative of
his sharing his insights into Jurassic palaeogeography
 28 1. B. Maynard et al.
a nd of t he oppo rtu nity to compa re our respective
expe rie nces w hile i n t he field, co nf ro nted by t he
dif ficult e
i s of t he actual rocks. T he staff of Cia.
Mi ne ra Autla n have bee n u nsti nti ng i n t heir suppo rt
of t his p roject , a nd we have be ne fitted f rom t heir
yea rs of effort i n u nde rsta ndi ng t he local geology.
We could not have p roceeded wit hout t he suppo rt of
A. Medi na.
REFERENCES
AGUAYO-C . , J . E. ( 1 977) Sedimentacion y diagenesis de Ia
formacion 'Chipoco' (Jurasico Superior) en aflora­
mientos; estados de Hidalgo y San Luis Potosi. Rev.
lnst. Mex. Petroleo 9 , 1 1 -37.
AGUILERA- H . , E. ( 1 972) Ambientes de deposito del
J urasico Superior en Ia region Tampico-Tuxpan. Sol.
Asoc. Mex. Geologos Petroleras 24, 129- 163.
ALEXANDRI- R . , R., FORCE, E.R. , CANO N , W . F., SPIKER,
E. C. & ZANTOP, H. ( 1 985) The sedimentary manganese
carbonate deposits of the Molango District , Mexico .
Ceo!. Soc. A m . , Program with Abstracts, 17, 5 1 1 .
ALEXANDRI- R . , R . & MARTINEZ-V . , A. ( 1988) Geologia
del distrito manganesifero de Molango, Hgo. In:
Geologia Economica de Mexico (Ed. by G. P . Salas) ,
pp. 40 1 -408. Fondo de Cultura Economica, Mexico.
A LLER, R.C. & Ru DE, P . O. ( 1988) Complete oxidation of
solid phase sulfides by manganese and bacteria in anoxic
marine sediments. Geochim. cosmochim. Acta 52,
75 1 -765.
BOARDMAN, M. R . & N E U MAN N , A.C. ( 1984) Sources of
periplatfonn carbonates: northwest Providence Channel,
Bahamas. J. sedim. Petrol. 54, 1 1 10 - 1 123.
BOARDMAN , M . R . , NEUMANN , A . C . , BAKER, P. A . , D U L I N ,
L. A . , KENTER, R.J. , H U NTER, G.E. & KIEFER, K.B.
( 1 986) Banktop responses to Quaternary fluctuations in
sea level recorded in periplatfonn sediments. Geology
14, 28-31 .
BoLTO N , B . R . & fRAKES, L.A. ( 1 985) Geology and genesis
of manganese oolite, Chiatura, Georgia, USS R . Geol.
Soc. Am. Bull. 96, 87- 102.
BoLTON , B . R . , fRAKES, L . A . & CooK, J. N . ( 1988) Petro­
graphy and origin of inversely graded manganese pisolite
from Groote Eylandt, Australia. Ore Geology Reviews
4, 47-69.
CANNON , W. F. & Fo RCE , E . R . ( 1983) Potential for high­
grade shallow-marine manganese deposits in North
America . I n : Unconventional Mineral Deposits (Ed. by
W.C. Shanks), pp. 1 75 -1 90 . AlMME, New York.
CANTU-C. , A. ( 1 971 ) La Serie H uasteca (Jurasico Media­
Superior) del centro este de Mexico. Rev. lnst. Mex.
Petroleo 3, 17-40.
CARRILLO- B . , J. ( 1 965) Estudio geologico de una parte del
anticlinoria de Huayacocotla. Sol. Asoc. Mex. Geologos
Petroleras 17, 73-96.
CREVELLO, P. O . & HARRIS, P.M. ( 1984) Depositional
models for Jurassic reefal buildups. l n : The Jurassic of
the Gulf Rim (Ed . by P.S. Ventress, D.G. Bebout,
R. F. Perkins & C. H. Moore), pp. 57- 102. Gulf Coast
Section, Society of Economic Paleontologists and
Mineralogists, Austin, Texas .
DEYOU N G , J . H . , SUTPHIN , O.M. & CAN N O N , W. F . ( 1984)
International strategic minerals inventory summary
report-manganese. US Geol. Survey Circular 930-A ,
22pp.
D u FF, K.L. ( 1 978) Bivalvia from the English lower Oxford
Clay (Middle Jurassic) . Palaeontographical Society
Monographs, London, 137pp .
EBERLI, G . P. ( 1987) Carbonate turbidite sequences
deposited in rift-basins of the Jurassic Tethys Ocean
(eastern Alps, Switzerland). Sedimentology 34, 363-388.
ENos , P. ( 1983) Late Mesozoic paleogeography of
Mexico. ln: Mesozoic Paleogeography of West-central
United States (Ed. by M.W. Reynolds & E.D. Dolly) ,
pp. 133- 141 . Rocky Mountain Section , Soc. Econ.
Paleont. Miner.
FoRCE, E.R. & CAN N O N , W . F. ( 1 988) Depositional model
for shallow-marine manganese deposits around black­
shale basins. Econ. Ceo!. 83, 93- 1 17.
FoRcE, E. R . , CAN NON, W . F . , KoSKI, R.A. , PASSMORE,
K.T. & DoE, B . R . ( 1983) I nfluences of ocean anoxic
events on manganese deposition and ophiolite-hosted
sulfide preservation. US Ceo!. Survey Circular 822,
26-29.
fRAKES, L.A. & B O LTON B . R . (1984) Origin of manganese
giants : Sea level change and anoxic -oxic history .
Geology 1 2 , 83-86.
fRIES, C. & RINCON-0 . , C. ( 1965) Nuevas aportaciones
geocronologicas y tectonicas empleadas en el laboratorio
de geocronometria. Sol. Jnstituto de Geologia de
Universidad Nacional A u tonoma de Mexico 73, 57 - 133.
FROELICH, P. N. , KLINKHAMMER , G. P. , B E N DER, M. L. ,
LUEDTKE, N . A., HEATH, G. R., C U L L E N , 0 . , D A U PHI N,
P . , HAM MOND, D. , HARTMAN , B. & MAYNARD, V. ( 1979)
Early oxidation of organic matter in pelagic sediments of
the eastern equatorial Atlantic: Suboxic diagenesis.
Geochim. cosmochim. A cta 43, 1075- 1091.
GERMA N N , K. ( 1973) Deposition of manganese and iron
carbonates and silicates in Liassic marls of the
northern Limestone Alps ( Kalkalpen). In: Ores in
Sediments (Ed. by G.C. Amstutz & A.J. Bernard),
pp. 129- 138. Springer, Berlin.
GooDFELLOW, W.O. & JONASSO N , I . R. ( 1984) Ocean
stagnation and ventilation defined by dei34S secular
trends in pyrite and barite, Selwyn Basin, Yukon.
Geology 1 2 , 583-586.
HALLAM, A. ( 1987) Mesozoic marine organic-rich shales.
In: Marine Petroleum Source Rocks (Ed. by J. Brooks &
A .J. Fleet), pp . 25 1 -261. Spec. Pub!. Geol . Soc. 26.
HALLAM, A. (1 989) A re-evaluation of Jurassic eustacy in
the light of new data and the revised Exxon curve.
In: Sea Level Changes - A n Integrated Approach
(Ed. by C. K. Wilgus). Spec. Pub!. Soc. econ. Paleont.
Miner. 42.
HALLAM, A. & MAYNARD, J.B. ( 1987) The iron ores and
associated sediments of the Chichali formation
(Oxfordian to Valanginian) of the Trans-Indus Salt
Range, Pakistan. J. geol. Soc. 144, 107 - 11 4 .
HERMOSO D E LA TORRE, C. & MARTINEZ-P . , J . ( 1 972)
Medicion detallada de formaciones del Jurasico Superior
en el frente de Ia Sierra Madre Oriental. Bot. Asoc.
Mex. Geologos Petroleras 24, 45-63.
 Manganese mineralization, Mexico
HOEFS, J. ( 1980) Stable lsowpe Geochemistry, 2nd edn.
Springer, Heidelberg, 208pp.
I M LAY, R.W. ( 1980) Jurassic paleobiogeography of the
conterminous United States in its continental setting. U S
Geol. Survey, Prof. Paper 1062, 134pp .
J E N KYNS, H .C . ( 1988) The early Toarcian (Jurassic) anoxic
event: stratigraphic, sedimentary, and geochemical evi­
dence. A m . J. Sci. 288, 101- 151.
JONES, T.S. ( 1 986) Manganese. US Bureau of Mines,
Minerals Yearbook 1 986 I, m 1 -ml3.
LEVENTHAL, J.S. ( 1983) An interpretation of carbon and
sulfur relationships in Black Sea sediments as indicators
of environments of deposition. Geochim. cosmochim.
Acta 47, 133-138.
L w , T-B. ( 1990) CIS relationships in shales hosting
manganese ores from Mexico , China , and
Newfoundland : I mplications for depositional environ­
ment and for mineralization. In : Manganese
Metallogenesis (Ed. by B. Bolton) . Elsevier, Amsterdam .
LONGORIA, J.F. ( 1 984) Mesozoic tectostratigraphic domains
in east-central Mexico. In: Jurassic- Cretaceous
Biochronology and Paleogeography of North A merica
(Ed . by G. E . G . Westermann) , pp. 65-76. Geol. Assoc.
Canada Spec. Paper 27.
LOPEZ-I. , M. ( 1986) Estudio petrogenetico de las rocas
igneas en las formaciones Huizachal y Nazas. Sol. Soc.
Geol. Mex. 67, 1 - 18.
MAYNARD, J.B. ( 1983) Geochemistry of Sedimentary Ore
Deposits, Springer, New York, 305pp.
OKITA, P.M. ( 1987) Geochemistry and mineralogy of the
Molango manganese orebody, Hidalgo State, Mexico.
PhD Dissertation , University of Cincinnati , 362pp.
0 KITA,P. M. , MAYNARD, J.B. & MARTINEZ-V . , A. ( 1986)
Molango: a giant sedimentary manganese deposit in
Mexico. A m . Ass. Petrol. Geol. Bull. 70 , 627.
0KITA, P. M. , MAYNARD, J.B. , SPIKER, E.C. & FO RCE , E . R.
(1988) Isotopic evidence for organic matter oxidation by
manganese reduction in the formation of stratiform
manganese carbonate ore. Geochim. cosmochim. A cta
52, 2679-2685.
0KJTA, P.M. & SHANKS, W .C. ( 1987) Stable isotope study
of the Molango Deposit, Hidalgo State , Mexico. Geol.
Soc. A m . (Abstracts with Programs) 1 9 , 793.
OKITA, P . M. & SHANKS, W.C. ( 1988) Del-13 C and del-34
S trends in sedimentary manganese deposits, Molango
(Mexico) and Taojiang (China): evidence for mineraliz­
ation in a closed system. Int. Assoc. Sedim. Proc. , pp.
188- 189. Beijing, China.
PADILlA Y SANCHEZ, R. J. ( 1982) Geologic evolution of
29
the Sierra Madre Oriental between Linares, Concepcion
del Oro, Saltillo, and Monterrey, Mexico . Unpubl. PhD
Thesis, Univ. Texas at Austin, 2 16pp.
PEDRAZZINI, C. & BASANEZ, M.A. ( 1978) Sedimen­
tacion del Jurasico Medio-superior en el anticlinoria
de Huayacocotla, Cuenca de Chicontepec, Estados de
Hidalgo y Veracruz, Mexico. Rev. Inst. Mex. Petrol. 1 0 ,
6- 19.
PINDELL, J . L . ( 1 985) Alleghenian reconstruction and sub­
sequent evolution of the Gulf of Mexico , Bahamas, and
proto-Caribbean. Tecwnics 4, 1-39.
P01TER, P . E. , MAYNARD, J.B. & PRYOR, W.A. ( 1980)
Sedimentology of Shale. Springer, Berlin, 306pp .
RAISWELL, R . & B ERNER, R. A . (1985) Pyrite formation in
euxinic and semi-euxinic sediments. A m . J. Sci. 258,
7 10-724.
READ, J .F. ( 1985) Carbonate platform facies models. Bull.
A m . Ass. Petrol. Geol. 69 , 1 - 2 1.
RU I Z , J . , PATCHETT, P.J. & ORTEGA-G . , F. ( 1988)
Proterozoic and Phanerozoic basement terranes of
Mexico from Nd isotopic studies. Geol. Soc. Am. Bull.
100, 274 -281.
SALVADOR, A . ( 1987) Late Triassic-Jurassic paleo­
geography and origin of Gulf of Mexico Basin. A m . Ass.
Petrol. Geol. Bull. 7 1 , 49 1 -55 1.
SCHMIDT-EFFING, R. ( 1980) The Huayacocotla aulacogen in
Mexico (Lower Jurassic) and the origin of the Gulf of
Mexico. In: The Origin of the Gulf of Mexico and the
Early Opening of the Central North A tlantic Ocean (Ed.
by R.H. Pilger) , pp. 79-86. Louisiana State University
Press , Baton Rouge.
SHANKS, W.C. , WOODRUFF, L . G . , JiLSON , G.A. , JENNINGS,
D.S . , MoDE N E , J . S. & RYAN , B . D . ( 1987) Sulfur and
lead isotope studies of stratiform Zn-Pb-Ag deposits ,
Anvil Range, Yukon: Basinal brine exhalation and
anoxic bottom-water mixing. Econ. Geol. 82, 600-634.
STANLEY, S. M. ( 1972) Functional morphology and
evolution of bysally attached bivalve mollusks . J. Paleo.
46, 165-2 12.
VAIL, P. R. , HARDENBOL, J. & TODD, R.G . ( 1984)
Jurassic unconformities, chronostratigraphy and sea­
level changes from seismic stratigraphy and biostrati­
graphy. A m . Ass. Petrol. Geol. Mem. 36, 129- 144.
WiLSON , J.L. ( 1975) Carbonate Facies in Geologic History .
Splinger , Heidelberg, 471 pp.
WiNKER, C.D. & BuFFLER, R . T . ( 1988) Paleogeographic
evolution of early deep-water Gulf of Mexico and
margins , Jurassic to Middle Cretaceous (Comanchean).
Bull. Am. Ass. Petrol. Geol. 72, 318-346.
Spec. Pubis int. Ass. Sediment. ( 1990) 1 1, 31-38

Manganese and iron facies in hydrolithic sediments

G.A. G R O S S
Geological Survey of Canada*, 601 Booth St., Ottawa, Canada, Kl A 0£8

ABSTRACT

Manganese-rich facies in Algoma, Lake Superior and Rapitan types of iron formation are an important
part of the stratafer group of siliceous metalliferous sediments. Manganese oxide and carbonate facies
associated with iron formation, chert, carbonate, shale, turbidites, tuff and lava are up to 30 m thick
and have iron to manganese ratios ranging from 0·2 to 2. The major and minor element contents of
stratafer manganese sediments are compared to typical oxide facies of iron formation and to modern
protolithic facies on the seafloor that formed by hydrothermal effusive and hydrogenous processes.
Cherty manganiferous facies and their gondite metamorphic equivalents occur throughout the geological
record, provide major resources of manganese, and are the most common protore for high-grade
manganese deposits that formed by secondary enrichment processes.

RELATED FACIES

Many manganese and iron ore deposits have been
studied separately in the past without recognizing
spatial and genetic relationships of the associated
manganese- and iron-rich facies of protore. The
cherty iron-, manganese- and sulphide-rich facies
are the most common and abundant members of the
stratafer group of hydrolithic metalliferous sedi­
ments. Typical relationships between manganese­
and iron-bearing facies are outlined in this paper to
give a better understanding of the metallogeny of
stratafer sediments and its application in exploration
and development of the extensive mineral resources
hosted in them.
The term stratafer has been adopted ( Gross &
McLeod, 1987) to include the great variety of litho­
logical facies that are genetically a part of or related
to cherty iron formations, including the associated
manganese, polymetallic sulphide and various other
facies formed by chemical, biogenic and hydro­
thermal effusive or exhalative processes (Gross,
1988). They are commonly composed of banded
chert and quartz interbedded with oxide, sulphide,
carbonate, and silicate minerals containing ferrous,
nonferrous, and/or precious metals.
'
Geological Survey of Canada Contribution No. 4 1888.
Manganese facies and their equivalent meta­
morphosed strata, known as gondite, host important
syngenetic ore deposits and are protore for many
large manganese deposits formed by oxidation,
leaching and secondary enrichment processes (Roy,
1981). The world's largest syngenetic deposits of
copper, zinc, lead and gold are hosted in sulphide
facies of iron formations, and large deposits of rare
earth elements, tin, tungsten and barite occur in
oxide and other facies (Gross, 1986). Many banded
chert and siliceous metalliferous facies containing
less than 15% iron that developed separately or
within iron-formation units are important host rocks
for gold.
Lithological facies from one or more of the three
main groups of stratafer sediments are frequently
interbedded or traced laterally through transitions
from facies to facies, and a common origin or direct
genetic relationship between them is evident. Gen­
etic models developed for both ancient and Recent
stratafer sediments indicate that they formed by
volcanogenic or hydrothermal effusive processes
(Gross & McLeod, 1987). Their composition, distri­
bution, facies development and depositional en­
vironment appear to have been controlled mainly by
the tectonic setting and physical, chemical and bio­
logical factors in the depositional basins (Gross,

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun

31
and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
32 G. Gross
l983a). Stratafer sediments occur on all continents
from early Precambrian to Recent (Gross, 1986) and
the deposition of the great variety of lithological
facies developed within them does not appear to
coincide with events or environmental factors that
were peculiar or unique to a particular period in the
Earth's history. Much attention has been given to
the extensive thick sequences of Lake Superior type
iron formation which developed on the shelves and
tectonically active marginal parts of Proterozoic
platforms or cratons (Gross, 1965, 1968; James &
Sims, 1973). Iron formations of this type and age
appear to represent the largest and most extensive
stratigraphic units of hydrolithic sediment. There
are also many Archaean iron formations such as the
Hamersley in Australia or Kudremuk in India, or
late Proterozoic and younger iron formations of the
Rapitan type, that are of a similar order of magnitude
as the Lake Superior type formations. Some of the
sedimentary manganese deposits such as Nikopol
and Chiatura in the USSR have been considered to
have formed by non-volcanogenic or hydrothermal
processes. The manganese and iron in these and
other deposits of a similar type could have been
derived from a continental source by erosion pro­
cesses, by the reworking and redeposition of
manganese from submarine volcanogenic sediments,
crusts or nodules, or by hydrothermal processes.
Probably geochemical data and the presence of
banded chert in sequences of stratafer sediments
provide the best criteria for identifying volcanogenic
or hydrothermal primary sources of the metals.
MANGANESE-IRON DEPOSITS
Descriptive data from a survey by Gross (1983b) of
facies rich in manganese and iron in many parts of
the world that are associated with iron formations
are summarized in Table 1. The following
generalizations are based on these data.
1 Manganese carbonate and oxide facies are the
most common and abundant manganese ores, or
protore for enriched deposits.
2 Manganese-rich facies are commonly associated
with oxide and carbonate facies of iron formations.
3 Chert and siliceous facies are associated in varying
amounts with nearly all of the deposits studied.
4 The associated sediments and their metamor­
phosed equivalents vary from mature sandstone,
quartzite and dolomite deposited in shelf and mar­
ginal basins, to turbidites, greywacke and shale from
deeper-water environments in graben basins, island
arc and spreading-ridge tectonic systems.
Banded siliceous manganiferous facies are as­
sociated with cherty iron formations in most of the
iron ranges of the world, except in North America
where they are not well developed. They are com­
monly interbedded with oxide and carbonate facies
but they may occur in all kinds of mineralogical
facies of iron formation and stratafer sediments.
Fine-grained clastic facies at the margins of depo­
sitional basins evidently mark transitions from
chemical to clastic deposition.
Highly metamorphosed manganese-rich facies
form gondite (Roy, 1980), which is a common type
of protore for enriched manganese deposits.
Sedimentary features and evidence of the primary
nature of many gondite rocks have been destroyed
by recrystallization and migration of elements during
later stages of metamorphism. Review of the litera­
ture indicates that manganese facies occur more
frequently, but are generally thinner or less
abundant, in Algoma than in Lake Superior type
iron formations. They appear to be more common
in Phanerozoic and Mesozoic than in Precambrian
basins.
Manganese facies related to iron formations occur
as three types.
1 Those within stratigraphic units of iron formation
that contain sufficient manganese, usually from
1-5%, to provide manganiferous iron ore and
protore. Examples are found in the Cayuna Range
in the Lake Superior Region, at Wabush Mines in
Labrador, McLeod Mine at Wawa, Ontario, in
Minas Gerais in Brazil and in many other iron
formations.
2 Manganese facies interbedded in or transitional to
cherty iron formations, with manganese : iron ratios
greater than one. This type is widespread throughout
the world and is protore for most of the large
manganese ore deposits. Important examples are:
the Postmasburg and Kuruman deposits in Lake
Superior type iron formations in the Transvaal of
South Africa; Morro do Urucum in Brazil;
Karadzhal in Kazakhstan; Jalisco in Mexico;
manganese facies in the Kitakama, Ashio and Tambo
belts in Japan; Marra Mamba iron formation and
others in the Pilbara Goldfields, Phillips River and
Yilgarn Goldfields in Australia; in the Guyana shield
in Brazil and Guyana; in the Spanish-Portuguese
pyrite belt; Maliy Khingan in the USSR; in the
Orissa, Karnataka and Andhra Pradesh regions
of India; Moanda in Gabon; at Woodstock, New
 Manganese and iron facies
Brunswick; and on the Nastapoka Islands in Canada.
3 Shale-hosted manganese facies, commonly
manganese oxide and/or carbonate associated with
muds and fine-grained clastic sediment which may
be transitional to or isolated from iron-rich facies
and chert beds. Occurrences of this type commonly
form thin facies of limited extent and are widely
distributed. Nikopol in the Ukraine and Chiatura in
Georgia, USSR, are outstanding examples, and
other examples are the Tangganshan and Taojiang
deposits near Changsa in Hunan Province, and
Wafangzi in Liaoning Province in China, and
numerous other deposits on all continents.
Karadzhal and San Francisco manganese-iron
deposits
Research on two deposits has been very instructive
m understanding the genetic relationships of
manganese- and iron-rich facies of stratafer
sediments.
The Karadzhal iron-manganese deposits in the
Dzhail'min syncline in central Kazakhstan occur in
a succession of quartz-magnetite-hematite and
carbonate facies of iron formation in a thick sequence
of Devonian sandstones, conglomerate, reddish-grey
limestones, cherty calcareous shales and volcanic
rocks. The iron formation is closely associated with
reddish limestone and ranges in thickness from
1 to 24 m over a distance of 15-20 km. Manganese
and carbonate beds are intermixed with jasper and
chert-carbonate facies of the iron formation. The
jasper facies are associated with spilitic rocks in the
northwest part of the syncline where they achieve
their greatest thickness, and contain up to 60% iron
and probably average over 30%. In the eastern part
of the area the iron-formation beds are 1-5 m thick
and contain up to 40% manganese and 6-10% iron.
The iron : manganese ratios in the iron formation
change from 10: 1 to 7: 1 in the west to 1: 1 and 1 : 1·5
in the east (Sapozhnikov, 1963; Kalinin, 1965).
Probably the siliceous iron formations in the western
part of the area were deposited closer to the effusive
hydrothermal source of the metals while deposition
of the thinner manganese-rich facies may have been
distal from the metal source.
Manganese facies in iron formations similar to
those described at Karadzhal occur in other Algoma
type iron formations in Kazakhstan and the southern
Ural Mountains.
A transition from iron oxide to manganese oxide
facies in iron formation is found in the San Francisco
33
manganese deposit at Jalisco, Mexico (Zantop, 1978,
1981). Banded cherty iron and manganese oxide
facies of iron formation are developed in a Tertiary
lacustrine basin in association with tuff, andesite
flows, red mudstones and siltstones, conglomerates
tuffs and shales. The iron formation forms a stratified
lens up to 3 m thick and 1·6 by l km in extent. Iron :
manganese ratios range from 40 : 1 in the iron oxide­
rich facies at one side of the lens to 1 :50 in the
manganese-rich part with an overall ratio of 2: 1.
Zantop (1981) concluded that the higher concen­
trations of arsenic, barium, copper, molybdenum,
lead, tin, zinc and vanadium in the manganese and
iron oxide facies were evidence of a hydrothermal
volcanogenic contribution to their formation.
MANGANESE FACIES IN IRON
FORMATIONS IN CANADA AND THE
UNITED STATES
The banded cherty manganiferous Algoma type iron
formation near Woodstock, New Brunswick, Canada
forms part of a succession of thinly bedded grey,
grey-green and red slate, sandstone, greywacke
and limestone of Silurian age. The manganiferous
jasper-hematite facies of the iron-manganese­
formation are up to 30 m thick and have an iron
content ranging from 11 to 30%, a manganese con­
tent from 12 to 25% and an overall iron: manganese
ratio of about 1: 5. Several hundred million tons of
potential manganiferous resource material have been
outlined in the Woodstock area, and manganiferous
facies are present in this group of rocks where they
extend westward into the state of Maine (Gross,
1967; Anderson, 1986).
Manganese facies in the extensive Lake Superior
type iron formations in North America are thin and
of limited lateral extent. Beds rich in manganese in
carbonate facies iron formation have been traced
for several kilometres on Belanger and Flint Islands
of the Nastapoka Chain on the east side of Hudson
Bay ( Bell, 1879; Chandler, 1982). A bed of rhodonite
up to 20 em thick was observed in the Mount Reed
iron formation in northern Quebec and some beds in
magnetite-hematite facies of iron formation near
Wabush Lake in southwest Labrador, Newfound­
land contain up to 2% manganese (Gross, 1968).
Manganiferous facies in the Cayuna Range in
Minnesota have been investigated as a source of
manganese.
 Table 1. Manganese-iron facies associated with iron formation

Country Region Deposit Age Manganese Fe: Mn Range Facies Facies

rock group content (%) Average MnO, MnC, MnSi FeO, FeC, FeSi, FeS

Australia Pilbara Proterozoic MnO FeO

Phillips Rv Archaean MnO Fe
Yilgarn Archaean MnO FeO
. Africa West Mokta, Nsuta, Precambrian MnO, MnC, MnSi FeO
Tambao
Zaire Katanga Kisenge Precambrian <20-40 MnC, MnSi
South Africa Transvaal Kuruman Proterozoic 25 1: 3 4: 1-1: 45 MnO, MnC FeO, FeC
Botswana Kalahari Palapye Proterozoic 4: 1-1: 4 MnO FeO
Gabon Moanda Proterozoic 10-20 1: 8 1: 40-30: 1 MnO, MnC, MnSi FeO
Sinai Um Bogma Mesozoic MnO FeO
Brazil Bahia Bandarra Precambrian 4: 1-15: 1 MnO, MnC, MnSi FeO
Minas Gerais Proterozoic 1:5-1: 20 MnO, MnC FeO, FeC, FeSi
Para Proterozoic 32-47 1: 10 MnO, MnC, MnSi FeO, FeS
Amapa Serrade Precambrian 1: 10 MnC, MnSi
Navio
Mato Grosso Morrodu Cambrian 1: 4 MnO FeO
Urucum
Canada Appalachian Woodstock Silurian 1: 1 2·4: 1-1: 12 MnO, MnC FeO
Nastapoka Is Proterozoic MnC FeO
Table I. (continued)

Associated rocks

Country Region Amphibolite Schist Gneiss Gonditc Chert-silica Carbon shale Shale Limestone Sandstone Turbidites Tuff Volcanic
(Amp) (Sch) (Gn) (Gond) (Ch-Si) (CSh) (Sh) dolomite quartzite (Tb) (Tf) (V)
(LD) (SQ)

Australia Pilbara Chert Sh

Phillips Rv Chert
Yilgarn Chert
Africa West Amp Sch Gn Gond Ch-Si CSh Sh SQ Tf v

Zaire Katanga Amp Gn Gond CSh SQ

South Africa Transvaal Chert Sh LD SQ Tb Tf v

Botswana Kalahari Chert Sh SQ Tb Tf v

Gabon Chert CSh Sh LD SQ Tf v

Sinai Sh LD SQ
Brazil Bahia Amp Sch Gn Ch-Si
Minas Gerais Ch-Si Sh LD SQ
Para Amp Sch Gn Ch-Si CSh Sh LD SQ Tb v
Amapa Sch Ch-Si CSh LD SQ
Mato Grosso Ch-Si Sh SQ
Canada Appalachian Ch-Si Sh LD Tb
Nastapoka Is Chert Sh SQ Tf
China Liaoning Chert Sh LD s
Hunan Chert CSh Sh L s
Hunan Chert CSh Sh L s

Mexico Jalisco Chert Sh Tf v

USA California Chert Sh Tb Tf v

India Karnataka
Dharwar Amp Sch Gn Ch-Si Sh LD SQ v
Orissa Gond Ch-Si CSh Sh SQ Tf v
Andhra Pradesh Amp Sch Gn Gond Ch-Si Sh LD SQ
Madhya Pradesh Gond Ch-Si LD
USSR Kazakhstan Ch-Si Sh LD SQ Tf v
Urals Ch-Si Sh LD SQ
Y enisey Ridge Ch-Si Sh LD SQ Tf v
Transcaucasia Ch-Si Sh LD SQ Tf v

Japan Ashlo Mts Ch-Si Sh LD SQ Tb Tf BY

Kitakami Mts Chert Sh SQ Tb Tf BY
Tamba Mts Chert Sh Tf v

Germany Alps Mts Chert Sh LD SQ Tf

Hungary Bakony Mts Chert Sh LD SQ
Finland Ch-Si Sh LD Tb Tf v

Portugal-Spain Pyrite Belt Ch-Si Tf v

New Zealand Northland Ch-Si Sh SQ Tb Tf v

Table 1. (continued)

Country Region Deposit Age Manganese Fe:Mn Range Facies Facies

rock group content (%) Average MnO, MnC, MnSi FeO, FeC, FeSi, FeS

China Liaoning Wafangzi Middle Proterozoic 16-30 1: 1-1: 2 MnO, MnC FeO
Hunan Tangganshan Lower Sinian 18-20 MnC, MnO, MnSi, MnS FeO
Hunan Taojiang Ordovician 20 MnC, MnO FeO
Mexico Jalisco San Tertiary 2: 1 40: 1-1: 50 MnO FeO
Francisco
USA California MnO, MnC, MnSi FeO
India Karnataka
Dharwar Proterozoic MnO FeO
Orissa Archaean 28-42 1: 1·5-1: 1·3 MnO FeO
Andhra Pradesh Pakhal Proterozoic 14-32 1: 1·8-1: 4 MnO, MnC, MnSi FeO, FeS
Madhya Pradesh Aravalli Proterozoic 1:25 MnO, MnC, MnSi FeO
USSR Kazakhstan Karadhzal Devonian 10: 1-1: 1·5 MnO, MnC FeO, FeC
Urals· Permian 2: 1 MnO FeO
Yenisey Ridge Proterozoic 10 MnC FeO, FeC
Transcaucasia Armenia Cretaceous-Eocene 1: 2
Japan Ashlo Mts Palaeozoic 1: 1 MnO, MnC, MnSi FeO
Kitakami Mts Permian-Jurassic MnO, MnC FeC
Tamba Mts Miocene MnO, MnC FeC
Germany Alps Mts Jurassic 1:2 MnO, MnC, MnSi FeO, FeC
Hungary Bakony Mts Epleny Mesozoic 1: 2 1: 20-1: 5 MnC FeC, FeS
Finland Kittila Proterozoic 0.4-15 MnC, MnSi FeO, FeC, FeSi, FeS
Portugal-Spain Pyrite Belt Silurian MnO, MnC, MnSi FeS
New Zealand Northland Auckland Mesozoic 1:20 MnO FeO
 Manganese and iron facies 37

Table 2. Composition of typical iron and manganese facies (wt%)

Type-area: Algoma Superior Bathurst Woodstock Nastapoka Red Sea Santorini Baur B.
Fe-Mn facies: oxide oxide oxide oxide carbonate oxide ox-carb oxide
n-samples: 963 176 85 14 2 43 25 19
Data set: (1) (2) (3) (4) (5) (6) (7) (8)

Si02 47·8 47·7 29·77 22.84 4 1·75 9-45 1 1·5 23·8

Ah03 2·6 1·3 4·19 5·16 0·35 1·6 1·2 6·5
Ti 0·07 0·02 0·22 0·1 1 0·009 0·04 0·03
Na20+K20 1·0 0·2 0·72 1·06 0·12 1·8 5·7
MgO 1·6 1·2 1·91 1·77 1·23 1·1 1·2
CaO 1·7 1·6 3-43 3·92 3-43 4-4 1·1 36·6
FeO 12·7 7·8 17·5 8·35 6-45 7·8
Fe Tot. 30. 1 30·9 35·26 19·84 9·04 30·2 31·6 21·5
Mn 0·1 0·5 2·16 17·98 16-47 1·3 0·03 5·7
P z Os 0·2 0·05 1·76 1·65 0·02 0·2 0-4
H20 Tot. 0·8 1· 1 2·09 3-46 0·6 55-4 48·7
C02 0·9 2·7 3·89 9·2 18·8 3·7 10·5
s 0·2 0·02 0·52 0·06 2·8 0·5
Ba 0·02 0·017 0·05 0·14 0·01 0·03 0·008 1·35
v 0·006 0·003 0·01 0·005 0·005 0·013
Cr 0·008 0·0 1 1 0·004 0·005 0·001 0·002 0·003
Co 0·004 0·003 0·007 0·01 0·001 0·005 0·015
Ni 0·008 0·003 0·006 0·003 0·01 0·003 0·0007 0·062
Cu 0·005 0·00 1 0·008 0·00 1 0·002 0·547 0·0015 0·135
Zn 0·006 0·003 0·14 0·005 0·002 1·78 0·006 0·051
Pb 0·067
Sr 0·007 0·003 0·01 0·03 0·002 0·038 0·008

Sources of data. Data set ( 1) and (2): Gross ( 1986). Data sets (3)-(5): Geological Survey of Canada, IFCHEM FILE -
Chemistry of Iron Formations in Canada. Data set (6): Red Sea, Atlantis Deep, amorphous goethite facies, Bischoff
( 1969). Data set (7): iron-rich muds at the Kameni Islands, Santorini, Greece, Bostrom & Widenfalk ( 1984). Data set (8):
metalliferous sediment from Baur Basin, East Pacific, Dymond eta!. (1976) and Sayles eta!. (1975).

Algoma type siderite facies in the Michipicoten
District of Ontario contain up to 2% manganese.
RECENT PROTOLITHIC FACIES OF
MANGANESE-IRON FORMATION
The global distribution of protolithic manganese
facies on the modern seafloor has been outlined in·
recent work by Gross & McLeod (1987). Manganese
deposition related to recent active hydrothermal
fields takes place in areas distal from the hydro­
thermal vents in the outer margins of the sedimentary
basins, and manganese is usually transported beyond
the main depositional areas for siliceous iron-rich
facies (Gross, 1987). Deposition of manganese in
large quantities is commonly related to the cooler
hydrothermal effusive centres and marginal to the
higher temperature centres. Manganese facies on
the modern seafloor are associated with or closely
related to hydrothermal fields located along
spreading ridges, deep-fracture systems or island
arcs, in tectonic settings that are closely analogous
to those of their ancient counterparts.
Manganiferous facies in the Red Sea and in many
other areas of the ocean floor have bulk compositions
and element distribution patterns that are similar to
those found in oxide facies of iron formations (Table
2) (Bischoff, 1969; Dymond et al., 1976; Bostrom &
Widenfalk, 1984; Gross & McLeod, 1987). The
element distribution patterns in the Algoma type
Woodstock manganiferous facies, and in the Lake
Superior type Nastapoka manganiferous facies, are
very similar to the characteristic patterns found in
about 50 other iron formations of these types (Gross,
1990).
In conclusion, the syngenetic relationship of
manganese- and iron-rich facies of iron formations
has been demonstrated in the examples of stratafer
sediments mentioned above and in the extensive
literature on hydrolithic sediments from most
parts of the world. The close similarities in bulk
compositions, element distribution patterns
and geochemistry in ancient and Recent iron- and
38 G. Gross
manganese-rich facies are convincing evidence of
their development by similar genetic processes.
Many examples of Recent hydrolithic sediments on
the seafloor, which are known to be forming by
volcanogenic, hydrothermal effusive and exhalative
processes, clearly show that they are protolithic
facies of iron formation and associated manganese­
and sulphide-bearing facies of stratafer sediments.
ACKNOWLEDGEMENTS
This paper comprises contribution number 41888 of
the Geological Survey of Canada, and is published
with the permission of the Survey.
REFERENCES
ANDERSON, F.D. (1986) Woodstock, Millville, and
Coldstream Map-Areas, Carleton and York Counties,
New Brunswick. Geological Survey of Canada, Memoir
353, 45-55.
BELL, R. (1879) Report on an Exploration of the East Coast
of Hudson's Bay, Nastapoka Islands. Geological Survey
of Canada, Report of Progress for 1877-78, 15c-18c.
BISCHOFF, J. L . (1969) Red Sea geothermal brine deposits:
Their mineralogy, chemistry, and genesis. In: Hot Brines
and Recent Heavy Metal Deposits in the Red Sea (Ed. by
E.T. Degens & D.A. Ross), pp. 368-406. Springer,
New York.
BosTROM, K. & WlDENFALK, L. (1984) The origin of iron­
rich muds at the Kameni Islands, Santorini, Greece.
Chem. Ceo/. 12, 203-218.
CHANDLER, F.W. (1982) The structure of the Richmond
Gulf Graben and the geological environment of lead­
zinc mineralization and of iron-manganese formation
in the Nastapoka Group, Richmond Gulf area, New
Quebec-Northwest Territories. In: Current Research,
Part A, Geological Survey of Canada, Paper 82-1A,
1-10.
DYMOND, J., CORLISS, J.B. & STILLINGER, R. (1976)
Chemical composition and metal accumulation rates of
metalliferous sediments from sites 319, 320, and 321. In:
Initial Reports on the Deep Sea Drilling Project, Vol. 34
(Ed. by R.S. Yeats et a/.), pp. 575-588. Superintendant
of Documents, US Government Printing Office,
Washington DC.
GRoss, G.A. (1965) Geology of Iron Deposits in Canada,
Vol. 1, General Geology and Evaluation of Iron De­
posits. Geological Survey of Canada, Economic Geology
Report No. 22, 181 pp.
GRoss, G.A. (1967) Geology of Iron Deposits in Canada,
Vol. 2, Iron Deposits in the Appalachian and Grenville
Regions of Canada. Geological Survey of Canada,
Economic Geology Report No. 22, 111pp.
GRoss, G.A. (1968) Geology of Iron Deposits in Canada,
Vol. 3, Iron Ranges of the Labrador Geosyncline.
Geological Survey of Canada, Economic Geology Report
No. 22, 179 pp.
GRoss, G.A. (1983a) Tectonic systems and the deposition
of iron-formation. Precambrian Res. 20, 171-187.
GRoss, G.A. (1983b) Low grade manganese deposits- a
facies approach. In: Cameron Volume on Unconventional
Mineral Deposits (Ed. by W.C. Shanks), pp. 35-47.
Society of Mining Engineers, American Institute of
Mining, Metallurgical, and Petroleum Engineers Inc.,
New York.
GRoss, G.A. (1986) The metallogenetic significance of
iron-formation and related stratafer rocks. I. Ceo/. Soc.
India, 28 (2,3), 92-108.
GROSS, G.A. (1987) Mineral deposits on the deep seabed.
Marine Mining 6, 109-119.
GRoss, G.A. (1988) A comparison of metalliferous
sediments, Precambrian to Recent. Krystalinikum 19,
59-74.
GROSS, G.A. (1990) Geochemistry of iron-formation in
Canada. In: Ancient Banded Iron Formations (Regional
Presentations) (Ed. by 1.-1. Chauval, Cheng Yugi, E.M.
El Shazly, G.A. Gross, K. Laajoki, M.S. Markov, K.L.
Raki, V.A. Stulehikou, S.S. Augustithis), pp. 3-26.
Theophrastus Publications, Athens.
GRoss, G.A. & McL EOD, C.R. (1987) Metallic minerals on
the deep seabed. Geological Survey of Canada, Paper
86-21 and Map 1659A, 65pp.
JAMES, H.L. & S tM S, P.K. (1973) Precambrian iron form­
ations of the World. Econ. Ceo/. 68, 913-1221.
KALINtN, V.V. (1965) The Iron-Manganese Ores of the
Karadzhal Deposit. Institute of the Geology of Ore
Deposits, Petrography, Mineralogy and Geochemistry,
USSR Academy of Sciences, Moscow, translation of
Russian, 123pp.
RoY, S. (1980) Manganese ore deposits of India.
fn: Geology and Geochemistry of Manganese, Vol.
2 (Ed. by I.M. Varentsov & G. Grasselly), pp.
237-277. Manganese Deposits on Continents. E.
Schweizerbart'sche Verlagsbuchhandlung (Nagele &
Obermiller), Stuttgart.
RoY, S. (1981) Manganese Deposits. Academic Press,
London, 458pp.
SAPOZHNlKOV, D.G. (1963) The Karadzhal Iron­
Manganese Deposits. Transactions, Institute of the
Geology of Ore Deposits, Petrography, Mineralogy and
Geochemistry, No. 89, USSR Academy of Sciences,
Moscow, Chap. 3, No. 89, translation of Russian, 193pp.
SAYLES, F.L., Ku, T.-L. & BowKER, P.C. (1975) Chemistry
of ferromanganoan sediment of the Baur Deep. Ceo/.
Soc. Am. Bull. 86, 1423-1431.
ZANTOP, H. (1978) Geologic setting and genesis of iron
oxides and manganese oxides in the San Francisco
manganese deposit, Jalisco, Mexico. Econ. Ceo/. 73,
1137-1149.
ZANTOP, H. (1981) Trace elements in volcanogenic
manganese oxides and iron oxides: the San Francisco
manganese deposit, Jalisco, Mexico. Econ. Ceo/. 76,
545-555.
Spec. Pubis int. Ass. Sediment. (1990) 11, 39-50

Manganese deposits of the

Proterozoic Datangpo Formation, South China:
genesis and palaeogeography

X . X U, H . H UA N G and B. L I U
Chengdu Institute of Geology and Mineral Resources, Renmin bei lu, Chengdu, Sichuan, China

ABSTRACT

The early Sinian (late Proterozoic) black manganese carbonate deposits of the Datangpo Formation are
distributed in eastern Guizhou and western Hunan provinces. The formation comprises a belt extending
for over 600 km along depositional strike and 150 km perpendicular to strike. The manganese deposits
are located in a rift belt on the margin of the Yangtze Craton.
The Datangpo Formation is interbedded between two sequences that have been interpreted as
glacial diamictites. The formation comprises manganese ore and manganese-rich shale which show fine,
graded laminae, with ABC and ABE Bouma sequences. The manganese-rich shale contains algae, fungi
and acritarchs as well as radiolaria which are reported for the first time. These features suggest that the
manganese deposits were deposited in relatively deep water which could have resulted from deglaciation
and an associated sea-level rise.
The manganese ore bodies include lens and pillow-shaped structures with a concentric internal
fabric, and are cut by fine barite and quartz veinlets.
It is suggested that the manganese originated from hydrothermal exhalation at the seafloor. It was
precipitated as successive concentric layers around a nucleus, building up a pillow-shaped body. It is
suggested that the glacial melting at the beginning of Datangpo Formation times brought about a major
sea-level rise and the resulting transgression established a relatively deep marine environment. Hydro­
thermal exhalation at the sea bottom could have resulted in a stratification of the water column with an
anoxic bottom layer in which the syngenetic manganese deposits were precipitated.

INTRODUCTION

The early Sinian (late Proterozoic) saw an important
phase of manganese mineralization in central South
China, on the southeastern margin of the Yangtze
Craton (Fig. 1). Strata-bound sedimentary manga­
nese deposits hosted by organic-rich black shales
occur in the Datangpo Formation (Lower Sinian) in
eastern Guizhou and western Hunan provinces.
These are typified by economically valuable deposits
at Datangpo and Minle.
The Datangpo Formation crops out over a wide
area, forming a narrow belt that extends over
600 km along depositional strike and about 150 km
perpendicular to strike. Possible correlatives may
occur farther to the east. The Lower Sinian strata
are characterized by rapid thickness and facies vari-
ations. Sedimentation occurred in extensional rift
basins.
This paper describes the sedimentary attributes of
the Datangpo Formation and its manganese miner­
alization, and discusses the palaeogeographic and
palaeoenvironmental context. An origin for the
manganese mineralization is suggested.
GEOLOGICAL SETTING
Tectonic framework
The Yangtze Craton is a major structural unit in
South China. Continental nucleation was initiated

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun 39

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
40 X. Xu, H. Huang and B. Liu

Xianganzhe Fault

Lishui Haifen Fault

Qinling Fault

Tanlu Fault

Q Manganese ore deposits

� Datangpo Formation areas

100 200 300 km .£. Continental tillite

6 Glaciomarine tillite

Fig. I. Lithofacies palaeogeographic map for early Sinjan times, South China.

during the late Archaean to middle Proterozoic.
Further episodes of continental accretion during the
Sibaoan and Jinningian orogenies saw final consoli­
dation of the cratonic block (Huang et al. , 1980).
Stratigraphy
The pre-Sinian basement comprises lightly meta­
morphosed sedimentary rocks which suffered defor­
mation during the later orogenic activity. The
southeastern margin of the block is the Guizhou­
Hunan (or Yangtze) fold belt which brings it
in contact with the South China block. The late
Proterozoic to early Cambrian was dominated by
intracontinental extensional tectonics, possibly in­
volving two phases of rifting. Extension produced
trough-like grabens along the marginal belt. Sub­
sequent continental break-up, possibly in the latest
Sinian or earliest Cambrian, initiated a passive
Atlantic-type margin.
In the eastern Guizhou and western Hunan region,
the Lower Sinian succession is subdivided into four
formations, from bottom to top the Liangjiehe For­
mation, Tiesiao Formation, Datangpo Formation
and Nantuo Formation (Guizhou Bureau of Geology
and Mineral Resources, 1987) (Fig. 2). All are
believed to be products of marine sedimentation.
The basal Sinian (the Liangjiehe Formation) rests
unconformably on middle Proterozoic metasedi­
mentary rocks of the Banxi Group. It comprises
 2 3 4 5 6 7 8
Kaiyang Wengan Datangpo Yanglizhang Minle Tongren Chongjiang Sanjiang
�SE

51 I.-;..
Datangpo Fm.
Fulu Fm.

2;;:
Fm.
�t:l
;::
f;;
"'
1------jLiangjiehe Fm.l Changan Fm. "'""
"'
�
()
"'

��·
t:J
t:l
Danzhou group IS"

�()
� sandstone with
�gravel
�sandstone( cross Ej massive sandstone \ --:-�� shale and siltstone �
�
�bedding)
Wunan
�
liiiiiiiJ siliceous rock 3o ·
��........ I ti
1: IIite � black shale � manganese ore �·
;::
0
E} tuff Cl fe\dspathic quartz B siliceous slate
tt3645
Changsha
�manganiferous
L_____:::J sandstone C1LJ dolomite
0 I 2 8
� graded bedding r=l pillow-shaped
'-=J structures I� I
slump structures [llJ rock
Mn-S iliceous Guiyang
7 110"

Fig. 2. Stratigraphic and facies correlation of early Sinian successions.

-!'>
42 X. Xu, H. Huang and B. Liu
conglomerates and sandstones and ranges from
tens of metres to 300 m in thickness. A nearshore
shallow-marine environment of deposition is
suggested. The conformably overlying Tiesiao For­
mation consists of a matrix-supported grey pebbly
coarse sandstone. Pebble types include quartzite,
siliceous rock and granite. Laminites with dropstones
occur locally. A glaciomarine origin has been pro­
posed for the unit (Guizhou Bureau of Geology and
Mineral Resources, 1987). Above the Tiesiao For­
mation is the Datangpo Formation itself. This is
described in greater detail below.
The upper part of the Lower Sinian is the tillite of
the Nantuo Formation. This has a widespread distri­
bution in South China, such that its base is an
important regional marker.
The Datangpo Formation
At the type section in Datangpo, eastern Guizhou,
the Datangpo Formation may be subdivided into
two members. Black carbonaceous shale of the lower
Fig. 3. Radiolaria in manganese-rich black shale,
Datangpo Formation, Datangpo, Guizhou.
member (Fig. 2) contains interbedded manganese
(rhodochrosite) layers and thin tuffaceous beds.
Coarse terrigenous clastic grains are rare. The
upper member mainly comprises mudstones and
siltstones.
The black shales of the lower member are lami­
nated, as are the intercalated manganese ore beds.
The principal ore-bearing unit includes lenticular
ore bodies enclosed in black shale. The member is
characterized by a great abundance of organic matter
made up of marine eukaryotic planktonic algae, i.e.
Huroniospora Barghoorn, Globophycus Schopf,
Trachysphaeriaium Tim, Nanococcus Oehler and
Eosynechococcus Hofman which lived in deep water
below the photic zone (Wang, 1988). Micrometre­
scale siliceous spheroidal biogenic structures are also
found; under the scanning electron microscope they
have a sieve-like surface texture (Fig. 3), with well­
developed spines. These features are similar to fea­
tures shown by modern radiolaria from Holocene
Pacific Ocean sediments. These spheroids may pos­
sibly represent early radiolaria, although this would
be the first report to our knowledge of radiolaria
from Upper Proterozoic strata.
Light-yellow silty mudstones and intercalated silt­
stones of the upper member are of terrigenous
origin (Wang & Wang, 1985). They exhibit hor­
izontal lamination and local slump structures.
Regional correlation
The Lower Sinian succession shows sharp lateral
variation in both thickness and facies (Fig. 2). To
the west at Kaiyang (Section 1), the Maluping For­
mation, probably equivalent to the four members of
the Lower Sinian marine strata from eastern Guizhoti
to western Hunan (Guizhou Bureau of Geology and
Mineral Resources, 1987), consists of purple-red
siltstone and mudstone which are interpreted as
fluviolacustrine deposits. At Wengan (Section 2),
the equivalent strata are quartz arenites, with subor­
dinate feldspar and glauconite, and the strata be­
neath the Nanto Formation are only 13 m thick.
The manganese-bearing succession of the
Datangpo Formation thins from west to east. The
facies change successively through manganese sil­
iceous shale, manganese-rich dolomite and black
siliceous shale (Figs 2 and 4). The upper member
passes from mudstone and silty shale to dark siliceous
shale.
In southeastern Guizhou and western Guangxi
(Sections 7 and 8), equivalent Lower Sinian strata
 Manganese deposits, Datangpo Formation 43

transport Chongj iang

Glacial Sediment transport

Continental tillite
""'�0�
Glaciomarine tillite

Fig. 4. Lithofacies

�
Submarine erosional area

palaeogeographic map of early ,...... Synsedimentary faults

,..,....
---
Sinian (early Datangpo age) of
__,..'1...... lsopachs ( m)
�Okm
eastern Guizhou and western
Hunan.

are assigned to the Changan and Fulu Formations
which are 2000-3000 m in thickness (Guangxi Bu­
reau of Geology and Mineral Resources, 1985). The
Datangpo Formation equivalent here is a thin bed of
manganese-rich siliceous shales.
Palaeogeography
Facies belts run parallel to the Yangtze Craton
margin (Fig. 4). The palaeocoastline, which is now
aligned northeast-southwest, is defined by a narrow
belt of quartz sandstone of littoral facies seen at
Wengan (Fig. 2, Section 2). To the west was the
Yangtze Palaeoland with a fringing fluviolacustrine
plain. Lithological features of the Datangpo Forma­
tion suggest that directly east of the palaeocoastline,
manganese-bearing black shales accumulated in a
relatively deep water, graben-like restricted basin.
Lateral facies and thickness variations suggest an
irregular seafloor topography, possibly arising from
syndepositional faulting. Faulting is also indicated
by the occurrence of slumped beds. East of the
Tongren fault, shallow-water facies prevail, indi­
cating a local submarine high. Farther eastwards,
the palaeogeographic relationships are not entirely
clear, although the very thick Lower Sinian suc­
cession probably indicates a separate, much deeper
rift sub-basin.
ORE MINERALIZATION
Manganese carbonates, mainly rhodochrosite and
calcirhodochrosite, dominate the ore mineralogy.
Based on the form and sedimentary features of the
ore, two main facies types are recognized in the
manganese-bearing succession: ( 1) lenticular or
pillow-shaped ore bodies; and (2) laminated ore
facies.
44 X. Xu, H. Huang and B. Liu

1 Lenticular-ore facies Surrounding this is the laminated ore facies which

shows a decrease in manganese ore content towards
The lenticular ore body facies is restricted to the
the margins.
lower part of the Datangpo Formation and contains
The pillow-shaped or lenticular ore bodies are
up to 25 wt% manganese (Fig. 5). This is the
entirely enclosed within black shale; they range from
principal economic ore facies.
1 to 20 m in length and from 0 ·2 to 3 m in thickness.
The lateral distribution of the manganese ore
The manganese ore includes 23 such bodies in a 65
facies displays a bull's eye pattern at Datangpo (Fig.
m wide field in Datangpo, Guizhou (Fig. 7). These
6). The high-grade pillow-shaped ore body facies
elliptical bodies may show convolute lamination and
occurs in central parts of the Datangpo ore body.
slump structures at their margins where they pass

Thick- Mn Content %
nes� (m)
Strata Column Lithology
0 10 20

"'
·--·
Siltstone
" -· --
..,
E
"

u 1.0
l
Black Carbonaceous shale

. 34
II Mn
� > Manganiferous dolomite

. 44
c( Black shale

Laminated manganese ore

.. .. Graded bedding
1.0 --- ... J -
--

c/
> Black carbonaceous shale

¢
c
0
·.;::;
El
�
2.4
0
u..
�

0 "
€);
" E
..0

" .11 Laminated manganese

� 2!
0 interbedded tuff
s
/
. 9b / ' / ' /
I/ .... I '

2
Pillow shaped
. 59
(-) manganese ore

. 74
- - . -
- - - - .
<p Graded bedding
. 53 Lamina ted manganese

� Fig. 5. Stratigraphic column

. 39 c( Black shale
T iesiao Fm. - showing manganese ore
Sandstone
,. . ... . bearing succession, Datangpo,
Guizhou.
 Manganese deposits, Datangpo Formation
250 500m
Fig. 6. Map showing relationship between the thickness of
manganese ore deposits and grade of ore. (From Wang,
1985. )
into black shales. Internally, the pillow-shaped
bodies appear to be made of nodular structures
showing concentric layering (Fig. 8). Each layer is
10 mm or less in thickness, and is cut by fine veinlets
of fibrous or granular barite and quartz. The veinlets
are generally less than 2 mm in width. They tend to
be concentrated in individual layers and usually
terminate at layer boundaries. The veinlets show a
wedge-like morphology, tapering toward the in­
terior. They seldom cut across several sets of layers.
Veinlets also occur along the boundary between
adjacent layers.
It is suggested that following the formation of a
single manganese-rich layer, shrinkage fissures were
formed in which the veinlet minerals were precipi-
!Om
Fig. 7. Sketch section showing
features of manganese ore bodies,
Datangpo, Guizhou (by Wang,
1985).
45
tated. Subsequently, this layer with fine cross-cutting
veinlets would have been enveloped by another
manganese-rich layer.
Rhodochrosite exhibits a micronodular colloidal
precipitation texture (Figs 9-11), with fibrous quartz
and granular barite filling fractures and pores. This
may be indicative of hydrothermal precipitation.
2 Laminated ore facies
Finely laminated manganese shales form the lower
grade ore of the Datangpo deposits. Graded laminae
also occur, individual laminae being less than 5 mm
in thickness (Fig. 12). ABE and ABC Bouma se­
quences are observed. The laminae consist of car­
bonaceous black shale, suspended sediments with
dark brown organic material, and manganese car­
bonate which shows a micropelleted fabric (Wang,
1988), and also contains algal microspheroids,
acritarchs (both replaced by rhodochrosite) and
possibly radiolaria (Fig. 13). Laminated ore facies,
averaging 15-20 wt% manganese, occurs at the
bottom and in the upper parts of the succession.
Discussion of palaeoenvironment
The manganese ore beds and their host black shales
are both highly enriched in organic matter. They
contain 2·68 and 2·02 wt% total organic carbon
(TOC), respectively (Wang & Wang, 1985). The
bitumen contains 6·78-20·78 wt% saturated hydro­
carbons and 2·54-8·66 wt% aromatic hydrocarbons
(Wang & Wang, 1985). These are probably derived
from the thermal breakdown of planktonic algae
and protists.
The o34S values for pyrite samples in the laminated
ore range from 42·9-57·3%o (Wang & Wang, 1985),
more than two times the value for present day
seawater sulphate. These values are very high for
sulphides generated by bacterial reduction of early
seawater sulphide, and may be the result of restricted
circulation in an anoxic environment. Hoefs (1987)
has pointed out that the H2S produced at a later
15 25 35 45 55 65m

Fig. 9. Rhodochrosite showing colloidal precipitation
texture in nodular manganese ore, Datangpo Formation,
Minle, Hunan.
Fig. 10. Fibrous quartz filling pore space within dark
rhodochrosite, Datangpo Formation, Minle, Hunan.
Fig. 8. Concentric layers with cross­
cutting veinlets of barite in nodular
manganese ore, Datangpo
Formation, Minle, Hunan.
Fig. 11. Granular barite filling pore space within dark
rhodochrosite, Datangpo Formation, Minle, Hunan.
stage exhibits heavier b34S values, and heavy sul­
phate may be found in the final stage of bacterial
activity in a closed-system environment. The pre­
cipitation and diagenesis of the manganese deposits
were both in a closed-system environment, and the
sulphur may have been supplied by hot brine at the
seafloor (Wang & Wang, 1985).
The organic-rich black shales appear to be related
to the development of an extensional basin, as indi­
cated by the sharp lateral thickness changes. Only
small amounts of terrigenous clastic material entered
the basin. The preservation of abundant organic
matter and high b34S values indicate a reducing
environment with anoxic conditions at the
sediment-water interface.
Numerous microfossils have been discovered 111
 Manganese deposits, Datangpo Formation
Fig. 12. Graded laminae in manganese-rich black shale,
Datangpo Formation, Datangpo, Guizhou.
the manganese ore by Wang (1988), who compares
the microfossils to the Precambrian Barney Creek
HYC Shale from the McArthur Basin and the
Urquhart Shale from Mount Isa, Queensland. These
microfossils indicate a reducing environment in the
deep water beneath the photic zone.
The finely laminated lithology, the occurrence of
grading, and the absence of coarse terrigenous clas­
tics and wave-formed structures suggest that the
Fig. 13. Graded laminae
comprising radiolaria (white),
rhodochrosite (dark), and
micropellets (grey), Datangpo
Formation, Datangpo, Guizhou.
47
Datangpo Formation was the product of deposition
in deep-water conditions below the storm wave base.
Abundant planktonic microorganisms presumably
accumulated from suspension. Low density turbidity
currents may account for the occurrence of graded
bedding.
The deeper-water facies of the Datangpo Forma­
tion occurs intercalated between two units of glacial
origin and shallow-water setting. Such a situation
could have resulted from a major phase of ice
melting and consequent sea-level rise. The resulting
transgression would have established relatively deep
water conditions over the basin.
Origin of manganese mineralization
The manganese mineralization of the Datangpo
Formation is in our opinion syndiagenetic and the
product of hydrothermal activity as opposed to a
supergene origin. Paucity of detailed geochemical
work precludes a conclusive answer.
Evidence for a hydrothermal origin is as follows:
1 The concentric layered nodular structures within
the pillow-shaped ore bodies indicate progressive
precipitation of manganese around a central nucleus.
Concentration of veinlets in individual layers sug­
gests cooling of the manganese-rich layers to create
tensional fractures and a break in precipitation.
2 The colloform texture of rhodochrosite suggests
colloidal precipitation from hydrothermal solutions.
Seven homogenization temperature measurements
 48 X. Xu, H. Huang and B. Liu
NW
melt waters
,
SW
Fig. 14. Model for manganese deposition in the Datangpo Formation.
from quartz fluid inclusions in the manganese ore
give an average fluid palaeotemperature of 194°C
(uncorrected), which is in accordance with a hydro­
thermal origin.
3 The high-grade pillow-shaped ore bodies occur in
the centre of the ore-bearing structure, and are
surrounded by lower-grade deposits which decrease
in manganese content toward the margins. This bull's
eye pattern may indicate the presence of an ancient
vent, possibly fault-related, in the central area.
4 The occurrence of intercalated tuff beds in the
manganese ore and host black shale succession indi­
cates contemporaneous mineralization.
The occurrence of black shales containing abun­
dant organic microfossil remains associated with the
manganese mineralization is striking. The role of
microorganisms in the deposition of manganese is as
yet uncertain. It could be that biogeochemical pre­
cipitation may have been a significant factor in the
concentration of manganese.
MODEL FOR MINERALIZATION
Early Sinian glaciers of pre-Datangpo Formation
times debouched into the sea from the northwest
glacial sediment transport
(Fig. 14). At the close of this episode of glaciation, a
major phase of ice melting would have brought
about a sea-level rise. The resulting transgression
would have established a relatively deep marine
environment in the basin.
Deglaciation may have caused stratification of the
seawater column, with a lower layer of normal
seawater and an upper freshwater layer derived
from ice melting. A consequence of sea-level rise
and stratification of the seawater column would have
been to restrict circulation in the basin which would
lead to oxygen-depleted or anoxic conditions being
established in bottom waters. As a result, preser­
vation of abundant organic matter would be possible.
Microorganisms may have played an important role
in manganese precipitation.
Extensional faulting would have allowed rapid
subsidence of the basin and development of variable
submarine topography. This would also have allowed
the development of a restric;ted circulation and
anoxic conditions. Submarine hot spring activity
related to hydrothermal exhalation vents was prob­
ably concentrated in the vicinity of such extensional
fractures. Deposition of high-grade manganese ore
occurred at these sites and lower-grade ores ac­
cumulated marginally to them. Minor manganese
 Manganese deposits, Datangpo Formation
precipitation may have occurred due to supergene
concentration.
ACKNOWLEDGEMENTS
Y. Wang and L. Wang are thanked for their support
and for supplying information. S. Gupta made use­
ful suggestions and corrected the English version of
the manuscript.
REFERENCES
GUANGXI BUREAU OF GEOLOGY AND MINERAL RESOURCES
(1985) Regional Geology of Guangxi Province. People's
Republic of China, Ministry of Geology and Mineral
49
Resources, Geological Memoirs, Series 1, No. 3. Geo­
logical Publishing House, Beijing (in Chinese).
GUIZHOU BUREAU OF GEOLOGY AND MINERAL RESOURCES
(1987) Regional Geology of Guizhou Province. People's
Republic of China, Ministry of Geology and Mineral
Resources, Geological Memoirs, Series 1, No. 7. Geo­
logical Publishing House, Beijing (in Chinese).
HOEFS, J. (1987) Stable Isotope Geochemistry. Springer,
Berlin.
HUANG, J., REN, J., JIANG, C. , ZHANG, Z. & QIN,
D. (1980) Geotectonics and Development of China,
pp. 35-37. Science Publishing House, Beijing (in
Chinese).
WANG, F. (1988) Precambrian Algal Fossils from South­
western China, and their Geological Significance,
pp. 229-231. Chongqing Publishing House (in Chinese).
WANG, Y. & WANG, L. (1985) The Stratigraphy, Sedimen­
tary Environment and Manganese-Forming Process of
the Datangpo Formation in Eastern Guizhou. People's
Publishing House of Guizhou, Guiyang (in Chinese).
Spec. Pubis int. Ass. Sediment. (1990) 11, 51-56

Manganese enrichment in a Triassic aulacogen graben

in the Lijiang Basin, Yunnan Province, China

H . LIU
Southwest Research Institute of Metallurgy and Geology, Erxianqiao, Chengdu, China

ABSTRACT

The Lijiang Basin developed during the Norian stage of the late Triassic on the western passive
continental margin of the Yangtze plate adjacent to the Tethys plate. A small aulacogen striking
approximately east-west developed in the southwest part of this basin east of the Jinshajiang fault and
the boundary of the plate near Jianchuan. The Runanshao fault forms a depression along the centre of
the aulacogen. Tholeiitic olivine basalt and volcaniclastic rock in the middle and lower part of the
Songgui Formation (Norian stage) are interbedded or intercalated in olistostromes of middle Triassic
limestone, which are characteristic of the early stage of development of the aulacogen. During this
stage, manganese ore bodies at the base of the volcanic rocks were formed by volcanic exhalation,
sedimentary and diagenetic processes.

INTRODUCTION

An axial trough basin striking northeast-southwest
in the Lijiang area of western Yunnan Province
developed on the basement rocks of the western
passive continental margin of the Yangtze plate
adjacent to the Tethys plate, from the early Permian
to the late Triassic. The high-grade Heqing man­
ganese deposit occurs in the southwest part of the
basin in the Lower Songgui Formation of Upper
Triassic age (Liu Hongjun, 1987).
BASIN ANALYSIS
Palaeotectonic background
The Kang-Dian axis located in the eastern part of
the region (Fig. 1) was uplifted to form a land mass
as early as pre-middle-Devonian and became the
main source of sediments in the Lijiang Basin. The
eastern border of the basin was controlled by the
Chenghnai fault on the western border of this old
land mass. Much ultrabasic and basic lava was
extruded along this fault during the Hercynian. The
Jianchuan fault situated on the eastern side of the
Shigu Rise controlled the western border of the
basin. Thick Triassic strata were deposited east of
the fault but very little Triassic strata occur to the
west.
Geophysical data indicate that the Xiaojinhe fault
is a deep structure and formed the boundary of a
passive continental margin during the Norian stage.
A eugeosyncline developed between the Jianchuan
and Xiaojinhe faults. Triassic strata in the active
tectonic unit of the Tethys plate were extensively
metamorphosed. Basement movement at the passive
continental margin located east of this fault involved
elevation and subsidence during the middle-late
Triassic. Permian basalt was extruded from the sea­
floor along the Lijiang fault through the centre of
the basin. The southwest end of the Lijiang fault
joins the Jinshajiang fault near Jianchuan.
A small aulacogen developed east of the junction
of the Lijiang and Jinshajiang faults near Jianchuan
in the Lijiang Basin and its depocentre strikes east­
west along the Runanshao fault (Fig. 1).
Lijiang Basin sediments
The main sediments of the Lijiang Basin belong to
the Songgui Formation of the Norian stage and are

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun 51

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
52
TETHYS 1oo· @ 101"
Ling rang
PLATE
FS
0 10
�
Fig. 1. Norian palaeotectonic map in Lijiang, western
Yunnan Province. PtlKn, Proterozoic Kunyang Group;
AnDsn, Shigu Group (pre-Devonian); Fl, Jinshajiang
fault; F2, Xiaojinhe fault; F3, Lijiang fault; F4, Chenghai
fault; F5, Junying fault; F6, Runanshao fault.
composed of five units. The lithological character­
istics of these beds are as follows:
1 thick black mudstone and pillow basalt at the base
of the aulacogen;
2 greyish-white sandstone;
3 black mudstone in the lowest part of the aulacogen
intercalated with basic and ultrabasic volcanic rock
and olistostromes;
4 greyish-white sandstone;
5 coal-bearing grey-black silt-mudstone.
Two shallowing-upward sequences can be iden.t­
ified which range from black mudstone, through
turbiditic sandstone to coal-bearing mudstones,
representing two transgressive- regressive cycles.
Units 1 and 2 make up the first cycle, and units 3, 4
and 5 the second.
Macroscopic features studied in the field and grain­
size analyses show that units 2 and 4 developed from
large scale turbidity currents. A variety of flute casts
occur at the base of the sandstone beds, and Bouma
sequences are developed in facies in the centre of
the basin.
It should be noted that in the aulacogen the
thickness of the lower sandstone unit 2 exceeds that
of neighbouring units by a factor of 3-5. The thickest
part, up to 480 m, is close to the contemporaneous
H. Liu
Runanshao fault. Pillow structures occur in the basalt
and slump, scour planes and graded bedding features
occur in the sandstone unit. This sequence of sedi­
ments becomes progressively finer grained upwards
27"
and is transitional to the coal-bearing shallowing­
upward beds of delta-front facies. The sandstone
facies are interpreted as a delta-front collapse
turbidite fan (Rupke, 1985).
Basic facies zoning and manganese geochemistry
An obvious lithofacies zoning exists from east to
west in the basin from near the old Kang-Dian land
area to the Tethys Sea, including foreshore to near­
shore, intershelf, extra shelf and basin-centre facies
(Fig. 2).
A submarine rise was located in the middle of the
20km shelf. A suite of pelitic sediments dominated by
black mudstone was deposited in the southern basin.
The pelitic seafloor sediments provided a favourable
environment for perfect preservation of the fossil
organisms. The predominant fossils are bivalves and
Ammonoidea. There is an abundance of terrigenous
clastic sediment in the open shelf environment in the
northern part of the basin. Bivalves and other fossils
are commonly found on the bedding surfaces of
calcareous siltstone or micritic limestone. Great
varieties of fossils and biodetritus were distributed
in a disorderly fashion nearshore and transported to
the submarine rise.
The geochemjstry of the sedimentary microfacies
is indicated by the content of trace elements and by
their petrography. The content of manganese in the
main rock types of the area is shown in Table 1. The
manganese content is relatively high in the siltstone
and decreases with the coarsening of the grain size
of the rocks, with the exception of the mudstones
and limestones. The content of manganese is lower
in the shallow-water zone than in the deeper-water
zone, and lower in other parts of the basin than
in the aulacogen. Manganese was concentrated in
banded sediments in the black mudstones of the
Table 1. Manganese contents in rock types of the Songgui
Formation, Lijiang
Sample (n) Average Mn (ppm)
Conglomerate 3 557
Sandstone 88 808
Siltstone 11 1650
Mudstone 41 998
Limestone 11 994
 Manganese enrichment, Lijiang Basin 53

E:23 1
C::::::l

m2 .

I® I s
Fig. 2. Lithofacies
palaeogeographic map of Lijiang, [i[)6
western Yunnan, early Songgui time
(Norian). CD @
proximal turbidite;
intermediate turbidite;(D distal
I® 17
turbidite; 1, sand-mud association;
2, mud-sand association; 3, sand­
I® Ia
lime association; 4, mud-lime­
siliceous association; 5, aulacogen
m9
sequence; 6, subaqueous
depression; 7, shallow-water shelf; Ivvvllo
8, confined shelf (deeper); 9,
direction of sediment transport; 10,
t-'"''-� II

basic volcanics; 11, isopach

(metres).

aulacogen graben during early stages of the devel­
opment of the fault trough. It appears that there was
a lower rate of deposition of manganese in the
deeper water and that the aulacogen provided a
favourable environment for manganese deposition.
Co: Ni, Sr: Ba and B: Ga ratios vary with the
changing abundance of manganese in the mudstone
(Fig. 3). Manganese abundance and Co: Ni ratios
(0·82) are highest in the aulacogen and decrease to
0·18, the lowest, towards the shelf and coast. The
Sr: Ba ratios trend in the same way as the Co : Ni
ratios. On the contrary, the average values of the
B: Ga ratios vary from 0·85 to 1·66 in the aulacogen
to 14·70, the highest, in the submarine rise zone.
Manganese, cobalt, strontium and gallium are rela­
tively concentrated in the aulacogen.
Basin evolution
The main tectonic activity in the passive continental
margin which forms the basement of the Lijiang
Basin was gradual elevation during the Norian stage.
Because movements of the Tethys plate affected
this area the crustal structure was somewhat un­
stable. Extension (pull-apart) of the crust along the
Xiaojinhe fault at different stages and the formation
of the Runanshao fault caused the seafloor to sink
considerably between two stages of uplift (Liu,
1985). Turbidite sediments were deposited twice
during the sinking and elevation of the seabed,
giving rise to two shallowing-upward sequences in
the Songgui Formation in the Lijiang Basin.
During the early Norian stage rapid extension
(pull-apart) of the crust along the Runanshao fault,
the fault depression of the aulacogen, controlled the
formation of the delta-front collapse turbidite fan.
This fault was also a vent for the submarine eruption
of basalt magma that came from the deep crust or
upper mantle. The olistostromes filling the centre of
the fault depression consist of middle Triassic lime­
stone from the rising wall of the aulacogen graben.
Deposition of black mudstone extended over the
whole aulacogen basin following the eruption of
submarine basalt.
The sea retreated from this area in late Norian
times and folding took place in the western part of
54 H. Liu

'<t
0 1 02 c

�3 t±lEJ4

I
I.
I .

I ·.
/.· .
.
. ....
""/:.�
/ ·
.:
. :·,
/' .
. ··
.

Fig. 3. Manganese concentration

data and geochemical ratios in
o a 16 Km

.
�-�-�
Songgui Formation, Lijiang,
...... ..
. .
.
.
Yunnan. 1, Mn <100 ppm; 2, Mn
500-750 ppm; 3, Mn 750-1000
c.section point
ppm; 4, Mn >1000 ppm; 5, Co : Ni
ratio; 6, Sr: Ba ratio; 7, B: Ga ratio.

the region. The southern part of the region became
a piedmont plain. The Runanshao fault converted
from an extensional (pull-apart) to a compressional
structure. The primary aulacogen was covered by a
nappe outlier which is several kilometres wide and
about 15 km long, and composed of the middle
Triassic Baiya Formation.
MANGANESE MINERALIZATION
Ore-bearing formations
Manganese ore bodies occur only at the base of the
succession of basic volcanic and siliceous carbonate
rocks in the aulacogen. The olistolith shows dis­
orderly deposition with slump folding and irregularly
shaped blocks. Some of the olistolith blocks occur
within the ore bodies (Fig. 4). Black mudstones at
the base of the ore bodies formed in deep water with
low rates of deposition. Their manganese content is
relatively high but not high enough to form com­
mercial ore bodies.
The shapes of ore bodies in this area differ from
those in typical marine sedimentary manganese
deposits. The thickness of known ore bodies varies
greatly and their length is five to eight times greater
than their width. Their form is often concealed as
shown by the No. 1 ore body in Xiaotianjin where
the length of the outcrop is less than 100 m but it
extends westward (along strike) for about 800 m.
The prospective value of many ore bodies is greatly
enhanced when their extension along strike is
recognized.
Ore texture and composition
There are differences between the manganese ore
bodies at the base of the succession of volcanic rock
 Mallgal!ese enrichme11t, Lijia11g 8asi11
Fig. 4. Geologic section, line 45,
Hoqing manganese deposit. 1,
feldspathic quartz sandstone; 2,
limestone olistolith; 3, mudstone; 4,
olivine basalt; 5, pyroclastic rock; 6,
manganese ore body.
and those in the siliceous carbonate formation.
Oxidized manganese and iron-manganese charac­
terizes the former type but the latter type consists
mainly of manganese carbonate. The secondary ore
consists of oxide and mixed oxide and carbonate
minerals. The central parts of the ore bodies consist
of manganese carbonate which is surrounded by
manganese oxide that extends into the surrounding
rocks.
The principal ore minerals are pyrolusite,
psilomelane and rhodochrosite. Secondary minerals
are manganite and braunite, magnetite and other
minerals. Ore textures are allotriomorphic to
hypidiomorphic granular and microscopic granular.
Structures of the manganese carbonate ore include
sub-blocky to blocky, perthitic, striped and colloidal
forms. Structures in the manganese oxide ore are
mainly sub-blocky, brecciated and concentric col­
loidal forms.
The trace element content is similar in the two
types of ore. The zinc content is evidently related to
the content of manganese (average zinc in ore
3000-10 000 ppm). The content of cobalt, boron,
molybdenum and copper in the ore is three to tens
of times higher than that in the wall rocks at the top
and bottom of the section. The content of cobalt in
the ore at the base of the volcanic pile is up to 100-
150 ppm, and the Co: Ni ratio is as high as 3·39. The
high ratio of B: Ga (average 42·58) is characteristic
of the ore at the base of the siliceous carbonate rock.
No alteration has been found in the upper and
lower wall rocks and no minerals bearing zinc,
55
jt,r r I 4
§2�5
c--::-:13 � s
o sam
lead, molybdenum, etc. have been found although
fluid inclusion thermometry studies of individual ore
samples show temperatures of up to 20SOC.
Assessment of metallogenetic factors
The main controlling factors in the Heqing deposits
are the processes of formation and their palaeo­
geographic context. Some of the ore bodies are
overlain by volcanic rock that was extruded during
the development of the graben. Other ore bodies
are associated with siliceous carbonate rocks that
were produced by the volcanic eruptions. There is
no doubt that somehow volcanism was a part of the
metallogenetic process, which is also indicated by
the composition of the ore given above. However,
the position of the known manganese ore bodies in
this area is lower in the stratigraphic succession than
the volcanic rocks, suggesting that the formation of
the manganese ore ended during the eruption of the
magma. This implies that the metals (manganese,
iron) were carried directly from depth through the
vent. They were then involved in new geological
processes of sedimentation and diagenesis on the
seafloor. It is reported that submarine volcanoes
erupting iron and manganese have been identified in
the region of the Galapagos rift zone (Lisitsyn,
1985), which would support this model.
The deep-water pelitic environment that existed
in the centre of the fault depression would have
been favourable for the concentration and deposition
of manganese. The amount of terrigenous clastic
56
Runansao
Fault
turbiditic sandstone
.r 3 s�2
material entering this basin centre as a diluent of
the manganese minerals was small.
Metallogenetic model
Volcanic exhalations brought the metallic elements
for the ore into the water during the graben stage of
aulacogen development. The metals were deposited
in the low-lying parts or in depressions on the
seafloor. Much middle Triassic limestone was
deposited in the low-lying areas of the seafloor as
olistoliths after the deposition of manganese (Fig.
5). The topography of the low-lying seabed or
depressions controlled the shape of the ore lenses or
facies, and the shapes of the depressions were con­
trolled by the Runanshao fault with an east-west
strike (or axial) direction.
The relatively high oxygen fugacity near the
vent was favourable for the formation of oxidized
manganese and iron- manganese ores. The zinc did
not form as a sulphide mineral, which suggests that
the environment was free of sulphur. Reducing
environments in the topographic depressions far
away from the vents and the alkalinity of the sea­
water in which the siliceous carbonate rocks formed
were favourable for the formation of the manganese
H. Liu
sea level
Fig. 5. Schematic diagram showing
manganese entering basin along
extensional fault through seafloor,
and deposition of manganese ore
body.
carbonate ore. The lava did not extend to the de­
pressions distant from the vents and high-grade
manganese ore was formed entirely during the
diagenetic stage. The tenor of the ore far away from
the volcanic vents is 10-15% higher than that near
the volcanic vents.
ACKNOWLEDGEMENTS
I am grateful to G. Gross for criticism and correction
of an earlier version of the manuscript, and to E.
Mulqueeny for redrawing some of the figures.
REFERENCES
LISITSYN, A. P. (1985) Geochemistry of manganese in the
oceans. Int. Ceo!. Rev. 27, 979-983.
LIU, H. (1987) The Heqing manganese deposit, West
Yunnan: Its sedimentary-diagenetic environment and
metallogenic model. Geology and Prospecting 23, 1-7.
L1u, Z. (1985) Plate Tectonics, pp. 106-113. Sichuan
Scientific and Technical Pub!. Soc., Chongying, China.
RuPKE, N.A. (1985) Abyssal clastic seas. In: Sedimentary
Environments and Facies, Vol. 467 (Eel. by H.G.
Reading; Trans. Chinese by Zhou Minjian), pp.
502-517. Scientific Pubis Soc., Beijing, China.
Spec. Pubis int. Ass. Sediment. (1990) 11, 57-72

Processes of formation of iron-manganese oxyhydroxides

in the Atlantis-11 and Thetis Deeps of the Red Sea

G . Y U. B UT UZ O VA*, V. A. D R IT S *, A. A . M O R O Z O V '
and A . I. G O R S C H K O V r
*Geological Institute of the USSR Academy of Science, 7 Pyzhevsky per., 109017 Moscow, USSR; 'Institute of
Oceanography of the USSR Academy of Science, 23 Krasikova Street, 117218 Moscow, USSR; and *Institute of
Ore Geology and Mineralogy of the.USSR Academy of Science, 35 Staromonetny per., 109017 Moscow,
USSR

ABSTRACT

A complex of iron-manganese oxyhydroxide mineral phases is recognized in ore deposits of the

Atlantis-II and Thetis Deeps in the Red Sea. In the ore material of the Atlantis-II Deep goethite and
hematite predominate among the ferruginous phases; the manganese phases are mainly represented by
todorokite and manganite. In the Thetis Deep the iron ore material contains a predominant magnetite­
lepidocrocite association, and the manganese component is mainly represented by asbolanes. The bulk
of the iron - manganese oxyhydroxides in the ore material of the Red Sea is formed by oxidation of Fe 2+
and Mn 2+ supplied to near bottom water by hot brines. The processes of transformation of amorphous
hydrated particles into individual crystalline phases depend on physico-chemical conditions in the
mineral-forming medium, i.e. on the relative concentrations of manganese, iron and oxygen, and pH
value, as well as on the catalytic and adsorption activity of the amorphous hydrated particles. Stratified
brines in the Atlantis-II Deep determine different physico-chemical conditions. The process of forma­
tion of todorokite mainly takes place in the u pper part of the brines, where in an alkaline environment
with high oxygen content hydrated thixotropic macrostructures of nMn02·mH20 are formed. These
particles can adsorb cations, leading to the formation of minerals with losse tunnel structures.
Favourable conditions for manganite formation are found in the lower part of the brines with oxygen
deficiency, large amounts of manganese and low pH. Under these conditions the amorphous manganese
hydroxides are less hydrated and contain no adsorbed cations besides manganese. The bulk of goethite
and hematite is also formed in the lower part of the brines or in the sediments during diagenesis.
Ferrihydrite, present in the u pper parts of the sediment section, is formed through microbiological
processes in the layer of the b'rines transitional to seawater. In the Thetis Deep there is no bottom water
stratification. In the bottom water there, the manganese content is considerably lower than that in the
brines in the Atlantis-II Deep. Under such conditions, the Mn0 2 gel coagulates slowly and this leads to
the formation of asbolanes with layer structures. The main factor affecting the magnetite and
lepidocrocite formation is the kinetics of crystallization of the amorphous phase which in turn depends
on the iron : oxygen ratio. Due to an active supply of hydrothermal iron magnetite is formed, while
lepidocrocite crystallizes when the hydrothermal activity diminishes.

INTRODUCTION

The geothermal system of the Red Sea rift zone is
an object of intensive interest for researchers from
many countries through the prospect of industrial
exploitation and mining of ore deposits in that area.
Besides the economic value, this area is extreme­
ly important scientifically as a unique natural lab··
oratory for the study of the mechanisms of different
phases of ore formation.
A large part of the ores in the Red Sea basin is
composed of iron-manganese oxyhydroxides. The
physico-chemical conditions of the medium control
their mineralogy, structural and crystallochemical

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun 57

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
58 G. Yu. But uzova et a/.
characteristics, paragenetic assoCiatiOns and re­
ciprocal transformations. In this light the iron­
manganese oxyhydroxides may be regarded as im­
portant environmental indicators.
Although the Red Sea sediments are well studied,
the mineralogy of iron-manganese oxyhydroxides
is usually described in general terms, and the con­
ditions of formation of iron-manganese ore accu­
mulations and the mineral phases composing them
are almost unknown (Bischoff, 19 69; Backer &
Richter, 1973; Bignell et a/. , 197 6). An extremely
high dispersion of ore material, the low structural
regularity of minerals and the polycomponent
character of samples are all serious obstacles to the
study of fine crystallochemical peculiarities of the
different phases and their diagnosis. The traditional
X-ray diffraction methods are almost ineffective if
applied to such objects.
The present paper gives results of detailed studies
of iron-manganese oxyhydroxides in the ore
material of sediments in two rift zone basins of the
Red Sea, the Atlantis-II and Thetis Deeps. The
major purpose of the study is an accurate diagnosis
of mineral phases and the deciphering of the major
mineral-forming mechanisms. Besides the traditional
chemical, X-ray diffraction and CAMEBAX-micro­
probe analyses, we also applied methods of scanning
and transmission electron microscopy which in­
cluded micro-diffraction of electrons and local
energy dispersive analysis of individual micro­
particles. The research was prompted primarily by
the high ore-bearing capacity of sediments in these
basins and by essential differences in the morphology
between the basins. These differences justify the
description of each basin separately.
THE ATLANTIS-II DEEP
Sample descriptions and mineral compositions
The study of the mineral composition of iron­
manganese oxyhydroxides was carried out on the
basis of data from two typical sections. One of them
is site 1905 (4) with coordinates 21°22·8'N , 38°05·3'W
and thickness 5750 mm; the other is site 1905(5)
with coordinates 21°20·5'N, 38°06·1'W and thickness
5800 mm.
Backer & Richter (1973) distinguish five zones in
the section (from bottom upwards): detrital oxide­
pyritic (DOP), lower sulphide (SUt ) , central oxide
(CO), upper sulphide (SU2) and the amorphous-
silicate (AM) zone. Twenty samples were selected
for detailed mineralogical analysis from the different
lithological-facial zones, except the lowest DOP
zone which was not reached by our cores.
In this section of the Atlantis-II Deep the major
ore element in weight proportion is iron whose
content in individual interlayers reaches 60% and on
average is about 33%. The colour of iron ore inter­
layers and sequences is red-yellow, russet-ochre
and sealing-wax red; the Ept values in them are in
the range +170 to +250 mY. The manganese con­
centration varies from 0·1 to 2·7 %, while four­
valent manganese compounds are entirely absent.
The element is partly present as manganosiderites
irregularly dispersed throughout the sedimentary
layer.
The manganese-rich ore interlayers are dis­
tributed locally in the Atlantis-11 Deep, occupying a
distinct position both in vertical section and in hori­
zontal distribution. In the sedimentary column they
are found in the CO zone; on the area of the seafloor
they are confined to the relatively high parts and
the sides of the basin. In the studied sections the
manganese-rich interlayers occur in the intervals
3350-3500 mm at site 1905(5) and 4830-5000 mm
at site 1905(4).
The thickness of the manganese ore interlayers,
according to our data and information in the litera­
ture, is 150-400 mm (Bischoff, 1969; Butuzova,
1984a) and the content of manganese is 30-45%
and that of iron is 6-11%. The interlayers are
clearly identified in the section by their almost
black to dark red-brown colour, their typical 'oily'
consistency and sharp boundaries with the sur­
rounding muds. The sediments have high maximum
oxidation-reduction potential values for the ore
oozes of the Red Sea (Ept = +500 to +600 mY).
Iron oxyhydroxides
The ferrous phases of the ore material are, on the
whole, weakly crystallized with a large amount of
amorphous matter. Among the crystalline phases
goethite (cx- FeOOH) and hematite (Fe203) pre­
dominate in iron ore horizons, small quantities of
ferrihydrite (5Fe203 ·9H20) are present in the upper
parts of the section. In the manganese ore inter­
layers the major iron minerals are lepidocrocite (y­
FeOOH) and ferrihydrite.
1 Goethite forms platey microcrystals elongated
along the 'b' axis (Fig. 1a), or aggregates of finely
dispersed particles with 30-50 A diameter (Fig. lb).
 Iron-manganese oxyhydroxides, the Red Sea 59

Fig. 1. Morphology of goethite and hematite particles (Atlantis-11 Deep) . (a) Elongate platey crystals of goethite; (b)
aggregate of finely d ispersed goethite particles; (c) aggregate of finely flaked hematite; (d) monocrystal of hematite. Scale
bars (a)-(c) 0·5 >UTI, (d) 4 !J.ITI.

The structural order of the mineral increases with
greater depth.
2 Hematite is also present in two morphologically
different forms, i.e. as dense finely flaked aggregates
with goethite crystals (Fig. lc) and as flat 0·02-0·04
mm hexahedrons 2-4 f.tm thick (Fig. ld). We have
also found hematite in the sediments in the south­
western part of the Atlantis-II Deep in the immediate
vicinity of hydrothermal vents where hematite forms
lens-like patches and clearly delineated interlayers.
3 Ferrihydrite in iron-manganese ore deposits
occurs as mineral aggregates with bacterial form
(Fig. 2a).
4 Lepidocrocite occurs as elongated plates of less
than 1 �lm size, which develop from a spherical
jelly-like matrix (Fig. 2b). Individual samples of
60 G. Yu. But uzova et a/.
lepidocrocite, like ferrihydrite, have bacterial forms
of aggregates of mineral particles (Fig. 2c). This
lepidocrocite variety has a lower structural ordering
and is normally found together with ferrihydrite.
Manganese and iron-manganese oxyhydrox ides
Three major components are distinguished in the
manganese-rich interlayers: the basic finely
dispersed mass, solid kidney-shaped micronodules
and various concretions of complicated morpho­
logical type. The three components differ not only in
texture and morphology, but their mineral compo­
sition is essentially different; they also have differ­
ently crystallized minerals and some geochemical
peculiarities.
Fig. 2. Morphology of particles and microdiffraction
pattern of ferrihydrite and lepidocrocite (Atlantis-I I
Deep). (a) Aggregate o f particles o f bacterial ferrihydrite;
(b) globular aggregates of spicular crystals of lepidocrocite;
(c) aggregate of particles of bacterial lepidocrocite. Each
scale bar 0·5 �-tm.
1 The major mass of ore material is composed of
2-6 �m globules shaped like rosette lepispheres
with characteristic elongate crystals up to 2-4 �m
long at the edges (Figs 3a, b). Electron micrographs
show platey crystals sometimes forming twinned
crystals (Fig. 3c). The mineralogy of the major mass
is represented mainly by todorokite whose presence
is characterized on diffractograms by reflections with
d spacings of 9·58, 4·78, 2 4 0 and 2·20 A. We
· ,
emphasize here that the same set of reflections
characterizes at least four other mineral varieties of
manganese hydroxides which are structurally dif­
ferent from todorokite (Chukhrov et a/., 1987).
Therefore a reliable diagnosis of todorokite was
carried out by combining the X-ray and micro­
diffraction methods. The analysis of electron diffrac-
 Iron-manganese oxyhydroxides, the Red Sea 61

.. ...
I I

t
'

j
'
1 I

Fig. 3. Electron micrographs and electron diffraction

I I
pattern of todorokite from the major mass of manganese
' ' ore horizon (Atlantis- II Deep, site 1905(5), horizon 4830-
I 5000 mm). (a), {b) Globular todorokite particle; (c) triple
' '
cluster of todorokite; {d) electron diffraction pattern of the
..
triple cluster of todorokite with a = 9·75 A; (e) electron
8 diffraction pattern of todorokite with a = 24-4 A. Scale
bars (a) 10 f.lm, {b) 2 f.tm, (c) 0·5 [lm .
62 G. Yu. But uzova et a/.
tion patterns, obtained from the studied samples,
has shown that manganese ore horizons contain
three todorokite modifications with parameter a of
9·75 (Fig. 3d), 19·5 and 24·4 A (Fig. 3e). This is
associated with the different size of channels in the
tunnel structure of microcrystals of minerals. The
most common is todorokite with parameter a of
9 ·75 A.
Short columnar microcrystals 0 ·1-0·15 �lm in
size were revealed in the mass in association with
todorokite. Their electron diffraction patterns cor­
respond to the characteristics of goethite (cx­
FeOOH) and groutite (cx-MnOOH) which are
isostructural. The particles contain comparable
amounts of manganese and iron. These data seemed
to indicate the presence of isomorphic substitutions
of Mn3+ and Fe3+ in the structure of the compounds
or the growth of goethite and groutite at the sub­
microscopic level. H owever, a subsequent detailed
X-ray absorption spectroscopic study has shown that
this phase consists of Fe3+ and Mn4+ domains co­
existing within a uniform hexagonal packing. The
cation distribution in Fe3+ domains is similar to that
in goethite, while the Mn4+ cations in manganese
domains are distributed layerwise as in phyllo­
manganates. This phase is to be called manganese
goethite (Manceau et a!., 19 9 0).
Individual samples of the basic mass of ore ma­
terial, besides todorokite and manganese goethite,
have traces of buserite-II, a laminated 10 A man­
ganese oxide, the Mn4+ octahedron layers of which
have chains of vacant octahedrons: below and above
these octahedrons are located Mn3 + , Mn2+ , Ca2+
and other cations coordinated by H 20 molecules
(Chukhrov et a/., 1984).
A study of 10 samples by microprobe revealed
considerable chemical inhomogeneity of the finely
dispersed material. The manganese content varies
from 55 to 93%, with an irregularly distributed
admixture of iron (0·14-11·6% ), silicon (0 ·3-
6% ), calcium (0·3-1·7%) and magnesium
( 1-1·16% ). Among trace elements the most com­
mon are zinc (0·02-1·5%) and lead (0·05 -0·5% ).
The silicon, magnesium, calcium and some iron in
the major ore mass are probably associated with
insignificant and irregularly distributed admixtures
of the host sediment, with small amounts of au­
thigenic smectites and the presence of cations in the
adsorbed complex of manganese hydroxides. An
essential admixture of iron is found in manganese
goethite, lepidocrocite and ferrihydrite.
2 Kidney-shaped microconcretions are black and
shiny, 0 ·2-0·5 mm in size, seldom up to 1 mm. They
are quite varied morphologically, occurring in
rounded, oval, and dumb-bell forms, commonly
with pancake 'growths' attached to the principal
surface (Fig. 4a). The inner parts of microcon­
cretions are composed of randomly oriented crystals
(2-5 �lm) of elongate platey shape (Fig. 4b). The
microconcretions are composed of well-crystallized
manganite. No other cations other than manganese
are present in the manganite particles.
3 Morphologically complex concretions and crusts
are normally dark-grey, dull, friable and slaggy.
Their size does not exceed 1 mm, the shape is
extremely variable (branched, dendritic, angular:
Fig. 4c), and their surface is rough and bumpy.
Their mineral and chemical composition is inter­
mediate between the first two types. The dominant
minerals are todorokite and manganite. Some of
the samples show small admixtures of manganese
goethite. The set of associated microelements is the
same as in the basic mass, but their content is
generally less.
General descr iption of the phys ico-chemical
env ironment
The Atlantis-II Deep is the best-studied part of
the Red Sea rift area. A number of papers describe
the major structural features, the general
mineralogical-geochemical characteristics of the
sediments and physico-chemical parameters of brines
filling the Atlantis-11 Deep (Degens & Ross, 19 69;
Backer & Richter, 197 3; H ackett & Bischoff, 197 3;
Butuzova, 1984a,b).
The area of the Atlantis-II Deep is 7 0 km2; it is
filled with dense, highly mineralized thermal brines
about 17 0 m thick with distinct vertical stratification.
The lower and thickest layer has a temperature of
62 -65°C, salinity up to 320 %o, is completely devoid
of oxygen, and pH values in it reach 5·5-5 ·6. Above
this layer, a change in all parameters of the water
mass occurs at a definite boundary, i.e. the tempera­
ture falls to 51 °C, salinity is reduced to 153 %o, the
pH value is 5·9, and oxygen is present in small
amounts (0·05-0·06 mg/1). This layer is about 30 m
thick, and above an intermediate horizon of about
the same thickness is a layer of normal seawater
(Degens & Ross, 1969).
Data available in the literature on the structure of
the brine layers and their physico-chemical charac­
teristics were used to work out a scheme for the
formation of a complex of mineral phases (Fig. 5). A
 Iron-manganese oxyhydroxides, the Red Sea
rather informative addition to the scheme is a set of
data on iron and manganese distribution throughout
the brine layers, from the contact with bottom
sediments to the boundary with seawater (from
Brewer & Spencer, 1969) (Fig. 6).
The mechanism of formation of iron oxyhydroxides
Figure 6 clearly shows that a sharp change in iron
content in the brine layer occurs at the boundary
between the lower layer (A) and the overlying hor­
izon (B). This change in properties is caused by an
overall transition of the dissolved iron into solid'
phases in the zone where oxygen appears. A direct
confirmation of the formation of a major mass of
iron hydroxides at the boundary between two layers
in the brines is a perceptible rise in the amount of
63
Fig. 4. Morphology of solid aggregates in the major mass
of manganese ore material and diffraction pattern of
manganite (the Atlantis-II Deep, site 1905(5), horizon
4830-5000 mm). (a) Microconcretion of mangani te; (b)
platey crystals of manganite composing the
microconcretions; (c) aggregate of polycomponent
composition ( todorokite, manganite, manganese
goethite). Scale bars (a) 400 �-tm, (b) 1 �-tm, (c) 200 �tm.
rusty-brown suspended material in this area which is
completely amorphous (Hartmann, 1979). Holm et
a!. (1982), however, have established the presence
of the mineral phase �-FeOOH (akaganeite) in the
suspended material. Most workers believe that the
presence of chlorine (or fluorine) anions in solution
is a necessary condition for the formation of the
phase �-FeOOH, in addition to an acid or neutral
environment, as realized in the Atlantis-ll Deep.
Akaganeite is as yet the only crystallized phase of
3
Fe +, found in small amounts in suspension in the
brines of the Atlantis-II Deep. However, neither
previous research nor our studies have found this
mineral in the sediments. Taking into account the
metastable character of the phase FeOOH, we as­
sume a rapid transformation of akaganeite into
more stable crystalline phases (goethite, hematite).
 -- - -1-
64 G. Yu. Butuzova et al.

_P _!:I � �------ -;;�� -dp�;d- c;,-,- ;;::��W�O�E�- ; � � =��

m r h :x:e-
�!�)�o� :a�-------
F

J
matter -
[O,]>IMn2•1. pH>7.t < 500C
Corg

0JSSOCI3tiOO
H2Mn03-+2H+ + Mno}----::lll
Mn>+ + V20 20H--+Mn0 ·H20 - IMnOj· (nMn02·mH20)]2H+
2+ 2 Hydration polymerization
�

IC

II Mn2+ l/zO., + 2H,O -----. MnO , ·H, Q + 2H+

Mn2+ !
+

102] < 1Mn2•]: - - - - Polymerization

pH- 6 Mn2+ Mn0]�2Mn0(0H) -- nMnO(OH)·mH20
-
1- so·c

�,r I I
B

t
__ ____

[O,] = O
pH- 5
1- 6s·c
l
�n_'"_'-+
Fe(II)
� ��1.:_���'---�-
y
_______
o
- -- -
Amorphous hydrox1de Fe(III)
-_- _ _-_ _ _-_ _-_
,_ ----,t---H-
I
•1.
-----
nMnO,·mH,O

Manganite
I

.I
�

A
,. �4

Fig. 5. The scheme of iron-manganese mineral formation in the Atlantis-IT Deep. A, B, C- layers of brines (A- lower,
B- upper, C - transitional to seawater); I- upper zone of active oxidation; II - lower zone of slower oxidation. ( 1)
Amorphous phase of suspension; (2) mineral phases; (3) sedimentation and mineral formation (coagulation, dehydration,
crystallization); (4) migration in brine; (5) transformation of solid phases of the suspension and sediment; (6) area of
manganese ore deposits.

Another possible cause of the absence of akaganeite
in the sediments might be its destruction due to loss
of chlorine from the sediment in the process of
elutriation of samples by water to remove easily
soluble salts. Disintegration of akaganeite after
chlorine removal has been confirmed experimentally
(Chukhrov et al., 1975a).
The ore layer of the Atlantis-ll Deep has two
major mineral associations of iron oxyhydroxides:
the goethite-hematite association, typical of iron
ore deposits of all lithological-facies zones, and the
ferrihydrite-lepidocrocite association, confined
to manganese-rich interlayers. Small amounts of
ferrihydrite were also found in the iron ore sedi­
ments, mostly in the upper horizons of the sections.
Since the major mass of oxidized iron appears at
the boundary between two layers (Figs 5, 6, A and
B), the amorphous hydroxides formed at this place
may be the origin for the bulk of the goethite and
hematite in the ore material.
1 Goethite is formed over a wide range of con­
ditions, but experiments to synthesize ferrous phases
show that high concentrations of Fe2+ in the brine at
low oxygen content and rather low pH values stimu­
late goethite formation (Chukhrov et al., 1975b).
The environment in the region of formation of the
major mass of iron hydroxides fully complies with
these conditions. The regular increase in the struc­
tural ordering of goethite from top to bottom of the
ore section confirms the formation of its larger part
by crystallization of the amorphous phase. Another
means of goethite formation is related to a trans­
formation from lepidocrocite; the absence of lepido­
crocite in ferrous ore deposits could be due to its
transition into goethite at higher temperatures.
2 Hematite, in contrast to goethite, is formed as a
 Iron-manganese oxyhydrox ides, the Red Sea
depth
m
1920
1960
2000
2040
2080
Fig. 6. Distribution of iron and 2120
manganese in the layer of brines in
the Atlantis-II Deep ( after Brewer
& Spencer, 1969). (A) Lower layer 2160
of brines; ( B ) upper layer of brines;
2180
(C) layer transitional to seawater;
(D) seawater.
result of the crystallization of amorphous hydroxides
at higher temperatures. Accordingly, the maximum
amounts of well-crystallized hematite, in the form of
hexahedrons, are confined to regions in the immedi­
ate vicinity of hydrothermal vents. In the studied
sections the total hematite content is notably higher
in sediments at site 1905(5), which is nearer to the
vents, than in the core from site 1905(4).
The presence of finely flaked aggregates, which
form another morphological variety of hematite in
the sediments of both sections, is probably caused
by the transformation of ferrihydrite into hematite.
It is important to note that ferrihydrite in ferrous
ore deposits remains only in the upper parts of the
sections, which may imply that the major part of the
mineral was transformed into hematite in the course
of aging of the sediment.
3 Ferrihydrite is found both in ferrous ore deposits
and in manganese-rich interlayers. It contains par­
ticles with bacterial form which may testify to the
active role of microbiological processes in the for­
mation of this mineral. The C layer of the brines,
which is transitional to seawater, is the most favour­
able environment for active microbiological oxida­
tion-reduction reworking of the ferruginous
suspension. This layer is the gradient zone with a
perceptible change in density and an increase m
oxygen content (Fig. 5).
Consequently, the conditions of formation of
65
ma
� 30 50 70 90 100 ho 20 �0 60 ao 100 :J;
Fe
Mn
amorphous iron hydroxides, which are transformed
on the one hand into goethite and hematite, and on
the other hand into ferrihydrite, are spatially separ­
ated. The sources of iron are also different: in the
first case amorphous hydroxides are produced by
2
oxidation of Fe + which is supplied by hydrothermal
waters; while in the second case they are a result of
the transformation of ferruginous suspension from
seawater (Fig. 5).
4 Lepidocrocite includes particles with bacterial
form which develop from a biogenic matrix by the
same processes and under the same conditions as
ferrihydrite. The abiogenic lepidocrocite is probably
2
formed as a result of Fe + oxidation in the boundary
zone of brines between layers A and B. The extensive
production of hydrated forms of Mn02 and the
presence of amorphous Si02 in manganese ore
interlayers apparently stimulate the preservation in
the sediment of metastable hydroxide phases of
iron, i.e. ferrihydrite and lepidocrocite.
Mechanism of formation of manganese
oxyhydroxides
The behaviour of hydrothermal manganese in the
brine layer of the Atlantis-11 Deep is essentially
different from that of iron. Due to the higher oxi­
dation potential of manganese the transition of
2
hydrothermal Mn + from solution to the solid phase
66 G. Yu. But uzova et a/.
2
Mn + takes place in the brine layer into which the
seawater oxygen penetrates. The process of massive
manganese oxidation is shown in Fig. 6 as a sharp
change in manganese content in the C zone tran­
sitional to the normal seawater. According to the
data of Hartmann ( 1979), it is in this zone that
a notable amount of brown suspended material
appears composed of amorphous manganese
hydroxides.
The particles of hydrated manganese dioxide,
sinking into the brine layer and reaching the lower A
layer completely devoid of oxygen, are reduced by
2
the dissolved Fe +, and manganese again passes into
solution. This process obstructs precipitation of ox­
ide forms of manganese in brines and provides
high concentrations of the element in the solution
(80-90 mg/1), which is about 20 000 times as great
as the average manganese content in seawater. The
natural consequence of these processes is the almost
complete absence of manganese oxyhydroxides in
the sediments in extensive areas of the Atlantis-11
Deep. The local presence in the sedimentary layer
of manganese ore interlayers, confined by sharp
lithological contacts with the surrounding muds, is
evidence of the change of physico-chemical conditions
in the near-bottom water. This change occurs against
the background of a quiescent hydrological setting
with intensive mixing of water masses.
The most probable cause for the change of con­
ditions in the near-bottom water would have been
the lowering of the level of brines which in turn was
connected with a lower or temporarily discontinued
hydrothermal activity during the period of forma­
tion of manganese ore horizons. A number of
lithological-geochemical peculiarities of deposits in
the CO zone testify to this possibility, including an
appreciable admixture of the biogenic-terrigenous
component to the ore material, and a low content of
sulphides including diagenetic sulphides. Confine­
ment of manganese ore horizons to the relatively
high parts of the sea floor is also evidence because
these parts are in the upper layer B when the level of
brines is lowered (Fig. 5). It is in this region that
conditions are created to allow the possibility of
massive precipitation and preservation of manganese
hydroxide compounds in sediments, these con­
ditions being an increase in the oxygen content, a
2
sudden fall in Fe + concentration and temperature,
and a rise in pH.
In discussing the possible mechanisms of the for­
mation of manganese hydroxide compounds, it is
2
important to consider the nature of Mn + oxidation
processes and certain properties of the compounds
formed during these processes.
2
The act of Mn + oxidation by oxygen in solution
results in the appearance of Mn4+ in the form of a
hydrated dioxide according to the reaction:
2
Mn + + 1/202 + 20H- __,. Mn02·HzO
At a molecular level the hydrolized products of
2
the initial Mn + oxidation are coordinated hydrated
polymeric aggregates. Their coagulation produces
hydrated microstructures with adsorptive activity
capable of dehydration and intraphase oxidation­
reduction transformations by the scheme:
2
Mn + + Mn4+ � 2Mn3+
The development and direction of certain trans­
formations of the amorphous phase and the
formation of individual compounds are determined
2
mostly by the conditions of Mn + interaction with
2
dissolved oxygen and by the ratios of Mn + : 02
concentration, pH value, and adsorptive and cata­
lytical activity of the newly formed surface of hy­
drated Mn02.
In the environment of the Atlantis-11 Deep, the
stratification of the water layer provides differen­
tiation in the physico-chemical conditions of the
medium where mineral formation takes place; these
conditions control the polymineral composition of
ore material.
Formation of todorokite and manganese goethite of
the major mass
2
Figure 5 shows two Mn + oxidation zones with a
number of essentially different parameters.
Zone I of active oxidation generally coincides
with layer C of the brines, which is transitional to
seawater and has a high content of dissolved oxygen,
an alkaline environment, and relatively low tem­
peratures ( <50°C). The underlying zone I I is oxygen
deficient, has higher temperatures, and lower pH
values ( �6). The massive oxidation of divalent
manganese occurs in zone I where a hydrated man­
ganese dioxide (Mn02·nH20) is formed. An alkaline
(or close to neutral) medium stimulates dissociation
of the amphoteric oxide Mn02·nH20:
Mn02·nH20 __,. H2 Mn03 __,. Mnol- + 2H+
2
The Mn03 - anions formed in the process are
capable of being abundantly hydrated to form thixo­
tropic macrostructures of hydrated Mn02
(nMn02·mH20). Against the background of high
 Iron-manganese oxyhydrox ides, the Red Sea
salinity, the amorphous hydroxide acts as a cation­
exchanger irreversibly fixing dissolved and partially
hydrolized cations of different metals, including
Mn2+, which in the case of superfluous oxygen results
in the oxidation of this cation, thus additionally
increasing the mass of individual particles. The in­
crease of the mass of particles due to coagulation,
combined with the oxidation mechanism and parallel
dehydration, results in a loss of sedimentary stability
of particles and their sinking into the underlying
zone II (Fig. 5).
Under these conditions, the capacity of particles
to adsorb the cations of metals is drastically reduced
because of the lower adsorptive activity in general
(more acid environment) and competitive adsorption
of Mn2+ cations. The oxygen deficit restricts oxi­
dation of adsorbed Mn2+ and, consequently, the
appearance of new adsorption centres. As a result,
the change in the composition of particles ceases,
and the major means of their transformation be­
come dehydration and increasing density, paving the
way to subsequent crystallization and precipitation.
The crystallization of the amorphous phase is
caused to a great extent by the presence of large
hydrated cations in adsorptively saturated complexes.
Due to steric restrictions, the presence of adsorbed
cations obstructs crystallization of the amorphous
phase and the formation of structures with dense
packing of atoms, but stimulates the formation of
minerals with relatively friable anion complexes.
Therefore, the overall low degree of structural
ordering of the basic mass of manganese ore material
and the extensive development in its composition of
weakly crystallized todorokite with a loose tunnel
structure seem to be the natural consequences of the
transformation processes of amorphous hydroxides
formed in zone I of active oxidation.
The iron-manganese phase identified as man­
ganese goethite and found in small amounts in the
major mass of ore material in association with
todorokite is probably the final product of the trans­
formation of thixotropic mixed macrostructures of
amorphous iron and manganese hydroxides.
Formation of manganite microconcretions
The presence of monominerallic manganite in sedi­
ments is evidence for specific conditions for Mn2+
oxidation in the water layer, which provide for the
formation of the amorphous phase with no other
cations except manganese. Zone II entirely complies
with these conditions and is characterized by an
67
excessive amount of Mn2+ ions, an oxygen deficit,
rather low pH values (about 6), and higher tempera­
ture (about 50°C) (Fig. 5).
As noted earlier, oxidation of the Mn2+ ion by the
oxygen molecule results in the formation of hydrated
manganese dioxide (Mn0 ·nH 0). Within the struc­
2 2
ture of manganite the manganese cations are tri­
valent. One of the possible ways of Mn3+ formation
is the interaction of Mn0 ·nH 0 with Mn2+ cations,
2 2
as a result of which an intraphase oxidation­
reduction process takes place. This interaction can
be realized with the decrease in adsorptive activity
of the surface of particles of hydrated Mn0 in the
2
setting with excessive Mn2+, resulting in rapid trans­
formation of the adsorbed form into the compound
Mn2+Mn4+0 and its subsequent oxidation­
3
reduction transformation Mn2+ + Mn4+ --? 2Mn3+.
Despite the lack of precise experimental data, we
assume that this process is restricted to a specific
interval of pH values, because in weakly alkaline
conditions hydration of the Mn2+ ion and of adsorp­
tion centres of Mn0 stimulates stabilization of the
2
adsorptive Mn2+ form in the Mn0 ·nH 0 phase. In
2 2
acid media the trivalent manganese disproportion­
ation takes place.
In contrast to highly hydrated complexes formed
in zone I, the amorphous hydroxides formed in zone
II are considerably less hydrated and practically lack
adsorbed cations, which ensures their transformation
into an energetically favourable compact packing
typical of manganite.
Formation of morphologically composite nodules
Mutual precipitation of dehydrating gel particles
of todorokite and manganite composition (lesser
amounts of the latter) should be accompanied by the
appearance of mechanically mixed phases whose
final composition is probably determined only in the
sedimentary layer. In this case the most probable
process is the fixing of dissolved Mn2+ from inter­
stitial waters by the sorbently unsaturated areas
of Mn0 . Moreover, the achievement of the ratio
2
Mn2+ : Mn4+ = 1 : 1 allows the fragments of manga­
nite structure to form concurrently with todorokite
crystallization. Other processes related to the re­
grouping of structural blocks of Mn0 and the
2
intraphase oxidation-reduction interactions are also
possible.
In general, the absence of a notable accumulation
of manganese in the zone of its active oxidation is
68 G. Yu. But uzova et a/.

evidence for its removal from this zone by precipit­
ation of manganese hydroxides.
THE THETIS DEEP
Description of samples and their mineral composition
The mineralogy of oxide phases was studied in 13
samples from a core 510 em long taken from site
224 with coordinates 22°47 ·2'N and 37°35 ·5'E.
Studies conducted earlier on this section have
established the structure of the ore layer and its
general mineralogical features (Backer & Schoell,
19 7 2; Bignell et al., 197 6; Shanks, 1983; Butuzova,
1 985; Missack, 1988). Two basic varieties of deposits
were found to regularly alternate in the sediments
(Fig. 7). One of them (sequences II and IV) is
represented mostly by ferrous ore material with iron
content reaching 32-56%, manganese 0·35-0·47 %,
and manganese oxyhydroxides absent. The admix­
ture of biogenic-terrigenous components is ex­
tremely small (CaC03 <1 %). These sediments have

Fe,%
10 30 50

.50
i

100

350

Il
Fig. 7. Distribution of chemical elements in sediment section, site 224, Thetis Deep.
 Iron-manganese oxyhydroxides, the Red Sea
the highest copper and sulphur concentrations in the
sediment column. The other variety of sediments
(sequences I, III, V) has a high content of normal
sedimentary material (CaC03 20-40%) and a mixed
iron-manganese composition of ore material. The
iron and manganese contents are similar (average
Mn- 16 ·3%; Fe-18·2%).
The iron oxyhydroxides magnetite and lepido­
crocite are the most typical minerals among the
crystallized phases of the ore material.
1 Magnetite is found only in ferrous ore sediments
(Fig. 7, sequences II, IV) in the form of well-faceted
crystals several micrometres in size, as finely dis­
persed powdery material, and in collomorphic clots.
The magnetite-rich interlayers are identified in the
section by their sooty black colour.
2 Lepidocrocite forms small, platey crystals irregu­
larly distributed throughout the section. The
maximum amounts of the mineral are confined to
the upper part of the section (sequence I) where it is
almost the only iron oxide phase. The lepidocrocite
content decreases down the section.
3 Goethite and hematite are observed in individual
samples, mostly at the bottom of the core. Manga­
nese oxyhydroxides occur in the ore material of
sequences I, III, and V, predominantly in the form
of minerals with lattice structure.
4 Asbolanes are the most common minerals particu­
larly in the upper parts of the section (sequence 1).
Fig. 8. Characteristics of manganese oxyhydroxides from sediment recovered at site 224, Thetis Deep . (a) Aggregate of
flaked asbolane particles (horizon 2250-2350 mm), scale bar 0·5 fun; (b) electron diffraction pattern of X-phasc particles.
69
Asbolanes are mixed-layer phases (Chukhrov et a/.,
1983). In the sediments they form aggregates of
flaky particles (Fig. Sa). Their composition includes
aluminium, magnesium and calcium, in addition to
manganese. The structure of the minerals is built up
by octahedral layers of two types. In one of them the
major cation is Mn4+ and in the other it is MnH
in combination with aluminium, magnesium and
calcium. The quantity and the degree of structural
ordering of asbolanes regularly increase from the
top of the section downwards.
5 An asbolane-like stratified X-phase was observed
by us for the first time. It was found only in the
uppermost of the studied horizons (200-250 mm)
where it dominates the composition of the
manganese ore material; the asbolanes described
above are noted in small admixtures. The X-phase
particles are platey in shape, and they are domi­
nated by manganese cations.
The electron diffraction pattern of the X-phase
(Fig. 8b) is a superposition of three hexagonal nets
of reflections which differ in their distances from the
centre of the electron diffraction pattern. The triads
of reflections nearest to the centre have interplane
distances d = 2·49, 2·60 and 2·7 2 A, whereas the
triads of reflections farthest from the centre are
characterized by d values equal to 1·44, 1·50 and
1·57 A. Three hexagonal nets of reflections on the
electron diffraction pattern of the X-phase can be
70 G. Yu. But uzova et a!.
related to the three hexagonal sublattices of the
mineral, the basal parameters of which are a= 2·88,
3·00 and 3 ·40 A, respectively. The values of par­
ameter 'a' are different because the three types of
layers contain mostly cations Mn4+, Mn3+ and
Mn2+, respectively.
6 Manganese goethite, as in the Atlantis-II Deep, is
observed in the form of tabular crystals locally form­
ing almost monominerallic microaccumulations.
The manganese minerals are distributed regularly
in the Thetis Deep. Thus, the X-phase is observed
only in the uppermost of the studied horizons; the
asbolanes with low structural ordering dominate in
the sediments of sequence I approximately to a
depth of 1 m; and in the lower-lying deposits the
degree of structural ordering of asbolanes increases
but their quantities are definitely subordinate, and
manganese goethite becomes the dominant manga­
nese phase.
General characteristics of the physico-chemical
setting
The region of the Thetis Deep is one of the few
areas of the Red Sea rift which combines high
hydrothermal activity with an absence of strongly
mineralized near-bottom brines.
At the present time, the sediments are overlain
with water which is only 0·8°C and 0·4% salinity
higher than normal seawater. A slight rise in salinity
of interstitial waters in some parts of the sediment
column suggests periodic but insignificant changes in
the mineralization of near-bottom waters in the past.
Variations in the chemico-mineralogical character­
istics of the sediment section at site 224 reflect
periodic changes in the intensity of the hydrothermal
source. The iron ore horizons II and IV correspond
to stages when the near-bottom water received large
quantities of Fe2+ and Mn2+ as constituents of
thermal brines whose mixing with oxygenated sea­
water caused oxidation of the reduced forms.
Active oxygen consumption under conditions of
high Fe2+ concentrations resulted in rapid exhaus­
tion of oxygen and in the temporary filling of
the basin with oxygen-free waters rich in Mn2+ and
Fe2+. In this setting, the complete absence of
manganese oxide compounds in the ore material of
sequences II and IV is expected. During periods of
lower hydrothermal activity, the sedimentary se­
quences (I, III, V) were highly enriched in biogenic­
terrigenous material and contained mixed iron­
manganese ore material. At these times the water
mass parameters in the basin gradually equilibrated
with the seawater parameters. In this way conditions
were created for oxidation of Fe2+ remaining in the
solution and of Mn2+ accumulated there.
The mutual precipitation of iron-manganese
hydroxide forms in approximately equal proportions
indicates rather low Fe2+ concentrations insufficient
for appreciable reduction (in weakly alkaline con­
ditions) of hydrated Mn02 formed in the upper
more aerated water layers.
Mechanism of formation of iron oxyhydroxides
Experimental research has established that in neutral
or weakly alkaline solutions the oxidation of Fe2+
results in the formation of lepidocrocite or magne­
tite. It is suggested that the transformation of the
amorphous material into another mineral phase is
mainly controlled by kinetic factors. Rapid oxidation
stimulates crystallization of lepidocrocite; slow oxi­
dation favours magnetite formation (Murray, 1 9 7 9).
1 Magnetite is formed in the periods of maximum
hydrothermal activity when the Fe2+ concentration
is much higher than the oxygen concentration,
allowing mutual precipitation of amorphous hydrox­
ides of .multivalent iron. The possibility of the for­
mation of magnetite as a result of the dehydration
and crystallization of a gel containing both Fe2+ and
Fe3+ has been experimentally confirmed (Berz,
1 922).
2 Lepidocrocite represents periods of lower hydro­
thermal activity under conditions of excess oxygen
and lower Fe2+ contents in the solution. These
conditions are favourable for the high oxidation
rates of iron necessary to form lepidocrocite.
3 Goethite and hematite are in all probability the
products of lepidocrocite transformation. This alter­
ation is apparently greatly hindered by the presence
of amorphous silica and hydrated Mn02, and thus
takes time. This is confirmed by extremely low con­
tents of goethite and hematite in the uppermost part
of the section where l�pidocrocite is almost the only
3
mineral phase of Fe +.
Mechanism of formation of manganese
oxyhydroxides
Unlike the oxidation zone I of the Atlantis-II Deep,
the water layer of the Thetis Deep is more alkaline,
there is a deficit of oxygen as a result of the preceding
Fe2+ oxidation, and much lower Mn2+ concen­
trations. These conditions obviously obstruct the
 Iron-manganese oxyhydrox ides, the Red Sea
rapid growth o f the mass o f suspended Mn02
particles due to their coagulation. It is possible that
due to slower coagulation the hydrated structures
with low ordering initially appear and in them, from
above and below, the adsorbed Mn2+ cations and
H 2 0 molecules attach to the fragments of insular
octahedron Mn4+ layers. The intraphase oxidation­
reduction reactions between Mn4+ and adsorbed
Mn2+ slow down due to high hydration of the poly­
meric microaggregates. Condensation, adhesion and
reorientation of these microaggregates probably re­
sult in the layer by layer alternation of two­
dimensional associations of Mn4+ and Mn2+ .
Concurrently with the formation of an increasingly
well-crystallized structure, an intraphase Mn4+ and
Mn2+ oxidation-reduction interaction probably
takes place producing trivalent manganese. This
stage apparently correlates with the low-ordered X­
phase containing disproportionate layers occupied
by Mn4+ , Mn3+ and Mn2+ cations.
CONCLUS IONS
The bulk of the iron and manganese oxyhydroxides
in the ore material of the Atlantis-II and Thetis
Deeps is formed by oxidation of Fe2+ and Mn2+,
supplied by hydrothermal brines, and by precipi­
tation of amorphous hydrated particles from the
brine. Subsequent processes of their transformation
into individual crystalline phases depend on the
composition of particles and are controlled by a
complex of effects, including oxidation-reduction,
coordination, colloidal-chemical, adsorptive, sedi­
mentary and diagenetic processes. These transform­
ations are also influenced by the kinetics of gel
dehydration. All these effects are shown to be deter­
mined by distinct physico-chemical parameters of
the mineral-forming medium. The differences be­
tween these parameters in the water layers of the
studied basins result in the formation of different
mineral associations.
In the ore material of the Atlantis-11 Deep,
goethite and hematite predominate among the fer­
ruginous phases; the manganese phases are rep­
resented mainly by todorokite and well-crystallized
m;:mganite . This set of minerals is controlled by the
differentiated conditions related to the stratification
of the water layer, the lower layers of which have
low pH values, higher temperatures, a sharp de­
ficiency in oxygen, and a high concentration of
Mn2+ and Fe2+ ions; the parameters of the upper
71
layers are transitional to those of seawater and have
low Fe2+ and high Mn2+ contents.
In the Thetis Deep, the iron ore material contains
a predominant magnetite -lepidocrocite association
and the manganese component is represented mostly
by asbolanes. This basin has no stratified brines and
the mineral-forming environment is alkaline, low
temperature and oxygenated. The changes in con­
centration in the solution of Fe2+ and Mn2+ ions are
controlled by changes in their supply from hydro­
thermal brines.
ACKNOWLEDGEMENTS
The authors express their sincere thanks to two
anonymous reviewers and J . Parnell for critical
reading of the manuscript and numerous valuable
corrections. We also are indebted to A. Sivtsov for
selected-area electron diffraction, N. Gorkova
for supplying electron micrographs and B. Smoliar
for assistance in the preparation of the manuscript.
REFERENCES
Bii.CKER, H. & RICHTER, H. ( 1973) Die rezente
hydrothermal-sedimentare Lagerstatte Atlantis-II-Tief
im Roten Meer. Geol. Rund. 62, 697 - 741.
Bii.CKER, H . & ScHOELL, M. ( 1972) New deeps and metal­
l iferous sediments in the Red Sea. Nature 240,
153- 158.
BERZ, K.C. ( 1922) Uber Magneteisen in Marinen
Ablagerungen, pp. 569-577. Centralblatt fi.ir
M ineralogic, Geologie und Palaeontologie, Stuttgart.
BIGNELL, R . D . , CRONAN, D.S. & TOOMS, J . S . ( 1976) Red
Sea metalliferous brine precipitates. Geol. Ass. Canada
Spec. Pap. 14, 147- 149.
B ISCHOFF, J . ( 1969) Red Sea geothermal brine deposits,
their mineralogy, chemistry and genesis. In: Hot Brines
and Recent Heavy Metal Deposits in the Red Sea (Ed. by
E .T. Degens & D.A . Ross ) , pp. 368-401. Springer,
Berlin.
BREWER, R . G . & SPENCER, O . W . ( 1969) A note on the
chemical composition of the Red Sea brines. In; Hot
Brines and Recent Heavy Metal Deposits in the Red Sea
(Ed. by E.T. Degens & D.A. Ross) , pp. 174- 179.
Springer, Berlin.
BuruzovA, G . Y u . ( 1984a) Mineralogy and certain aspects
of genesis of metalliferous sediments in the Red Sea,
Communication 1. Litho!. Miner. Resources 2, 3 -23.
B uruzovA, G . Y u . ( 1984b) Mineralogy and certain aspects
of genesis of metalliferous sediments in the Red Sea,
Communication 2 . Litho!. Miner. Resources 4, 11-32.
B uTUZOVA, G.Yu. ( 1985) Singularities of hydrothermal­
sedimentary ore genesis in the Rift Zone of the Red Sea.
Litho/. Miner. Resources 5, 39-55.
72 G. Yu. But uzova et al.
CHUKHROV, F.V., ERMILOVA, L . P . , GORSHKOV, A . I . &
BuGELSKI, Y u . Y u . ( 1975a) Beta-hydroxide of iron and
akaganeite. In: 1-!ypergenic Oxides of Iron in Geological
Processes (Ed. by N . V. Petrovskaya) , pp. 6 1 -70. Nauka,
Moscow.
CHU KHROV, F.V . , ERMILOVA, L.P. , GORSHKOV, A . l . ,
ZHUKHLISTOV, A . P . , SIDORENKO, O . V . , ZVYAGIN , B . B . ,
B E LYATSKJ, V . V . , SAPOLNOVA, L.P. & KHOKHLOVA, M . M .
( 1975b) Experimental data o n the conditions o f iron
oxide formation (Ed. by N . Y . Petrovskaya), pp. 1 1 -33.
Nauka, Moscow.
CHU KHROV, F . V . , GORSHKOV, A . I . , D RJTS, V . A . ,
SHTERENBERG, L . E . , SIVTSOV, A . V . & SAKHAROV, B . A .
( 1983) Mixed-layered minerals asbolane-buserite and
asbolanes in oceanic Mn-Fe concretions. lzv. AN SSSR
(Ser. geol. ) 5, 9 1 - 100.
CHU KHROV, F.Y . , GoRSHKov, A . l . , DRITS, V.A . , SivTsov ,
A . V . , UsrENSKAYA, T. Y u . & SAKHAROv B .A . ( 1984)
Structural varieties of buserite. Izv. AN SSSR (Ser.
geol . ) 10, 65-74.
CHU KHROV, F.V . , SAKHARov, B . A . , GoRSHKov, A . I . ,
D RJTS, V . A . & BARJNOV, N . N . ( 1987) A new mixed­
layered phase of oceanic Fe- Mn nodules. Litho!. Miner.
Resources 5, 1 12- 120.
DEGENS, E.T. & Ross, D . A . ( 1969) Hot Brines and Recent
Metal Deposits in the Red Sea. Springer, Berlin, 600pp.
Metal Deposits in the Red Sea. Springer, Berlin, 600 pp.
HACKEH, J.P. & BISCHOFF, J.L. ( 1973) New data on the
stratigraphy, extent and geologic history of the Red Sea
geothermal deposits. Econ. Ceo!. 68, 553 -564.
HARTMANN, M. ( 1979) Untersuchungen von suspendieren
Material in den hydrothermal Laugen des Atlantis- l l­
Tiefs . Ceo!. Rund. 62, 742-754.
HOLM, N . G . , WADSTEU , T. & DOWLER, U . l . ( 1982) �­
Fe00H (akaganeite) in Red Sea Brine. Etud. Ceo!. 38,
367 - 3 7 1 .
MANCEAU, A . , GoRSHKOv, A . I . & DRJTS, V . A . ( 1990)
Structure of Fe and Mn hydrous oxides. I. Crystal
chemistry of Mn, Fe, Co and Ni in Mn hydrous oxides by
X-ray absorption spectroscopy and electron diffraction.
Amer. Mineral. (submitted ) .
MISSACK, E . A . ( 1988) Mineralogy a n d phase relations of
the massive sulphides and metalliferous sediments of the
axial rift valley, Red Sea. Heidelberger Geowissen­
Schaftliche Abhandlungen 23, 2 13pp.
MuRRAY, G.W. ( 1979) Iron oxides. In: Marine Minerals ,
Short course notes, Vol. 6, pp. 47- 107. Mineralogical
Soc. Am. , Washington.
SHANKS, W . C . III ( 1983) Economic and exploration signifi­
cance of Red Sea metalliferous brine deposits. In:
Unconventional Mineral Deposits , pp. 1 57 - 1 7 1 . Am.
Inst. Min. Eng.
Spec. Pubis int. Ass. Sediment. (1990) 11,73-88

Mineoka Umber: a submarine hydrothermal deposit on an Eocene arc volcanic

ridge in central Japan

A. I I J I MA*, Y. WATANABE*, S. 0 G I HA RA* and K. YA M A ZA K It

*Geological Institute, University of Tokyo, Hongo 7-3-1, Tokyo II3, Japan;t Mitsui Coal Mining
Company, Muromachi 2-1-1, Nihonbashi, Tokyo 103, Japan

ABSTRACT

A strata-bound iron-manganese umber, extending for 2 km along strike, overlies the top surface of an
Eocene submarine tholeiitic pillow lava of the Mineoka terrain in the southern Boso Peninsula, 70 km
southeast of Tokyo. The Mineoka Umber is divided into lower metalliferous and upper argillaceous
segments, changing upwards gradually to ferruginous, spicule-rich shale. The metalliferous umber
contains 41-54 wt% F�03 and 8·0- 16·8 wt% Mn02 + MnO, comprising massive aggregates of very
fine goethite, amorphous calcic manganese oxides and pyrolusite. The Mineoka Umber formed during
submarine hydrothermal activity following basaltic volcanism. Direct evidence of the hydrothermal
origin is the discovery of an umber-filled pipe, a conduit for hydrothermal water, within the pillow lava
beneath the strata-bound umber. Away from this conduit, the MnO : Mn02 ratio in the strata-bound
umber decreases, reflecting the redox potential of the umber formation, and thus the content of
pyrolusite increases. The high concentrations of rare earth elements and the strong negative cerium
anomaly in the umber are also explained by the submarine hydrothermal origin. Calcites filling pores
3
and contraction cracks in the pipe umber have 61 C and 6180 values of -8·5 to -10·6%o and -14·3
to -20-4%o PDB, respectively. These values suggest precipitation from heated Eocene seawater
at 55-68°C. The metal-carrying hydrothermal water was probably much hotter than the calcite­
precipitating water. Abundant spicules in the overlying shale are thought to represent a school of
sponges that fed on the nutrient-rich water. The Mineoka Umber accumulated at the foot of an Eocene
arc volcanic ridge in the supra-subduction zone off the Japanese continental arc.

INTRODUCTION

T he Mineoka Umber deposit is mainly composed of
manganese oxides and hydrated ferric oxides. A
short note by T asaki et al. (1980) reported the
occurrence of the umber from a roadside cut along
the Skyline Road of the Mineoka Hills in the
Mineoka terrain of the southern Boso Peninsula.
Another hematitic umber deposit was reported
briefly by lijima et al. (1981) from Setodani in the
Setogawa terrain of central Shizuoka, the western
portion of the Mineoka- Kobotoke-Setogawa
Tectonic Belt (Fig. 1). T he two umber deposits are
closely associated with Eocene submarine b asaltic
pillow lavas and they are considered to be related to
submarine hydrothermal activity following the
b asaltic volcanism. Similar metalliferous sediments
occur in the Cretaceous of the Tethys region
(Robertson & Boyle, 198 3). T heir depositional
setting is still controversial. The Cyprus Umbers
were once considered to have formed on the
T roodos Oceanic Ridge; their modern analogue is a
metalliferous red clay on the East Pacific Rise
(Eiderfield et al. , 197 2; Robertson & Hudson, 1973;
Robertson, 1975; Robertson & Fleet, 1976).
Robertson & Fleet (1986) have reasoned that metal­
liferous sed iments from the Oman Ophiolite as well
as the Cyprus Umbers formed on a volcanic ridge
above the subduction zone. However, Karpoff et al.
(1988) considered the Oman metalliferous sedi­
ments to have a spreading oceanic ridge origin.
The Mineoka -Setogawa-Kobotoke Tectonic
Belt, which comprises extensively folded and faulted
marine strata of Palaeogere to middle Miocene age

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun 73

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
74 A. Jijima et al.
139
0 c
138 �m
I=======:Oi50
I
Fig. 1. Locality map. Strata and rocks of the Mineoka-Kobotoke-Setogawa Tectonic Belt are hatched. Locality of the
Setogawa Umber marked by a cross.
and intrusive ultramafic rock masses, developed from
an arc volcanic ridge and a forearc basin in the arc­
trench gap on the Pacific Ocean side of central Japan
(Watanabe, 198 9). Recently a strata-bound umber
has been excavated at two quarries of the Chiba
Kenzai Industrial Company in the Mineoka Hills,
within 2 km distance from the original locality re­
ported byTasaki et al. (1980). Its occurrence, mineral
assemblage, chemical composition and carbon and
oxygen stable isotopic composition are described in
this paper. Furthermore, its origin and site of
deposition are discussed.
GEOLOGICAL SETTING
Stratigraphy
The Mineoka Hills are situated in the eastern portion
of the Mineoka-Kobotoke-Setogawa Tectonic
140 141
-
36
TOKYO
35 -
I C
I f
"'
I'
Belt. Here Palaeogene and Lower Miocene marine
strata of the Mineoka Group are extensively dis­
turbed by tectonic movements and by intrusion of
ultramafic rocks. The Mineoka Group is subdivided
into four stratigraphic formations as shown in Fig. 2.
T he lowest Kamogawa Formation, more than 200 m
thic k , is mainly composed of pillow lavas, pillow
breccia and massive lavas of tholeiitic, picritic and
alkali basalts. A dacitic tuff brecc ia to vitric tuff,
with a thickness of 60 m, is interbedded with the
basalts. Middle Eocene nannofossils, such as Coc­
colithus eopelagicus and Reticu/ofenestra cfr. um­
bilica, were found in interpillow limestone in the
pillow lava at Arayashiki on the coast of Kamogawa
(Watanabe, 198 9). T he Shirataki Formation, up to
250 m thick, represents a hemipelagic biogenic facies.
Its lower and midd le parts consist of. bedded
calcareous quartzose c hert, which originated from
calcareous diatomite, and bedded siliceous micritic
limestone with an interc alation of 30 m thick, silicic
 Mineoka Umber, Japan 75

THICKNESS
AGE FORMATION LITHOLOGY
FAULT (m)

HATCHO Fm. :;::::: 1000 Flysch

EARLY MIOCENE
--- - -
- - ---
-- - -
1 - ----
--- -
1-----
- -- - -
1-----
HEGURI Fm. --- - 50 300 Siliceous mudstone
1-----
--- -
-----
- ---
1-----
- -- - -
- - - --

.......
Glauconitic sandstone

OLIGOCENE

SHIRATAKI Fm. 300 Bedded chert and micritic limestone

'-l\/\./\1\ Silicic tuff (30 m)

LATE EOCENE

FAULT
6.5 Chocolate shale
1-2.5 MINEOKA UMBER
MIDDLE EOCENE 80 Pillow basalt
--·raul

r:-:: pault/ \ 1 '\

KAMOGAWA Fm. \./'-/'\./"\/
60 Silicic tuff

50 Pillow basalt
FAULT

Fig. 2. Columnar section of the Mineoka Group in the Mineoka terrain.

vttnc tuff. Its upper 80 m thick part grades into
b edded siliceous shale. L ate Eocene to early
Oligocene nannofossils such as Coccolithus pelagicus
and Dictyococcites cfr. bisectus were collected from
the lower micritic limestone at Shirataki, while
Theocotyle sp. nov. of late Oligocene radiolaria was
found in the upper siliceous shale (Iijima et al.,
198 4). Latest Eocene planktonic foraminifera were
also reported from the calcareous chert at Shirataki
(Suzuki et a!. , 198 4). Although the above two for­
mations are in contact with each other at thrust
faults, the Shirataki Formation probably overlies the
Kamogawa Formation, as inferred from the micro­
fossil biostratigraphy. The Shirataki Formation is
conformably overlain by the siliceous mudstone of
the 50-300 m thick Heguri Formation, containing
early Miocene radiolaria. Glauconitic sandstone,
less than 1 m thick, occurs locally at the b ase of the
Heguri Formation. The Mineoka Group terminates
with a non-volcanic sandy turb idite facies of the
Hatcho Formation , more than 1000 m thick, which
contains early Miocene radiolaria.
Depositional environment
T he Mineoka and Setogawa Umbers were deposited
at the foot of the Eocene submarine volcanic ridge
off th_e Japanese continental arc. Silt- to sand-sized
terrigenous grains were not derived from the conti­
nental arc during the umber deposition. A glau­
conitic sandstone bed is intercalated between bedded
chert of the Shirataki Formation and siliceous mud­
stone of the Heguri Formation. The lowermost
Miocene glauconitic sandstone contains 20-40 vol%
76 A. Iijima et a!.

authigenic glauconite pellets and siliceous clay
matrix. This sandstone and the glauconitic sand­
stones at the base of the Miocene siliceous sediments
in the northeastern Honshu arc ( Iijima et a!., 198 8)
suggest an offshore bank environment of 50-500 m
water depth. Late Eocene to Oligocene hemipelagic,
biogenic, calcareous and siliceous sediments of the
Shirataki Formation, as well as the Mineoka U mber,
probably acc umulated at the foot of the volcanic
ridge at depths greater than the offshore bank. A
volcanic island, which is represented by massive
tholeiite lava flows with clinkers and an overlying
basaltic boulder conglomerate, existed near Heguri
and Arakawa, about 20 km west of the Mineoka
Umber. T hus, open ocean water depths were not
reached.
OCCURRENCE AND SAMPLE
DESCRIPTION
Figure 3 shows the geological map of the Mineoka
Hills near Sengensan and Otsukayama, where the
Mineoka Umber is distributed. Strata of the Mineoka
Group are sliced into several thrust sheets. The
umber is observed at three localities near the ridge
of the Mineoka Hills (Fig. 3). Locality 1 reported by
Tasaki et al. (1980) is at a roadside cut on the
southeastern side of Otsukayama along the Mineoka
S kyline Road. This umber is disturbed by faults.
Locality 2 at the Sengensan Quarry is the site where
the umber is best observed, in three trenches.
Locality 3 at the Iimor iyama Quarry is the place in
which field evidence for the hydr othermal origin of
the umber was obtained. However, the umber has
already been covered by mine waste and can no
longer be seen at localities 2 and 3. The Mineoka
Umber directly overlies the pillow basalt of the
Kamogawa Formation. The contact was best ob­
served on the cut-faces of the trenches at locality 2,
where all strata are overturned toward the south
(Fig. 4a, b). The strata-bound umber with a thickness
of 2200 mm covers the uneven surface of the pillow
lava. At the contact, the pillows are oxidized through
a depth of approximately 1000 mm and they change
colour from dark green to reddish brown. In con­
trast, the umber is gr adationally over lain by
c hocolate-brown, sponge spicule-rich ferruginous
shale with a thickness of over 5000 mm. The top of
the shale is c ut by a thrust fault where it is in contact
with a younger light-grey sandstone. At locality 3,
the top of the 1600 mm thick umber is in faulted
contact with a sheared pillow basalt. Elsewhere,
sheared umber and overlying chocolate-brown shale

Early Miocene

Fig. 3. Geological map of the Mineoka Hills in the environs of Sengensan and Otsukayama, showing localities 1-3 of the
Mineoka Umber. Basalt masses encircled by broken line are landslide blocks. K = basalts of the Kamogawa Formation; S
= bedded chert and micritic limestone of the Shirataki Formation with a silicic tuff interbed; Gl glauconitic sandstone at
=

the base of the Heguri Formation; hatched = serpentinite; stipple= younger sandstone.
 Mineoka Umber, Japan
(a)
(b)
Fig. 4. Photographs showing the Mineoka Umber exposed
on the cut-faces of the Sengensan Quarry (locality 2) . (a)
Overturned pillow basalt (B), umber (U), chocolate­
brown shale (S), thrust (arrow), and younger sandstone
(Y). Scale is 1 m. (b) Enlargement of umber-basalt
contact (arrow) in (a).
were recognized within four small pits along the
east-west strike by the Mineoka Skyline Road b e­
tween localities 1 and 2. Consequently, the umber at
these localities is considered to represent one single
bed. This would mean that the Mineoka strata­
. the pressed-powder-disc method. Mineral identifi­
b ound Umber extends for at least 2 km along strike.
The Mineoka Umber is generally dull in lustre,
massive and structureless. A t locality 2 of the
Sengensan Quarry however, several intercalations
of steel-grey, metallic-lustred manganiferous bands,
5-10 mm thick, occur in the basal 600 mm thick
segment of the umber. Similar b ands are also
r ecognized at locality 1. It is very difficult to p repare
thin sections because the umber easily disintegrates
when in contact with water.
A round-shaped umber body occurs within the
77
Fig. 5. Cross-section of the umber-filled pipe with white
calcite veinlets within pillow basalt, about 1 m below the
strata-bound umber, locality 3. Hammer is 30 em length.
p illow lava about 1 m beneath the bottom of the
1600 mm thick strata-bound umber at locality 3 of
the Iimoriyama Quarry (Fig. 5). The cross-section of
this ore body is almost circular with 480 mm dia­
meter. In its outer part it shows radial and concentric
fr actures. White calcite precip itated in veinlets and
in contraction cracks which are probably due to
dehydration of the umber. In its inner par t, calcite
fills micropores of the umber. This occurrence
suggests that the calcite is almost coeval with umber
formation. As a whole, the umber appears to fill a
p ip e standing nearly perpendicular to the contact
between the strata-bound umber and the pillows.
T he umber is not brecciated but massive: therefore
the pipe was a hydrothermal conduit, not just a filler
from above.
METHODS
Wet c hemical analyses were made for specimens
collected from localities 2 and 3. Sampling positions
are shown in Fig. 6. Concentrations of minor and
trace elements were obtained by XRF analysis using
cation was p erformed by ordinary X-ray powder
diffraction (XRD) analysis.
Fracture surfaces of some chips that were taken
from the metalliferous umber at localities 2 and 3
were examined under a scanning electron micro­
scope (SEM). Semiquantitative c hemical analysis of
pyrolusite and amorphous manganese oxides in the
umber was performed on a JEOL 840 SEM with
electron dispersive system.
Instrumental neutron activation analysis (INAA )
78 A. Iijima et al.

LOCALITY +2 LOCALITY +3

No. (INTERVAL)

I
w
1-
< Sh-2 (450-460)
...J
0
(.)
0
I
(.) Sh-1 (230-240)

2-6 (205-215)
>- No. (INTERVAL)
w
a: >-
w < 2-5 (170-180) FAULT
...J
aJ
(.) (140-150)
::;: 3-4
:l
(/) (120-130)
2-4
< :l
:.:: 0
0 a:
w w 3-3 ( 75- 85)
LJ.. 2-3 ( 75- 85)
z
- ...J
2-2 ( 50- 60) 3-2 ( 50- 60)
::;: ...J
<
1-
w 3-1 10- 20)
2-1 10- 20)
::;:
Ocm Ocm
Bc,Bm
1-
3:: ...J
0 < Fig. 6. Columnar sections of the
...J
...J
(/) Mineoka Umber at localities 2 and
<
Cl. aJ 3, showing sample numbers and
UMBER PIPE sampling positions for various
analyses.

was undertaken for each specimen collected from
the lower metalliferous umber (No. 2-2), the upper
argillaceous umber (No. 2-5) and the basal part of
the overlying shale (No. Sh-1) at locality 2 of the
Sengensan Quarry. The specimens were irradiated
for neutron activation in the TRIGA 2 nuclear
reactor at Rikkyo University at the following con­
2 2
dition: thermal neutron flux 1 x 101 n/(cm S) and
irradiation time 12-24 h. Gamma-ray spectra were
measured with a Ge(Li) detector at the Radio­
isotopic Centre, University of Tokyo.
Stable carbon and oxygen isotopic compositions
of sparry calcites in the umber-filled pipe at locality 3
were analysed on a Finnigan MAT DELTA-E mass
spectrometer at the Geological Institute, University
of Tokyo. This was done to estimate the temperature
of hydrothermal water from which the manganese
oxides precipitated. For comparison, the isotopic
composition of calcites in late Eocene micritic lime­
stone of the Shirataki Formation at Shirataki was
analysed. The precision is within 0.02%o and 0.04%o
for the <513Cr08 and <5180r08 values, respectively.
RESULTS
Chemical composition and mineral assemblages
The results of chemical analyses and the mineral
assemblages are shown in Tables 1 and 2 and Fig. 7.
At locality 2, the lower 1400 mm thick segment of
the 2200 mm thick umber is metalliferous and con­
tains more than 50% ferric oxide and manganese
oxides in total, and 70% in its basal part including
the steel-grey, metallic-lustred bands. At locality 3,
the 1600 mm thick umber is metalliferous, containing
a total of 51-59% Fe203 and manganese oxides. In
the metalliferous segments, ferric oxide consists
almost exclusively of hydrous goethite. At locality
2, Mn02 predominates over MnO, and the
MnO: Mn02 ratio tends to increase upward from
0·05 to 0·15. In contrast, MnO predominates over
Mn02 at locality 3, except in the uppermost part.
The pipe-filling umber itself however shows low
MnO: Mn02 ratios (0·21: 0·22) and has a similar
chemical composition when compared with the
metalliferous segment of locality 2. The only
 Mineoka Umber, Japan 79

, w
� ;i (em)]
450
Oz
:s �
():?:
1
�� 250
()(!)

� 200 Ni+Co.f.Cu
a: >-
w <{
(!) _J
:::2 () 150
::J . - . - - . . . . - . - . . . . - . . . . . . · - - - - -

(/)
<{ ::J
:>:::
0 � 100 Zn
w w
z lL Zr
:::2 _J
v
_J
50

�
<{
I-
w
:::2
0
10 20 30 40 50 0 500 800
(wt.%) (ppm)

Fig. 7. Stratigraphic distribution of element contents and ratios for the Mineoka Umber at locality 2.

exception is the high CaO content that results from
calcite in cement and veinlets. Pyrolusite is the only
crystalline manganese oxide phase detected on the
diffractograms of the Mineoka Umber. According
to Tasaki et al. (1 980), pyrolusite is the main con­
stituent at locality 1. At localities 2 and 3 however,
most manganese oxides in the metalliferous umber
are present in an amorphous phase, except for the
appearance of a weak X-ray reflection at 28·5° (28
CuK) for pyrolusite in the steel-grey, metallic­
lustred bands at localjty 2. Here, the concentrations
of Mn02 and Fe203 gradually decrease upwards
together with the water content, whereas other
components such as Si02, Al203 and alkalis
gradually increase. Small amounts of quartz,
montmorillonite and illite were detected in the
metalliferous umber.
The upper 8 00 mm thick segment of the 2200 mm
thick umber at locality 2 is argillaceous, regardless
of its dark-brown colour. The concentrations of iron
and manganese oxides appear to decrease abruptly
to less than 15% at the boundary between the lower
metalliferous and the upper argillaceous segments.
Ferric oxide accounts for almost all of the iron,
although goethite was not detected. Mn02 dis­
appears, whereas the content of MnO is almost
constant in the upper segment from the top of the
lower metalliferous segment (1- 37-2-06% ). In con­
trast, most other components , with the exception of
CaO and P205, are much more abundant in the
argillaceous segment than in the metalliferous seg­
ment. The high contents of Si02 and K20 are par­
ticularly characteristic. Quartz, illite and chlorite are
the main constituents of the upper argillaceous
umber. Quartz does not occur as detrital grains but
as authigenic aggregates that originated from sili­
ceous organisms, such as sponge spicules, radio­
larian skeletons and possibly diatoms, which are
transformed to quartz probably through opai-CT
during burial diagenesis. At locality 3 the upper
argillaceous segment is missing, probably due to the
fault at the top of the umber.
The concentrations of minor elements in the strata­
bound umber at locality 2 are generally low, as
shown in Table 1 and Fig. 7. The copper, vanadium
and zinc contents decrease upwards; they decrease
rapidly at the boundary between the lower metal­
liferous and upper argillaceous segments, corre­
sponding to the contents of ferric oxide and
manganese oxides. In contrast, the zirconium con­
tent increases upward. Values of (Ni+Co +Cu)x 10
decrease upwards , resulting from the generally lower
copper concentration in the higher parts of the
section.
The basal part of the overlying chocolate-brown
ferruginous shale has a chemical composition similar
to the upper argillaceous umber. The composition of
the upper part of the shale is comparable to that of
 00
0

Table l. Chemical composition and mineral assemblage of the Mineoka Umber deposit (2-1 to 2-6), the underlying pillow basalt (Ba-c and Ba-m), and
the overlying chocolate-brown shale (Sh-1 and Sh-2) at locality 2, the Sengensan Quarry in the Mineoka Hills

Ba-c Ba-m 2-1 2-2 2-3 2-4 2-5 2-6 Sh-1 Sh-2

Si02 (%) 47·37 47·32 8·61 9·76 19·76 21·53 50·52 54-48 52·86 45·61
Ti02 1·83 1·67 0-40 0·38 0·47 0·50 0·68 0·82 0·59 2·04
AhOo 14·79 13·67 4·31 6·01 7·25 7·96 15·73 17-08 17·33 16·51
Fe203 5·14 7·54 54·27 50·91 44·13 41·82 12·01 9·69 8-48 12-48
Fe O 4·99 3-40 <0·1 <0·1 <0·1 <0·1 <0·1 <0·1 <0·05 1·74
Mn02 15·52 15·91 9·84 9·58
MnO 0·22 0·19 0·85 0·93 0·59 1-43 2·06 1·37 1·25 0·19 ::t.
MgO 7·38 7-10 1·30 1·39 1·87 1·98 3-48 3·35 2·74 3-06 ......
..:::·
CaO 10·26 10·12 1-07 1·39 2·05 2·35 2·34 1·32 3-01 8·26
0·62 0·70 0·68 2·97
§'
Na20 2·79 3·40 0·13 0·17 0·26 0·27 I:>

K20 0·33 0·96 0·79 0·93 1·81 1·86 3·98 4·15 3·85 1·26 �
H20 ( - ) 6·75 4·71 OAO 0-47 0·70 0·32 1-10 0·72 2·59 1-45 �
H20 ( + ) 2·62 0·19 11·70 11·13 10·02 9·96 6·21 5·66 6·29 4-45
P20s 0·14 0·19 0·89 1·06 1·55 1-43 0·84 0·38 0-47 0·26
Total 100·61 100·37 100·34 100·54 100-40 100·09 99·67 99·82 100·19 100·28

Mn0+Mn02
0·02 0·02 0·30 0·33 0·24 0·27 0·17 0·14 0·15 0·02
Fe203
MnO
--
0·055 0·058 0·060 0·149
Mn02
Ba (ppm) 769 880 929 939 928 853
Co 68 56 77 79 38 120
Cr 49 56 77 79 38 120
Cu 502 464 457 436 266 164
Ni 249 184 150 147 262 210
Rb 108 4 18 17 103 127
Sr 206 236 176 176 231 184
Th* 2 7 18
U* 9 4 3
v 215 216 190 191 121 125
Zn 224 215 227 229 175 153
Zr 70 81 107 107 163 174
Table 1. (continued)

Ba-c Ba-m 2-1 2-2 2-3 2-4 2-5 2-6 Sh-1 Sh-2

La* 624 218 94·8

Ce* 44 112 165
Nd* 750 299 120
Sm* 123 45·3 22·2
Eu* 19·9 16·7 5·19 �
Tb* 18 16 4·6 s·
"'
Yu* 38·1 16·3 7·75 C)
;:>;-
Lu* 4·90 2·05 1·19 .,

Goethite + + + + �
o-
Pyrolusite + "'
_..,
Amorphous
.......
Mn oxides + + + +
Smectite + + + +
�
.,
+ + + + + + ;::s
Chlorite
Illite + + + + +
Quartz + + + + + +
Plagioclase + +
Olivine + +
Cpx. + +

* INAA analysis. Other minor and trace elements are analysed by XRF.

co
82 A. Jijima et at.

Table 2. Chemical composition and mineral assemblages of the Mineoka Umber deposits (3-1 to 3-4) and the pipe-filling
umber (Pu-o and Pu-i) at locality 3, the l imoriyama Quarry in the Mineoka Hills. Those of the Setogawa Umber deposit
(S-U) and the host shale (S-sh) are also shown

Pu-o Pu-i 3-l 3-2 3-3 3-4 S-U S-sh

Si02 (%) 14·12 10·63 13·03 8·27 9·21 12·36 21·04 53·25
Ti02 0·53 0-41 0-45 0·26 0·36 0·41 0-45 0·71
Alz03 6·64 6·11 7·24 5·66 6·63 7·77 9·74 1 3·52
Fe203 45·61 48·75 47·66 44·17 42·98 45·63 45·65 15·78
FeO <0·1 <0·1 <0·1 <0·1 <0·1 <0·1 5·39 2·74
Mn02 8·79 7-42 4·00 5·97 4·26 5·50
MnO 1·87 1·61 5·99 9·35 8·27 4·26 0·20 0-48
MgO 1·62 1·18 1·77 1·23 1·57 1·85 3·96 2·87
CaO 3·31 6·51 3·39 2·24 2·73 1·90 5·98 1·03
Na20 0·06 0·06 0·03 0·03 0·03 0·15 0·31 1 -19
KzO 6·46 0·20 0·53 0·30 0·62 0·41 0·25 2·43
HzO ( ) - 9·59 11·03 3·47 11-00 12·03 6·96 0·45 1·16
HzO (+) 6·75 5·02 11·27 10·88 10·92 11·77 3·71 4·07
Pz05 0·87 1·13 1·57 0·94 0·96 1·05 2·96 0·53
NiO 0·18 0·12
Total 100-48 100·28 100·50 100-40 100·67 100·45 100·09 99·76

Mn0+Mn02
0·23 0·19 0·21 0·35 0·29 0·21
Fez03
Cr (ppm) 21 15 23 22 21 35 27 56
Ni 905 503 518 240 188 156

Goethite + + + + + +
Hematite +
Pyrolusite
Amorphous
Mn oxides + + + + + +
Smectite + + +
Chlorite + +
I llite + + + +
Quartz + +
Calcite + +
Plagioclase +

Fig. 8. Scanning electron

micrograph of pyrolusite in the
steel-grey, metallic-lustred band in
the metalliferous umber. Sample
No. 2-2 from locality 2. (A)
Pyrolusite crystals. (B)
Microcrystalline aggregates of
pyrolusite showing the same
dimensions as the spherular
aggregates of amorphous calcic
manganese oxides.
 Mineoka Umber, Japan 83

the underlying pillow basalt: illite, chlorite and small M

amounts of detrital plagioclase derived from basaltic Amorphous aggregate
n

material. Most of the quartz originated from sili­

ceous organisms.

SEM observation and EDX analysis

Pyrolusite
c
Crystalline manganese oxides were recognized in
the steel-grey, metallic-lustred band at locality 2 p M

(Fig. Sa). The crystals appear to have a tetragonal

prismatic habit and are less than 10 !A-m in length.
A semiquantitative energy dispersive X-ray (EDX)
M
analysis of these crystals does not show elements
Pyrolusite crystal
other than manganese (Fig. 9). Based on the above
evidence and XRD analysis the crystals are identified
as pyrolusite. Pyrolusite sometimes occurs in small
voids among the amorphous aggregates of manganese
oxides. Microcrystalline aggregates of pyrolusite
frequently show dimensions equivalent to the
spherular aggregates of amorphous manganese
oxides (Fig. Sb). p

Amorphous manganese oxides with todorokite-like M

composition n

p
Two morphological types of amorphous aggregates
of manganese oxides were observed under the 5. 020
SEM (Figs 10a,b). One type is a lepisphere-like,
spherular aggregate with a diameter of 10-15 !A-m. Fig. 9. Energy dispersive X-ray semiquantitative analysis
of the Mineoka Umber.
The spherular aggregate consists of micron-scale
curly ribbons or meshes, resembling todorokite in
deep-sea manganese nodules reported by Iizasa
(1988). The other type is a wafer-like aggregate

Fig. 10. Scanning electron

micrograph of aggregates of
amorphous calcic manganese oxides
in the metalliferous umber. Sample
No. 2-1 of locality 2. (A) Spherular
aggregates. (B) Wafer-like
aggregates.
84 A. lijima et a/.

which consists of septa that are arranged subparallel
to each other in intervals of less than 5 r-tm. This type
of aggregate is rather uncommon when compared
with the spherular aggregates.
The semiquantitative EDX analysis reveals that
both types of amorphous aggregates have the same
chemical composition. As shown in Fig. 8, the
amorphous aggregates consist mainly of manganese
with a significant amount of calcium (several per­
cent). Small peaks of silicon, aluminium and mag­
nesium are probably at background level.
The chemical composition of these aggregates
can be estimated from the bulk composition of the
pyrolusite-free metalliferous umber, assuming that
each of the oxides results from the umber-forming
constituent minerals (Table 3). It is estimated that
approximately half of the water content is due to the
presence of goethite, and that the remaining half is
associated with montmorillonite. Therefore, the
composition of the amorphous aggregates is roughly
estimated to be 15·52% Mn02, 0·85% MnO and
1·07% CaO, which are normalized to 8 9·0% Mn02,
4· 9% MnO and 6·1% CaO. The CaO content is
probably a maximum value, because small amounts
of CaO may contribute to montmorillonite and
apatite(?). This estimation is consistent with the
result of the EDX analysis. The MnO: Mn02
ratio of the amorphous aggregates is variable, as can
be seen in the values for the bulk composition of
different arrays (see Table 1). In the strata-bound
umber and pipe-filling umber, the MnO: Mn02 ratio
has a range from 0·21-1· 94.
REE d istribution pattern
The result ofiNAA is shown in Table 1 and Fig. 11.
The three specimens generally have a slightly heavy
rare earth element (HREE)-depleted pattern. The
concentrations of the lanthanides, except for cerium,
decrease upwards from the lower metalliferous
umber to the overlying shale through the upper
argillaceous umber, and are much hjgher than those
of the North American Shale Composite (Haskin &
Haskin, 1966). In contrast, the concentration of
cerium increases upwards, resulting in a strongly
negative cerium anomaly for the Mineoka Umber.
The REE pattern of the Mineoka Umber is very
simjlar to that of the Cyprus Umber reported by
Robertson & Fleet (1976), although the con­
centrations of the lanthanides are much higher in
Mineoka than in Cyprus.
Stable carbon and oxygen isotopic composition of
associated calcites
The micritic calcites of the Shirataki limestone have
3
01 CroB values of +0· 9% and + 1·1%o (Table 4),
suggesting a marine planktonic origin. In contrast,

Table 3. Estimation of the chemical composition (in percentages) of amorphous calcic manganese oxides in the
metalliferous segment of the Mineoka Umber at locality 2

Bulk composition of the metalliferous umber (sample No. 2-1)

Si02 8·61 Essentially montmorillonite

Ti02 0·40
Alz03 4·31 Montmorillonite
Fez03 54·27 Essentially goethite
FeO <0·1
Mn02 15·52 Essentially amorphous aggregates
MnO 0·85 Essentially amorphous aggregates
MgO 1·30 Montmorillonite
CaO 1·07 Largely amorphous aggregates
Na20 0·13 Montmorillonite
KzO 0·79 Montmorillonite
HzO (+, -) 12·20 Goethite (6·1%) and montmorillonite (approximately 6·0%)
PzOs 0·89 ?
Total 100·34

Composition of the amorphous calcic manganese oxides is roughly estimated as follows:

Mn02 1 5·52 89·0
MnO 0·85 4·9
CaO 1·07 (maximum) 6·1
Total 1 7-44 100·0
 Mineoka Umber, Japan 85

10000

w
1- 1000 1\
a:
Cl \ J .......
�\'/'IF�
z
Fig. 1 1 . The chondrite-normalized 0
� -
�
:I:
concentrations of REEs in the u 1
metalliferous umber (1 = sample w
--' 100
-------
No. 2-2), the argillaceous umber
(2 = sample No. 2-5) and the
0..
::;:
<
-----\fl- --- - - --
------ - ' � ,__ 2

overlying ferruginous shale (3 en -- - �· 3

=
-- -
sample No. Sh-1) at locality 2. The - --
North American Shale Composite
---·--- --- --- _____N_
10
(N) is shown for comparison. La Ce Nd Sm Eu Tb Yb Lu

Table 4. Stable oxygen and carbon isotopic composition of calcites in the Mineoka Umber and the Shirataki limestone

013CPDB (%o) 01R0PDB (%o) Temperature (0C)

Pore-cement calcite in the

inner part of the umber pipe -14·3 -9-4 60·1
Veined calcite in the
inner part of the umber pipe
(1) -17·9 -10-4 66·5
(2) -20-4 -8·5 54·5
Veined calcite in the outer
part of the umber pipe -16-4 -10·6 67·9
Calcite in micritic limestone
of the Shirataki Formation
(1) 1·1 -7·3
(2) 0·9 -10·6

the sparry calcites with a nearly pure composition in
veins and cements of the umber-filled pipe have
613CPDB values of -14· 3 to -20·4%o which are
much lower than those of the limestone (Table 4).
These 613 C-depleted calcites precipitated in the
pipe approximately 5 m below the seafloor and
indicate a hydrothermal origin.
The 6180p08 values of the micritic calcites
are -7· 3 and -10·6%o, much lower than those of
the older Tertiary marine planktonic fossils. The
Shirataki limestone recrystallized at temperatures
approximately between 80 and 120°C during burial
diagenesis. This is inferred from zone III (analcime­
quartz) of the zeolitic burial diagenesis of the inter­
calated silicic vitric tuff (Iijima, 1986). The original
oxygen isotopic composition of microfossil calcites
most probably changed during recrystallization.
The sparry calcites in the umber-filled pipe possess
0180ros values of -8·4 to -10·6%o (Table 4). No
significant differences in the oxygen isotopic com­
position of the calcites were recognized between
cement and veins, nor between the inner and outer
parts of the pipe. Temperatures of the hydrothermal
water from which the calcites precipitated can be
calculated from the 6180 values of the calcites,
assuming that the hydrothermal water would be
heated Eocene seawater with a 6180 value of -1·2%o
SMOW (Savin & Yeh, 19 8 1), and that the calcites
did not recrystallize in the course of diagenesis. The
temperatures calculated are 55-68°C.
DISCUSSION
Hydrothermal origin
The aforementioned geologic occurrence of the
Mineoka U mber strongly suggests formation during
hydrothermal activity which followed middle Eocene
86 A. Jijima et al.
submarine basaltic volcanism. Direct evidence
for the hydrothermal origin is the existence of the
umber-filled pipe at locality 3 (the limoriyama
Quarry), because the pipe undoubtedly acted as a
conduit for the hydrothermal water. It is interesting
that the thickness of the metalliferous umber is
1600 mm and more above the conduit, decreasing to
1200 mm at locality 2 (570 m southeast of locality 3).
The REE patterns in both the lower metalliferous
and upper argillaceous segments of the Mineoka
Umber are characterized by a strong negative cerium
anomaly. ln contrast, REE patterns in deep-sea
iron-manganese nodules, particularly from greater
than 3500 m depth, show a strong positive cerium
anomaly (Piper, 1974). Oceanic deep waters, pelagic
biogenic sediments and pelagic authigenic minerals
such as phillipsite are cerium-depleted (Piper,
1974). Matsumoto et al. (1985) investigated the con­
centrations of REEs in Pacific pelagic sediments and
pointed out that red and brown clays with very slow
sedimentation rates in the central Pacific have normal
or even slightly cerium-enriched patterns, whereas
red metalliferous clays on the East Pacific Rise show
a strong negative cerium anomaly. Matsumoto et al.
attributed the strong negative cerium anomaly of the
metalliferous clays to their submarine hydrothermal
origin. We therefore interpret the strongly cerium­
depleted patterns of the Mineoka Umber to be
indicative for a submarine hydrothermal origin. At
least the basal part of the overlying chocolate-brown,
spicule-rich and ferruginous shale seems also to be
affected by the hydrothermal water, considering the
high REE concentrations in this part of the section.
There are also similarities in the REE pattern when
compared with the umber, regardless of the slight
negative cerium anomaly. Abundant spicules in the
shale suggest that a school of sponges fed on the
nutrient-rich warm water, which can be seen as
additional support for a hydrothermal origin for the
umber.
The sparry calcites filling pores and contraction
cracks in the umber pipe precipitated from hydro­
thermal water at 55-6 8°C, as calculated from their
6180 values. The temperature of the metal-carrying
hydrothermal solution that preceded the calcite­
precipitating water was probably much higher
(>100°C). The amorphous aggregates of colloidal
calcic manganese oxides of the Mineoka Umber
suggest rapid precipitation when the manganese­
enriched hot solution mixed with the cold seawater.
The rate of sedimentation for the Mineoka Umber
and the overlying chocolate-brown shale was prob-
ably much greater than the 18 mm/ 103 a for the
hemipelagic biogenic sediments from the Shirataki
Formation, because planktonic organisms such as
radiolarian skeletons are rarely found, even in the
shale.
The pyrolusite of the steel-grey, metallic-lustred
bands appears to have crystallized from the spherular
aggregates of the amorphous manganese oxides,
because a transitional morphology between the
spherular aggregates and the microcrystalline pyro­
lusite was observed under the SEM (Fig. 8b).
Pyrolusite generally forms under more oxidizing
conditions when compared with the amorphous
aggregates of calcic manganese oxides, which still
contain variable amounts of MnO. The MnO: Mn02
ratio in the strata-bound metalliferous umber de­
creases from 0 77 to 1·94 at locality 3, where the
·
pipe-filling umber exists, to 0·05-0·15 at locality 2,
where small amounts of pyrolusite occur. Pyrolusite
dominates at locality 1 (Tasaki et al., 1980), which is
most distant from locality 3. It is therefore concluded
that the conditions became more oxidizing with in­
creasing distance from the conduit at locality 3.
The ratios between manganese and iron oxides
in the metalliferous umber are comparable in the
different localities: 0·24-0·33 at locality 2 and
0·19-0·35 at locality 3. Consequently, a separation
of manganese and iron during precipitation has not
been identified.
Site of d eposition
The Mineoka Umber was deposited on a submarine
volcanic ridge during the Eocene. The ridge ex­
tended from the southern Boso Peninsula to central
Shizuoka in the Mineoka- Kobotoke-Setogawa
Tectonic Belt (Fig. 1). At Setodani, in the Setogawa
terrain, a small lenticular body of ferruginous umber
of 500 x 200 mm size occurs in a radiolarian black
shale of the Takisawa Formation, about 10m above
a basaltic pillow lava (Table 2). The Setogawa
Umber consists of microcrystalline aggregates of
hematite, chlorite and limited quartz, which suggest
a diagenetic modification. The Setogawa Umber has
also been interpreted to have formed by submarine
hydrothermal activity following the basaltic
volcanism (lijima et a/., 1981).
There are two different theories for the ongm
of submarine pillow basalts of the Mineoka­
Kobotoke-Setogawa Tectonic Belt:
1 accretion of the oceanic crust (Ogawa &
Taniguchi, 1988); and
 Mineoka Umber, Japan
2 an arc volcanic ridge. The following points favour
the arc volcanic ridge theory: (a) the bulk chemical
composition of the pillow basalt from the Kamogawa
Formation matches that of the island arc tholeiites
(Arai & Uchida, 1 978); (b) the distribution patterns
of minor and trace elements in the tholeiite of the
Kamogawa Formation and in the alkali basalt of the
Setogawa terrain coincide with those of island arc
basalts (Watanabe, 1989); (c) a dacitic tuff, >60 m
thick, is closely associated with basalts of the
Kamogawa Formation in the Mineoka Hills. On
Kuroshima Isle at the base of the pier of the
Kamogawa fishing port and in the north of Wada, it
changes to a lapilli tuff/tuff breccia, suggesting that
it erupted on the basaltic volcanic ridge ; (d) two
tectonic blocks composed of crystalline schists and
amphibolite crop out at the Kamogawa fishing port.
The pelitic to psammitic biotite schist consists of
biotite, quartz, microcline and plagioclase (Kanehira
et al. , 1968), and its K/ Ar age is 38 Ma (Yoshida,
1974). Moreover, a large float of mylonitized and
albitized biotite granite has recently been found on
Kainagisa Beach in the south of the Kamogawa
fishing port. The biotite schist and mylonitized
granite are considered to have formed the basement
of the arc volcanic ridge and to have been uplifted
together with ultramafic rock masses. We therefore
conclude that the Mineoka Umber accumulated on
the arc volcanic ridge in the suprasubduction zone
off the Japanese continental arc during the Eocene,
when the Sea of Japan was not yet open, except for a
late Oligocene embayment in the south (Iijima
et al., 1988). A very similar setting is now postulated
for the Troodos, Oman and Baer-Bassit settings.
However they are primitive arcs built up before the
genesis of major calc-alkaline edifices (Robertson &
Fleet, 1986).
CONCLUSION
The Mineoka Umber, which is mainly composed of
manganese oxides and hydrated ferric oxides,
formed during submarine hydrothermal activity that
followed basaltic volcanism. It was deposited at the
foot of an arc volcanic ridge in the suprasubduction
zone off the Japanese continental arc during the
Eocene, when the Sea of Japan was not yet open.
The temperature of the metal-carrying solution was
probably much higher than the 55-68°C of the
metal-free water from which calcite precipitated in
pores and cracks of the conduit-filling umber.
87
ACKNOWLEDGEM ENTS
This study was partly supported by a Grant-in-aid
for Cooperative Research (A) from the Ministry
of Education, Science and Culture (Project No.
60303010). We are indebted to the Chiba-Kenzai
I ndustrial Company for permission to collect the
umber samples. We are grateful to S. Roy, B.R.
Bolton and J.R. Hein for their invaluable dis­
cussion and comments at the lAS ISOSRMD Beijing
meeting. Our thanks are due to J. Parnell, A.H. F.
Robertson and B. Pracejus for critical reading of the
typescript, H. Haramura for wet chemical analysis,
H. Matsuda for isotopic analysis, R. Matsumoto for
advice on interpretation of the isotopic compositions,
and T. Fukuhara for preparing the typescript.
R E F E RENCES
ARAI, S. & UcHIDA, T. (1978) Highly magnesian dunite
from the Mineoka Belt, central Japan. J. Japan. Ass.
Min. Petrol. Econ. Geol. 73, 176-179 .
ELDERFIELD, H . , GASS, I . G . , HAMMOND, A. & BEAR, L . M .
(1972) The origin o f ferromanganese sediments associ­
ated with the Troodos Massif of Cyprus. Sedimentology
19, 1 -19.
HASKIN , L.A. & HASKIN, M.A. (1966) Rare earths
in European shale: a redetermination. Science 145,
507-509.
lmMA, A. (1986) Occurrence of natural zeolites. Clay Sci.
26, 90-103.
IuiMA, A. , MATSUMOTO, R. & IGUCHI, T. (1981) Occurrence
and properties of the Setogawa 'Umber'. Abstracts
Paper, Geol. Soc. Japan, 235.
liHMA, A. , TADA, R. & WATANABE, Y. (1988) Devel­
opments of Neogene sedimentary basins in the North­
eastern Honshu Arc with emphasis on Miocene siliceous
deposits. J. Fac. Sci. Univ. Tokyo , Section II , 2 1 ,
417- 446.
lUIMA, A., WATANABE, Y . & MATSUMOTO, R. (1984) Geo­
logic age of the Setogawa-Mineoka Tectonic Belt. In:
Biostratigraphy and International Correlation of the
Paleogene System in Japan (Ed. by T. Saito & H. Okade),
pp. 69-74. Yamagata Univ., Yamagata.
IlZASA, K. (1988) Metasomatism in manganese
nodules. Bull. Sci. Univ. Tokyo 7, 21-24.
KANEHIRA, K. , OKJ, Y . , SANADA s . , YAKOU, K. &
ISHIKAWA, F. (1968) Tectonic blocks of metamorphic
rocks at Kamogawa, southern Boso Peninsula. J. Geol.
Soc. Japan, 74, 529 - 534.
KARPOFF, A.M., WALTER, A.V. & PFLUMIO, C. (1988)
Metalliferous sediments within lava sequences of
the Sumail Ophiolite (Oman) : Mineralogical and geo­
chemical characterization, origin and evolution. Tec­
tonophysics , 1 5 1 , 223-245.
MATSUMOTO, R . , MINAI, Y. & IIHMA, A. (1985) Manganese
content, cerium anomaly, and rate of sedimentation as
aids in the characterization and classification of deep-sea
88 A. Iijima et al.
sediments. I n : Formation of Active Ocean Margins (Ed.
by N. Nasu). pp. 913-939. Terrapub, Tokyo.
OGAWA, Y. & TANIGUCHI, H. (1988) Geology and tectonics
of the Miura - Boso Peninsulas and the adj acent area.
Mod. Ceo!. 12, 147-168.
PIPER, D.Z. ( 1974) Rare earth elements in the sedimentary
cycle: a summary. Chemical Ceo!. 14, 285-304.
RoBERTSON, A.H.F. ( 1975) Cyprus Umbers: basalt­
sediment relationships on a Mesozoic oceanic ridge. J.
Ceo/. Soc. Land. 131, 51 1-531.
ROBERTSON, A.H.F. & BoY LE, ] .F. ( 1983) Tectonic setting
and origin of metalliferous sediments in the Mesozoic
Tethys. I n : Hydrothermal Processes at Seafloor Spreading
Centres (Ed. by P.A. Rona) , pp. 595-663. NATO.
Conf. Ser. , Plenum Press, New York.
RoBERTSON , A.H.F. & FLEET, A.J. ( 1976) The origins of
rare earths in metalliferous sediments of the Troodos
Massif, Cyprus. Earth Planet. Sci. Letts 28, 385-394.
ROBERTSON , A.H.F. & FLEET, A.J. ( 1986) Geochemistry
and palaeo-oceanography of metalliferous and pelagic
sediments from the Late Cretaceous Oman Ophiolite.
Marine Petrol. Ceol. 3, 315-338.
ROBERTSON , A.H.F. & HuDSON , J.D. ( 1973) Cyprus
umbers: chemical precipitates on a Tethyan ocean ridge.
Earth Planet. Sci. Letts, 18, 93-101.
SAVIN, S . M. & YEH , H . W . ( 1981) Stable istopes in
ocean sediments. I n : The Sea. The Oceanic Lithosphere ,
Vol. 7 (Ed . by C. Emiliani) , pp. 1521- 1554. Wiley­
lnterscience, New York.
SuzuKI, Y . , KoNDO, K. & SAITO, H. ( 1984) Latest Eocene
planktonic foraminifers from the Mineoka Group, Boso
Peninsula. J. geol. Soc. Japan 90, 497-499.
TASAKI, K . , INOMATA, M. & TASAKI, K. ( 1980) Umbers
in pillow lava from the Mineoka Tectonic Belt, Boso
Peninsula (Short notes). J. geol. Soc. Japan 86,
413-416.
WATANABE, Y . (1989) Evolution of the forearc basin of the
Setogawa- Kobotoke - Mineoka Tectonic Belt, central
Japan. Unpubl. PhD Thesis, Geological I nstitute, Univ.
Tokyo.
YosHIDA, Y. (1974) Discovery of foraminifers from the
Mineoka Hills, Chiba. Chishitsu News, Ceol. Survey
Japan , 233, 30-36.
Spec. Pubis int. Ass. Sediment. ( 1990) 1 1 , 89-108

Mineralogy, geochemistry and genesis of manganese-iron crusts

on the Bezymiannaya Seamount 640, Cape Verde Plate, Atlantic

l. M . V A R E N T S O V*, V . A . D R I T S*, and A .I. G O R S CH K O Vj

1
*Geological Institute of the USSR Academy of Sciences, 7 Pyzhevsky per. , 109017 Moscow, USSR; "1nstitut e of
Ore Geology and Mineralogy of the USSR Academy of Sciences, 35 Staromonetny per. , 109017 Moscow,
USSR

ABSTRACT

Manganese-iron oxyhydroxide encrustations overgrow and impregnate hydrothermally phosphatized

Middle Eoce;1e limestones, which blanket the Bezymiannaya Seamount 640 (the Rocett Seamount) on
the Cape Verde plate. In chemical composition, the manganese-iron crusts are transitional between
hydrothermal and hydrogenetic types . The major minerals are iron vernadite and manganese feroxyhyte.
The presence of goethite, mixed-layered asbolane-buserite, magnesium asbolane, and birnessite in the
crusts is interpreted as a result of postdepositional transformations of the initial manganese-iron
oxyhydroxide material.

INTRODUCTION

Manganese- iron oxyhydroxide crusts occur on the
surface of seamounts, guyots, ridges and various
rises on the ocean floor. There is a definite distinction
between the manganese - iron oxyhydroxide crusts
of hydrothermal origin and hydrogenetic origin ,
which is evident i n the geological settings o f the
deposits and their structure, mineralogy and geo­
chemical characteristics (Crorian, 1976; Toth , 1980;
Cronan et a/ . , 1 982; Varentsov et a/ . , 1983 ; Aplin &
Cronan, 1985; Thompson et a/., 1 985; Lalou et a/.,
1986; Carlo et a/ . , 1 987). The most common, how­
ever, are the manganese-iron encrustations formed
as a combined accumulation of components of dif­
ferent genesis. An important problem in the miner­
alogy and geochemistry of oceanic manganese-iron
ore formation is the objective and substantiated esti­
mation of the contribution of hydrothermal and
hydrogenetic sources.
The studies described here were based on
materials collected during the first cruise of
RV 'Akademik Nikolai Strakhov' and on the
data of geological - geophysical studies on the
Bezymiannaya Seamount 640. The samples were
collected by a dredge and a shovel sampler.
The Bezymiannaya Seamount 640 (on some maps:
the Rocett Seamount) is situated about 750 km
west- southwest of the rise of the Cape Verde
Islands, a large volcanic structure of the Cape Verde
plate composed of oceanic crust of early Cenozoic
(Palaeogene) age. The base of the Bezymiannaya
Seamount 640 lies at depths of 4500- 5000 m, and
the top of the seamount is at 640 m. This rise is a
submeridionally oriented block of oceanic crust
about 74 km long. According to subsea photography
and sample collection , the seamount surface is
covered with moderately lithified limestones of
lower Middle Eocene age. Moreover, the lime­
stones exhibit an increasingly shallow-water
character towards the top of the seamount. The
hydrothermal alteration of limestones irregularly
increases in the same direction (recrystallizatio n ,
silicification, phosphatization, etc) . The intensity
of formation of the manganese- iron oxyhydroxide
crusts increases from the middle part of the slopes
towards the top (Fig. 1 ) .
METHODOLOGY
The samples were studied in thin section under the
microscope, and by X-ray diffraction and other

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun 89

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
90 I. M. Varentsov, V . A . Drits and A./. Gorschkov

m
STn39

5 15 25 35 45 47.41 km

lt'\�;e1h �2 �31tli141e¥1s
r 16 !II]y rz=lal-· _:_.=-Jgjv v v 11o
Fig. 1. Sublatitudinal lithological profile across the central part of the Bezymiannaya Seamount 640. Arrows show stations
of sample collection (dredge). (1) Biogenic limestone: (2) biogenic limestone with relatively weak alteration; (3) altered
limestone; (4) altered limestone, rudaceous; (5) altered limestone with manganese-iron oxyhydroxide crusts on bedding
planes; (6) manganese-iron oxyhydroxide crusts; (7) modern coral structures; (8) foraminiferal sand; (9) silty mud; and
(10) basalt.

physical methods of analysis (Varentsov et al., 1989).
The study of mineral composition was much more
effective using electron microdiffraction, in combi­
nation with microprobe energy dispersive X-ray
(EDX) analysis.
The chemical composition of samples was deter­
mined by classical wet chemical analysis combined
with the plasma spectroscopy of small masses (about
0· 1 g) . Heavy metals and trace elements were de­
termined by emission spectroscopy. High concen­
trations of cobalt, antimony and silver were deter­
mined by instrumental neutron activation analysis.
GEOLOGICAL SETTING, STRUCTURE,
AND MINERAL COMPOSITION
Three stations (34, 38 and 39) were selected for
the study of m ineralogy and geochemistry of
manganese - iron oxyhydroxide crusts and of changes
in the substrate rocks (Fig. 1 ) . The description of
samples, hauled at these stations, and their mineral
compositions are given in the captions to Figs 2a,b
and 3a,b. Moreover, the structural and crystallo­
chemical characteristics of the manganese- iron oxy-
hydroxide minerals discussed below are given in a
previous paper (Varentsov et al., 1989 ) .
1 Station 34 was set up on the eastern slope of the
Bezymiannaya Seamount 640 with coordinates
1 5°51-0'N, 36°07 ·0'W 1 5°50·0'N , 36°08·0'W; the
depth interval was 2 100- 1400 m. Blocks of altered
phosphatized limestone were torn off the parent
deposit and collected; they are covered with a crust
50- 100 mm thick and intensively impregnated by
manganese - iron oxyhydroxides. Samples 1 -34-D-1-
1 1 5-(A) (Fig. 2a) and 1-35-D-1 1 5-(2) (Fig. 3a) were
selected for detailed study of mineralogy and
geochemistry as characteristic manganese -iron
crusts and typical substrate rocks.
2 Station 38 (Fig. 1) is located at the top western
part of the Bezymiannaya Seamount 640 with coor­
dinates 1 5°51-s'N and 36°09·7'W. Blocks of deeply
altered bioclastic limestones were torn from the
parent rock; they are up to 400 mm in size with an
uneven lumpy surface covered with crust growths of
manganese- iron oxyhydroxides.
3 Station 39 (Fig. 1) is at the top of the Bezymian­
naya Seamount 640. A plate-like block (200 x
700 mm) was broken off the parent deposit by a
dredge; the block is composed of manganese - iron
 Manganese- iron crusts, Bezymiannaya Seamount 640 91

1-34-D-1-115-A
(a)

Fig. 2. (a) Structure of manganese-iron oxyhydroxide crust on altered substrate, a recrystallized, phosphatized limestone.
Sample 1-34-D-1-115-(A), the Bezymiannaya Seamount 640. a, the upper finely botryoidal crust (40 mm), black
manganese-iron oxyhydroxides with ochre (iron oxyhydroxides) and white cavities filled mainly with relict material
residual after limestone dissolution . The material is mostly represented by manganese feroxyhyte, iron vernadite and
subordinate quantities of goethite. b, relics of substrate represented by white recrystallized phosphatized limestone. c,
black, dull, sooty manganese-iron oxyhydroxides impregnating substrate (40-80 mm) . They are represented mostly by
iron vernadite, manganese feroxyhyte and subordinate amounts of goethite. The presence of relict patchy areas of the
substrate is characteristic (see b ) . d, patches and lens-like areas of ochrous material which is a rather early product of
substitution (b ) embedded in the mass of manganese-iron oxyhydroxides (c). They are represented by goethite,
manganese feroxyhyte, an almost isotropic iron X-phase, probably vernadite, calcite, with admixtures of kaolinite, traces
of chlorite, francolite and hydroxyl apatite.
(b) Structure of crust of manganese-iron oxyhydroxides on altered substrate, a hydrothermally reworked (intensively
phosphatized) limestone. Sample 1-39-D-126, the Bezymiannaya Seamount 640. a, the upper crust of manganese-iron
oxyhydroxides with rough botryoidal surface (20 mm). The material contains mostly iron vernadite and manganese
feroxyhyte with an admixture of goethite. b, a part of manganese-iron oxyhydroxide crust with microlayered structure
(10-15 mm). Iron vernadite dominates with a somewhat subordinate amount of manganese feroxyhyte and admixture of
goethite. c, a shiny, massive, dense, rather homogeneous material of manganese-iron oxyhydroxides (10-20 mm)
composed predominantly of iron vernadite with lesser amounts of manganese feroxyhyte, admixture of goethite, and rather
small quantities of mixed-layered asbolane-buserite. d, intensively reworked material of initial limestone almost entirely
composed of phosphates; it is locally intensively impregnated and substituted by manganese-iron oxyhydroxides (20 mm).
d-1, phosphate (hydroxyl apatite and francolite) interlayer intensively impregnated by manganese-iron oxyhydroxides
(10 mm). e, the lower crust composed of loose sooty manganese-iron oxyhydroxides (20 mm). Iron vernadite and
manganese feroxyhyte dominate with admixture of goethite and very small amounts of mixed-layered asbolane-buserite.
 No 1-34-D-115 (2)
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�3�4
X X X X X
X X X fR X X X j,J/ZlJ ))1 �
x x
x x x x x x x x x
x x x x x x x x �8 �
.,
�
.,
x x x x x x x x x x
;:s

X
X XX X
X yoH r - APT
FR
X
X
X
X
X
X
X
�788 1)5
"'
I
�·
�10 ;:s
(")
i2
"'

� ���*! _o:;
� 11 p* 12 i;);j
�
;::!
;;·
0,635 ;:s

�
.,

Fig. 3. (a) Distribution of values of ratios AI: Ti, Si: Ti, Mn : Ti, Fe: Ti and P: Ti in the components of a crust of manganese-iron oxyhydroxides and in the
�
altered substrate, an intensively hydrothermally phosphatized limestone. Sample 1-34-D-115-(2) (Table 1); the Bezymiannaya Seamount 640. Mineral ;::!
Q
;:
composition: (1) The upper crust of manganese-iron oxyhydroxides. Manganese feroxyhyte and iron vernadite dominate with subordinate amounts of goethite
and traces of quartz. (2) The lower crust of manganese-iron oxyhydroxides. The major components are manganese feroxyhyte and iron vernadite with subordinate ;;
amounts of goethite and admixture of mixed-layered asbolane-buserite. (3) Altered cream-coloured rock (phosphatized limestone) confined in the limestone 0\
mass. The material is represented by calcite and francolite with admixture of hydroxyl apatite. (4) Altered cream-coloured fragments of breccia (recrystallized �
phosphatized limestone with admixture of kaolinite and siliceous material). Major components are calcite with admixture of kaolinite, traces of mica, chlorite,
francolite and hydroxyl apatite. (5) Phosphatized basalts, the Cruiser Seamount (Table 1). (6) Iron vernadite. (7) Manganese feroxyhyte. (8) Goethite. (9) Mixed­
layered asbolane-buserite. (10) Calcite. (11) Francolite. (12) Hydroxyl apatite. (13) Kaolinite.
(b) Distribution of values of ratios AI: Ti, Si: Ti, Mn: Ti, Fe : Ti and P: Ti in the components of a crust of manganese-iron oxyhydroxides and in the altered
substrate, an intensively hydrothermally phosphatized limestone. Sample 1-38-D-124; the Bezymiannaya Seamount 640. Mineral composition: (1) The upper crust
of manganese-iron oxyhydroxides (2-15 mm). The major phases are iron vernadite, manganese feroxyhyte, magnesium asbolane with subordinate amounts of
mixed-layered asbolane-buserite and admixture of goethite and traces of birnessite. (2) The lower crust of manganese-iron oxyhydroxides (2-15 mm). It is mostly
composed of iron vernadite with subordinate quantities of manganese feroxyhyte and asbolane-buserite and admixture of goethite. (3) Light grey-cream-coloured
material of the general mass of altered rock (intensively phosphatized limestone). The major components are francolite, hydroxyl apatite, admixture of calcite and
probably farringtonite (?). (4, 5) As (3). (6, 7) Buff-coloured veinlets of phosphate pigmented by iron oxyhydroxides. The major components are hydroxyl apatite
\0
and francolite with probable admixture of hureauLite and brushite. (8) Iron vernadite. (9) Manganese feroxyhyte. (10) Magnesium asbolane. (11) Mixed-layered
asbolane-buserite. (12) Goethite. (13) Birnessite. (14) Hydroxyl apatite and fancolite. VJ
94 I. M. Varentsov, V.A. Drits and A.!. Gorschkov
oxyhydroxides (80-90% ). The middle part of the
plate contains finely grained phosphatized rock with
typical white, rose- and orange-coloured patches
and local patches of unaltered bioclastic limestone
(Fig. 2b).
GEOCHEMISTRY
Distribution of titanium, aluminium and silicon
It has been established that in manganese - iron
oxyhydroxide crusts of hydrogenetic origin (Ridout
et al. , 1984; Aplin & Cronan , 1985; Hein et a!.,
1988) the titanium content reaches 0·34-0·48% ,
whereas in the hydrothermal manganese - iron oxy­
hydroxides (Cronan, 1976; Toth, 1980; Varentsov et
a/ . , 1983) the titanium concentration is no more than
0 · 1 % (at aluminium up to 0· 1 -0·3% ) . In the ana­
lysed crusts the content of titanium changes from 0·6
to 1 · 1 % and that of aluminium reaches 2·43% . In
the light of these data, the higher titanium and
aluminium values characterize them as residual from
the dissolution of the substrate. This conclusion is
on the whole also true for silicon (Figs 3a,b; Tables 1
and 2). There is a well-defined tendency for the
intensity of accumulation of manganese- iron oxy­
hydroxide growths to increase towards the top of the
seamount. The thickness of manganese -iron oxy­
hydroxide growths is directly controlled by the in­
tensity of hydrothermal alteration of limestone and
its phosphatization which develops irregularly and
by patches, as shown in Figs 2 and 3.
Analysis of aluminium-manganese relationships
The analysis of aluminium-manganese relationships
(Tables 1 and 2; Fig. 4) and their comparisons with
data on hydrothermal and hydrogenetic crusts and
nodules allow us to identify three major genetic
fields from the correlation diagram: (I) the field of
hydrothermal accumulations with extensive vari­
ations of manganese-iron contents but extremely
low aluminium concentrations, less than 0·25%
(Cronan, 1976; Toth, 1980; Cronan et al., 1982;
Varentsov et al. , 1983); (II) the field of points
corresponding to manganese-iron oxyhydroxide
deposits of the intermediate group between the
hydrothermal and hydrogenetic crusts; (III) the
field of hydrogenetic crusts whose boundary is drawn
tentatively along the line of the aluminium concen­
tration value of more than 2·5% . Therefore , accord­
ing to aluminium- manganese relations, the man-
ganese-iron oxyhydroxide crust accumulations
belong to deposits whose appearance was essentially
affected by hydrothermal processes. At later stages,
these deposits experienced a hydrogenetic influence,
as distinctly shown in the trend of the continuum
from hydrothermal deposits to hydrogenetic ones
(Fig. 4).
The manganese : iron ratios
The manganese: iron ratios in oxyhydroxide growths
vary within a limited range and normally are close to
1 · 0 (Tables 1 and 2; Fig. 5). In the studied samples
the lower or bottom crusts are either slightly more
ferruginous than the upper ones or insignificantly
different.
It should be emphasized that laterally the total
manganese content of crusts increases towards the
top of the seamount accompanied by the general
rather deep substitution and intensive development
of oxyhydroxide phases. Thus, about three-quarters
of the initially limestone plate (Fig. 5) is made up of
manganese and iron compounds, the remaining part
being composed of the phosphate material which
almost entirely substitutes the bioclastic limestone.
The distribution of ratios Ni : Mn, Cu : Fe, Ba : Ti
The behaviour of heavy metals in the process of
crust formation can be illustrated by the distribution
of Ni : Mn and Cu: Fe ratios in the crusts. This
distribution is characterized by the absence of any
considerable variations, as can be shown by the
representative example near the top station 39
(Fig. 1 ) where manganese, iron and phosphate
mineralization are most intensive.
Unlike heavy metals, the B a : Ti distribution
clearly shows an increase in this ratio from the
surface layers to the lower parts of the crust on the
boundary with the phosphatized substrate , for ex­
ample in sample 1-39-D-126 (Fig. 5) . As in the
manganese-iron crusts from the Krylov Seamount,
also situated on the Cape Verde Abyssal Plate of the
eastern Atlantic (Varentsov et al., 1989), such re­
lations may imply the lessening of the role of hydro­
thermal components in ore-bearing solutions, which
are mixtures of hydrothermal water and seawater, at
the late stages of accumulation.
Analyses of nickel-manganese relationships
From the analysis of nickel-manganese relation-
Table 1. Chemical composition of manganese-iron crusts and the altered substrate (an intensively hydrothermally phosphatized limestone): samples 1-34-D-1-115-(A); 1-34-D-115-(2); the
Bezymiannaya Seamount 640; and of alkalic basaltoids of the subsea Cruiser Rise, Cape Verde Plate, eastern Atlantic (major components: wt%; heavy metals: ppm)

Sample 1-34-D-1-115-(A) l-34-D-115-(2) Cruiser Seamount

Component a b c d a b c d 2 4 6 7 8

Si 1·457 2·414 0·948 10·816 1·733 1-485 0·658 4·128 16·168 17-335 9·317 9·826 12·646
Ti 0·839 0·078 1·012 0·623 1·003 0·839 0·012 0·108 1·677 1·725 1-414 0·91 1·725
AI 1·09 1-19 0·984 3·544 1·264 1-428 0·587 2·343 8·157 8·205 5·517 4-772 8·131
Fe (total) 18·345 1·021 13-575 14·89 16·925 18·471 0·2798 1·322 15·762 12·98 13·908 13·91 17·153
Mn (total) 16·889 0·31 12·7 10·207 16·913 16·301 0·194 0·279 0·108 0·093 0·186 0·403 0·155
Mg 1·152 0·88 1-14 1·387 1·315 1·345 0·386 0·808 2·466 2·714 1·236 1·236 0·494
Ca 2·209 34·034 11·133 1·716 2·567 1·952 37·051 30·774 4·683 6·921 16-481 16·688 6·099
p 0·271 0·323 0·546 0·362 0·34 0·34 3·073 0·253 0·55 0·681 4·679 4-452 1·397
Na 1·091 0·378 1·469 1-195 1·573 1·247 0·297 0·252 2·404 1·974 1-491 1·603 2·1
K 0·274 0·241 0·208 0·697 0·232 0·241 0·116 0·49 0·697 0·697 0·739 0·78 0·863
Fe3+ - - - - - -
13-904 11·449 11·498 11·715 16-492
Fe2+ - 1·858 1·531 2·4096 2·192 0·661
Mn2+ 0·139 0·341 0·07 0·163 0·108
Mn4+ 16·752 12·36 10·155 16·752 16·196
Ba 0·116 0·009 0·081 0·072 0·108 0·116 0·125 0·018
Ni 0·22 0·008 0·157 0·252 0·212 0·354 0·008 0·016
Cr <65 <65 <65 <65 <65 <65 <65 <65
v 350 <50 315 310 300 370 <50 <50
Cu 120 <65 <65 230 140 200 <65 <65
Co >1000 135 >1000 >1000 >100 >1000 <50 78
Co* 7385 103·0 9157 2150 80·0 6425 14·3 60·7
Pb >1000 <50 = 1000 410 >1000 >1000 <50 <50
Ga <55 <55 <55 <55 <55 <55 <55 <55
Mo >110·0 6-4 >110·0 >110·0 >110·0 >110·0 6·0 6·3
Mn:Fe 0·92 0·30 0·94 0·69 1·00 0·88 0·69 0·21
Sb* 49-4 63-1 52·8
Ag* 0·52 0·22 -
4·3

The characteristics of components of manganese-iron oxyhydroxide crusts and of the substrate, a hydrothermally phosphatized limestone, samples 1-34-D-1-115-(A), 1-34-D-115-(2), are given
in captions to Figs 2a, 3a.
The chemical composition of hydrothermally altered, phosphatized alkaline basaltoids from the Cruiser Seamount, eastern Atlantic, is also given for comparison; samples 2,4,6,7,8 (data by
B.P. Zolotarev and Y.A. Eroschev-Shak).
* Determinations by instrumental neutron activation analysis.
 \0
a-

Table 2. Chemical composition of iron-manganese crusts and of altered substrate (an intensively hydrothermally phosphatized limestone); samples 1-38-D-
124: 1-39-D-126; the Bezymiannaya Seamount 640, Cape Verde Plate, eastern Atlantic (major components: wt%; heavy metals: ppm)

Sample 1-38-D-124 1-39-D-126

Component a b c d a b c d e

Si 0·602 0·85 0·299 1·196 0·99 0·794 0·822 1·597 1·139

Ti 0·635 0·701 0·018 0·03 0·928 0·701 0·635 0·252 1·03 :--
AI 0·926 1·016 0-460 0·783 0·92 0·577 0·608 1·106 1·01 s:
Fe (total) 13·275 15·135 0·546 6·064 17·198 14·534 15·282 5·861 15·988
Mn (total) 21·022 20·705 0·194 0·317 18·003 20·937 20·975 4·327 18·22 �
....
Mg 1·592 1·658 0·507 0·627 1·254 1·278 1·14 "'
;::,
0·724 1·375
Ca 4·254 2·724 35·435 31·56 2·159 2·488 2·36 27·485 2·638 <:;;-
p 0·71 0-445 15·14 11·58 0·345 0·395 0·32 10·945 0·34 a
·""'
Na 1·425 1·373 1·514 1·158 1·217 1·313 1·202 0·934 1·514
K 0·299 0·315 0·149 0·307 0·241 0·299 0·274 0·291 0·257 :<:::
Fe3+ 0·266 �
Fe2+ - - 0·28 - \:::1
Mn2+ 0·163 0·116 0·147 0·062 0·139 0·217 0·108 :::!.
- <:;;-
Mn4+ 20·872 20·59 17·87 20·891 20·84 4·114 18·123
Ba 0·143 0·134 0·009 0·116 0·143 0·143 0·036 0·108 �
Ni 0·354 0·346 0·008 0·008 0·322 0·322 0·307 0·149 0·275
�
�
-
Cr <65 <65 120 <65 <65 <65 130 <65
v 320 325 <50 - 325 315 340 130 310 (1000)
()
a
Cu <65 <65 <65 <65 <65 <65 <150 <150
Co >1000 >1000 <SO >1000 >1000 >1000 >1000 >1000 �
"
Co* 14134 12745 19·2 82·9 11256 12980 12644 1947 11739 ;::-
;>;-
Pb >1000 >1000 <50 >1000 >1000 >1000 340 >1000 a
Ga <55 <55 <55 <55 <55 <55 <55 <55 ""'

Mo >110·0 >110·0 <6·0 >110·0 >110·0 >110·0 46·5 >110·0

Mn : Fe 1·58 1·37 0·36 0·05 1·05 1-44 1·37 0·74 1-14
Sb* 14·5 16·1 71·9 15·0
Ag* 0·013

Characteristics of components of manganese-iron oxyhydroxide crusts and of the substrate, a hydrothermally phosphatized limestone, are given in
captions to Figs 3b and 5; samples 1-38-D-124; 1-39-D-126.
* Determinations by instrumental neutron activation analysis.
 Manganese- iron crusts, Bezymiannaya Seamount 640 97

Mn (/o,wr)
60.0
f. 0
2. @)
J. t:,.
4. 11£,
5. 0
6. 0
40,0 7. •

8. @
9. ®
I· I 10. •
.30.0
11I· '
'
I II. &.
Iq ll\ j ill
I ' X 12. �
II ',
_
_
I 13. -·-·-

20,0
i�
. 1 41. l-·---
I
14. -x-x-x

I��
\ 1
X
I 0'........
•

I
X •
10.0 0
• ....._

I y ....
J
I
X

I
.,x

(0 2.0 4,0 6.0 8,0 10,0

Al(/o, wr)
Fig. 4. Aluminium-manganese relationships in the components of crusts of manganese-iron oxyhydroxides and in the
altered substrate, an intensively hydrothermally phosphatized limestone. Samples: 1-34-D-1-115-(A); 1-34-D-115-(2); 1-38-
D-124; 1-39-D-126 (Tables 1 and 2), the Bezymiannaya Seamount 640. The data on hydrothermal and hydrogenetic
manganese oxyhydroxide crusts and diagenetic nodules of the ocean are shown for comparison (Cronan, 1976; Cronan
eta!., 1982; Toth, 1980). (1) Components of crust of manganese-iron oxyhydroxides; sample 1-34-D-l-115-(A) (a, c, d).
(2) Substrate, phosphatized limestone; sample 1-34-D-1-115-(A) (b). (3) Components of crust of manganese-iron
oxyhydroxides; sample 1-34-D-115-(2) (a, b) . (4) Substrate, components of phosphatized limestone; sample
1-34-D-1-115-(2) (c, d) . (5) Phosphatized alkalic basalts; the Cruiser Seamount, eastern Atlantic. (6-8) Manganese
oxyhydroxide crusts and nodules from the ocean (Cronan, 1976; Cronan et al., 1982; Toth, 1980): 6-hydrothermal; ?­
hydrogenetic; 8-diagenetic. (9) Components of crust of manganese-iron oxyhydroxides; sample 1-38-D-124 (a, b). (10)
Components of the substrate, a phosphatized limestone; sample 1-38-D-124 (c, d) . (11) Components of crust of
manganese-iron oxyhydroxides; sample 1-39-D-126 (a-c, e). (12) Substrate, a phosphatized limestone; sample 1-39-D-
126 (d). Fields of manganese-iron oxyhydroxide crusts: I-hydrothermal; II-mixed; III-hydrogenetic. (13) Borderline
of hydrothermal crust field. (14) Borderline of hydrogenetic crust field.

ships (Fig. 6) the fields of hydrothermal ( I ) , tran­

sitional (II), and hydrogenetic ( I I I ) crust growths
are distinctly separated on the correlation diagram .
The studied components o f manganese -iron crusts
of the Bezymiannaya Seamount 640 belong to de­
posits of intermediate origin. These crust growths,
which were formed under a strong hydrothermal
influence, have experienced extensive hydrogenetic
effects, i . e. the accumulation of heavy metals from
the bottom seawater.
Geochemical behaviour of cobalt
The geochemical behaviour of cobalt displays two
well-expressed tendencies: (a) clear association with
manganese; and (b) increasing cobalt concentration
with decreasing of water depths, i.e. towards the
summit areas of the seamount (see Tables 1 and 2).
Similar contents of cobalt and manganese were re­
ported from the seamounts of the central Pacific
(Aplin & Cronan , 1985; Hein et al. , 1988).
 1-39-D-126

Mn/Fe Ni/Mn Cu/Fe Ba/Ti

0 25 50 75 (%) 0 1P 2.0 0 0.02 0.04 0 0,0002 0,0006. 0 0105 0.10 0.15
lv<:A:>. I I KAXA1 I • lv<?vl I I
0.20
bvv<t1 1
I

-1 �2
�3 .4
ITJii]5 �6
��f:��1tl7
X
X
)(
X

)(
X
"GEclx x
X
X FR
1fr,4 1 .. Ill�
fiiif
X X X

X
X

X
)(

X g9
-APT X X
X X X OH
X )(
x x x
)( )( _}(_
x

){X.
x x x x
BFrF1I
�11
�X
)( X
X X X )( X ? ? ?
){ " X )(

Fe - VRT JLJ!.
11 �B) Mn·F
ii""F*

I' �

�u·ut.t
Fig. 5. Distribution of values of Mn: Fe, Ni: Mn, Cu: Fe and Ba: Ti ratios in the components of the crust of manganese-iron oxyhydroxides and in the altered
substrate, an intensively hydrothermally phosphatized limestone. Sample 1-39-0-126 (Table 2); the Bezymiannaya Seamount 640. Mineral composition: (1-6) (see
Fig. 2b). (7) Iron vernadite. (8) Manganese feroxyhyte. (9) Mixed-layered asbolane-buserite. (10) Goethite. (11) Francolite and hydroxyl apatite.
 Manganese- iron crusts, Bezymiannaya Seamount 640
Distribution of antimony and silver
The distribution of antimony and silver reveals con­
siderable association with manganese and increasing
concentrations towards the summit areas (see Tables
1 and 2). It is of interest that values of antimony and
silver concentrations are several times higher than
the average contents of these metals for oceanic
manganese- iron nodules and crusts.
GENESIS
Accumulation of manganese-iron oxyhydroxide
crusts
Crusts , patches, deep impregnation by manganese­
iron oxyhydroxides of phosphatized calcareous
rocks, covering like a blanket the alkalic basalts of
the Bezymiannaya Seamount 640, are extensively
distributed on this topographic high. The intensity
of development of crust growths increases from the
middle part of the slopes (station 34; Figs 1 , 2 and
3), where their thickness seldom exceeds 2-40 mm,
to the top of the seamount (station 39; Figs 1, 2b and
5) , where their thickness is no less than 60- 1 00 mm.
The crusts are composed of globular and micro­
layered accumulations of manganese -iron oxyhy­
droxides (Figs 7 and 8) . These formations are poss­
ibly the products of substitution of the calcareous
deeply phosphatized substrate: the mass of oxy­
hydroxide patches distinctly contains relics of
foraminiferal shells, nannofossils and other bio­
detritus. The relationship between the formation of
crust accumulations and manganese-iron oxy­
hydroxide patches and dissolution of limestones is
also manifested in relatively higher titanium and
aluminium contents which represent residual matter
after dissolution (Tables 1 and 2). It is important to
note that the formation of phosphates, represented
mostly by francolite and, to a lesser degree, by
hydroxyl apatite, is associated with earlier hydro­
thermal alterations of limestones in the substrate
which preceded the massive deposition of man­
ganese-iron hydroxides. Phosphatization of basalts
of the substrate is also observed in other regions of
the Cape Verde plate (the Cruiser Rise, the Krylov
Seamount).
Accumulation of manganese- iron oxyhydroxides
occurred as a result of hydrolythic precipitation ac­
companied by autocatalytic oxidation in the process
of adsorption of transition metals involving micro-
99
biological phenomena. These processes took place
during the mixing of hydrothermal solutions with
near-bottom or interstitial seawater (Varentsov &
Pronina, 1973; Craig, 1974; Varentsov, 1976;
Varentsov et al. , 1979a ,b, 1983).
The values of Ba : Ti ratios perceptibly decrease
from the lower interlayers to the surface parts of the
crust accumulations (Fig. 5) . The M n : Fe ratios can
be regarded as an indicator of Eh and pH gradient.
These ratios are distinctly different in various parts
of the crust deposit on the Bezymiannaya Seamount
640. The values are rather low for the crusts of
the middle part of the slope (station 34, Mn : Fe-
0·685: 0·999 , average 0·885; Table 1) but are higher
near the top (station 39, Mn : Fe- 1 ·047: 1 · 584, av­
erage 1 · 326; Table 2). The comparison of these data
leads to the conclusion that towards the summit of
the seamount pH and Eh values notably increase ,
affecting the composition of crust growths.
The Mn : Fe ratios are fairly close to those of the
seamounts of the Cape Verde plate (Varentsov et
al., 1989); they are observed in oxyhydroxide crusts
from the hydrothermal field 'TAG' which is a part of
the Mid-Atlantic Ridge at 26°N (Lalou et al., 1986).
Lalou et al. ( 1986) demonstrated that the tempera­
ture of hydrothermal sources increases with depth ,
with a concomitant increase in iron content. If the
total hydrothermal activity covered the time interval
from 20 to 4 kyr, then the manganese oxyhydroxide
deposition continued from 16 to 4 kyr, which means
that during the interval from 20 to 16 kyr an accumu­
lation of iron compounds predominated. These
data present evidence of a distinct separation of
manganese and iron in the transport by hydro­
thermal solutions mixed in variable proportions with
seawater, both in time and laterally, in the process
of movement of the Cape Verde Plate towards the
African continent.
The hydrothermal activity was particularly inten­
sive during the accumulation of relatively old inter­
layers of manganese - iron oxyhydroxide crusts at
the time when this part of the Cape Verde Plate was
near the axial zone of the Mid-Atlantic Ridge. A
hole drilled on the Mid-Atlantic Ridge south of the
Kane transform fault passed through a sequence of
volcanic rocks in the field of active hydrothermal
activity (Detrick et al., 1 986) . This is another case of
intensive manganese - iron oxyhydroxide mineraliz­
ation and extensive activity of the 'black smokers' in
the zone of the Mid-Atlantic Ridge marked by
massive accumulation of iron, copper and zinc
sulphides. A similar situation might also have oc-
100 J. M. Varentsov, V . A . Drits and A.l. Gorschkov

Ni
('fo, wr.)
@ 1. 0
f,OO 2. @
3. 8
't. �
5. (:;
I
6. •
I
0,75 7. @
I
8. @
I
I 9, @
I
I I 10. A
I I II. �
I I
0,50 12.
I I ][ 13. -x-x-x-
I
-x x x x x x x �x x� x ,x x x x x x x x x x x x �
- - - - - - - - - - - - - - - - - - - - -

//8� iLl
/
/ A? 1I
0.25 /0
8/ /
/
/ 0
-/-if.-.-.- 0;;- L - · - - - .-.- . -.- -
· ·-. .-.-.-. . . · ·-

/ /
/ l
/
/

10.0 20,0 30,0 40.0 50,0

Mn ("/o,wr.)

Fig. 6. Manganese-nickel relationships in the components of crusts of manganese-iron hydroxides and in the altered
substrate, an intensively hydrothermally phosphatized limestone . Samples: 1-34-D-1-115-(A); 1-34-D-115-(2); 1-38-D-124;
1-39-D-126 (Figs 2-5; Tables 1 and 2). The Bezymiannaya Seamount 640. The data on hydrothermal and hydrogenetic
manganese-iron crusts and diagenetic nodules of the ocean are shown for comparison (Cronan, 1976; Toth, 1980; Cronan
eta!., 1982). (1) Components of manganese-iron oxyhydroxide crust; sample 1-34-D-1-115-(A) (a, c, d) . (2) Substrate, a
phosphatized limestone; sample 1-34-D-1-115-(A) (b). (3) Components of manganese-iron oxyhydroxide crust; sample 1-
34-D-115-(2) (a, b). (4) Substrate, components of phosphatized limestone; sample 1-34-D-115-(2) (c, d) . (5-7)
Manganese-iron oxyhydroxide crusts and nodules from the ocean (Cronan, 1976; Toth, 1980; Cronan et al., 1982): 5-
hydrothermal, 6-hydrogenetic, ?-diagenetic. (8) Components of manganese-iron oxyhydroxide crusts; sample 1-38-D-
124 (a, b). (9) Components of the substrate, a phosphatized limestone; sample 1-38-D-124 (c, d). (10) Components of
manganese-iron oxyhydroxide crusts; sample 1-39-D-126 (a-c, e). (11) Substrate, a phosphatized limestone; sample 1-39-
D-126 (d). Genetic fields of manganese-iron oxyhydroxide crusts; I-hydrothermal, U-mixed; III-hydrogenetic. (12)
Borderline of hydrothermal crust field . (13) Borderline of hydrogenetic crust field.

curred in the early Palaeogene when this part of the substrate rocks are shown by generalized schemes in
Cape Verde Plate was situated near that area of the Figs 3 and 5. Although the schemes represent with
axial zone of the Atlantic. considerable approximation the quantitative re­
lations of mineral phases composing individual
interlayers, nonetheless on the whole they show the
MINERAL COMPOSITION OF true relations. The comparative analysis of these
MANGANESE-IRON OXYHYDROXIDE schemes gives certain data on the distribution of
CRUSTS manganese-iron minerals both in the secti9n of the
crusts and along the profile of the Bezymiannaya
The data on the distribution of minerals m the Seamount 640 from the middle part of the slope to
manganese - iron oxyhydroxide crusts and m the the summit through stations 34-38-39 (Fig. 1).
 Manganese- iron crusts, Bezymiannaya Seamount 640 101

Fig. 7. Scanning electron micrographs of

manganese-iron oxyhydroxide crusts
(mostly iron vernadite and manganese
feroxyhyte). Sample 1-34-D-1-115-(A); the
Bezymiannaya Seamount 640 (a, b)
(Photomicrographs with increasing
magnification.) Indistinctly layered step­
like growths of manganese-iron
oxyhydroxides . (c-e) (Photomicrographs
with increasing magnification .) Growth of
small apatite crystals on the walls of
channel caverns in the mass of
manganese-iron oxyhydroxides .
Fig. 8. Scanning electron micrographs of manganese-iron oxyhydroxide crusts (mostly iron vernadite and manganese
francolite). Sample 1-34-D- 1- 1 15-(A). The Bezymiannaya Seamount 640. (a) Small crystals of apatite growing on the
surface of channel microcavities in the mass of manganese-iron oxyhydroxide crust . (b) Crystallization of a fine
microlayered structure of manganese-iron oxyhydroxide crust with local caverns and globular texture. (c and d)
Indistinctly microlayer�d structure of manganese-iron oxyhydroxide crust. (e) Areas of intensive development of
microcavernous porosity in indistinctly layered mass of manganese-iron oxyhydroxide crust (relict products of limestone
dissolution and its substitution by manganese-iron oxyhydroxides). (f) Remnants of coccoliths, and a part of manganese­
iron oxyhydroxide crust with globular texture.
 Manganese- iron crusts, Bezymiannaya Seamount 640
1 In all studied samples (except sample 1-38-D-124;
Fig. 3b) the upper crust interlayers 2-7 to 30-
35 mm thick are composed mostly of manganese
feroxyhyte and iron vernadite with subordinate
amounts of goethite.
2 I n the lower and therefore older crust interlayers
lying directly on the substrate (deeply phosphatized
limestone), the relative quantities of manganese
feroxyhyte are perceptibly less and of iron vernadite
are greater than in the surface interlayer. Moreover,
these old interlayers show the presence of asbolane­
buserite, a mixed-layered mineral.
3 It is of interest to note that the mineral compo­
sition of oxyhydroxide crusts , growing at the base of
plate-like blocks of altered limestones, differs from
that in the superficial parts of crusts and has an
affinity with relatively old interlayers of the crust
lying directly on the substrate (e.g. sample 1-39-D-
126, Fig. 5). The difference in the mineral com­
position of crusts growing on the top and at the base
of plates of altered limestones is manifested by
sample 1-34-D-1 15-(2) , i .e. the crust at the base
contains a notable admixture of mixed-layered as­
bolane -buserite, besides iron vernadite , manganese
feroxyhyte and subordinate amounts of goethite.
4 A special case of sample 1 -38-D-124 (Fig. 3b)
shows relatively thin (2 - 15 mm) crusts composed of
a fairly wide set of minerals. The major phases of
the upper crust are iron vernadite, manganese fer­
oxyhyte, magnesium asbolane , subordinate amounts
of mixed-layered asbolane - buserite, goethite and
traces of birnessite. The composition of the lower
crust is somewhat different: iron vernadite domi­
nates and manganese feroxyhyte is in subordinate
quantities.
In order to know how the change in mineral
composition of microlayers of oxyhydroxide crusts is
connected with the variations of components ac­
cumulated in the course of depositional history and
how significant are the postdepositional transform­
ations, it is necessary to take into account the geo­
chemistry of manganese, iron and other elements
(Tables 1 and 2).
In most cases the manganese and iron content
rather insignificantly changes along the section of
the crusts , and normally Mn : Fe is close to 1 . In the
intervals of crust sections, which show perceptible
variations of Mn : Fe ratio (e.g. sample 1-39-D-
126 from the top part of the seamount, in which the
surface layer 0-20 mm thick (a) has Mn : Fe =
1 ·047 , whereas an interlayer 20-35 mm thick
(b) has Mn : Fe = 1 ·44 1 ) , these variations reflect
103
an increase in the relative quantity of iron verna­
dite and a corresponding decrease 111 manganese
feroxyhyte.
In previous research (Varentsov et a!. , 1989) ,
fairly detailed crystallochemical characteristics of
iron vernadite, manganese feroxyhyte and other
minerals were given. We should mention only the
major aspects which are necessary to discuss the
postdepositional changes.
Iron vernadite
I n typical hydrogenetic crusts the accumulation rates
of manganese -iron oxyhydroxides which produce
iron vernadite are, as a rule , rather low. Iron ver­
nadite is a mineral which experienced minimal
postdepositional alteration .
Manganese feroxyhyte
The manganese feroxyhyte structure is described by
Chukhrov et a/. ( 1975, 1976) and Varentsov et a/.
( 1 989). The energy dispersive spectra of the studied
particles record the presence of iron and manganese
(at Fe > Mn) thus giving grounds to call this phase
manganese feroxyhyte. It has been established that
feroxyhytes (o'-FeOOH) are relatively unstable
products of fairly rapid oxidation of Fe2 + in weakly
alkalic or weakly acid media which transform into
goethite in an oxidizing environment (Chukhrov et
al. , 1975; Murray, 1979). The observed maximal
quantities of manganese feroxyhyte in the surface
interlayers (in this case 'a' interlayer 0-20 mm
thick) of rather thick crusts (e.g. sample 1-39-D-
126, Figs 2 and 5) can be interpreted in this context,
as can the presence of subordinate amounts of
goethite. The experiments have shown (M urray,
1979) that the formation of goethite ( cx-FeOOH) as
a result of direct oxidation of Fe2+ or hydrolysis of
Fe3+ is hardly probable in subsea near-bottom
conditions or in the area of hydrothermal vents,
because the synthesis of this mineral is inhibited by
the presence of Cl - ions in the system. Therefore ,
the reduction of quantities of this phase in older
interlayers of crust growths, caused by the relative
instability of manganese feroxyhyte, results in a
respective increase of relative quantities of goethite
and other minerals, which shall be discussed later.
Mixed-layered asbolane-buserite
In the manganese- iron oxyhydroxide crusts the
104 I. M. Varentsov, V . A . Drits and A.!. Gorschkov

mixed-layered asbolane- buserite phases dominate
only in the lower relatively old interlayers of rather
thick crusts (e.g. interlayer 'c' is 35-65 mm thick;
sample 1-39-D- 126; Fig. 2b). They are also ob­
served in most of the bottom crusts (Figs 3a and b ) ,
o r i n the crust growths (2- 15 mm) , which experi­
enced notable postdepositional alterations (Fig. 3a) .
It can be supposed that the mixed-layered asbolane ­
buserite mineral was formed as a result of trans­
formations of iron vernadite in the process of
dehydration and aging of the oxyhydroxide material
of the crusts. This process is stimulated by the
presence in vernadite of relatively long two­
dimensional fragments, which can be regarded as
nuclei of octahedral Mn4 + layers. Moreover, the
mixed-layered asbolane- buserite should be con­
sidered as one of the early products of diagenetic
mineral formation. It is natural to suppose that the
mixed-layered mineral preceded the formation of
birnessite (Chukhrov et al. , 1987 ) , which perhaps
appeared later than buserite( I ) . Although the latter
was not found in the studied crusts, its presence in
this series of transformations is highly probable.
Asbolanes
The structure of the minerals of this group is de­
scribed in a number of papers (Chukhrov et al. ,
1983a ,b, 1987).
Perceptible amounts of magnesium asbolane
(Fig. 3b) were identified in the upper thin crust (2-
15 mm) accompanied by iron vernadite, manganese
feroxyhyte and mixed-layered asbolane-buserite.
There are grounds to suppose that the observed
magnesium asbolane is the product of solid phase
transformations occurring in the following suc­
cession : iron vernadite (manganese feroxyhyte?)
----> buserite(I) ----> mixed-layered asbolane-buserite
vernadite and manganese feroxyhyte. It was also
noted that the existence of the intermediate vanished
buserite( l ) phase, preceding the formation of
mixed-layered asbolane -buserite and magnesium
asbolane, can be assumed. The presence of birnessite
in this sample is also evidence in favour of this
assumption.
THE MODEL OF FORMATION OF
MANGANESE -IRON CRUSTS
AND NODULES
In previous papers (Varentsov & Pronina, 1973;
Varentsov, 1976; Varentsov et al. , 1979a, b ;
Varentsov e t al. , 1989) i t has been noted that man­
ganese -iron oxyhydroxide crusts are extremely
important for the understanding of the processes of
formation of oceanic ores since they are relatively
simple deposits. The relative simplicity of crust
structure and the often clearly delineated stratifi­
cation offer possibilities for the study of the evolution
of the ore-forming medium and of the succession of
postdepositional transformations of manganese­
iron oxyhydroxides (Shterenberg et al. , 1986;
Chukhrov et al. , 1987). The data discussed above on
the distribution of manganese and iron phases and
the analysis of the structural features of these min­
erals (Chukhrov et al. , 1987) produce the generalized
scheme shown in Fig. 9.
Fe + M n ( solution + suspe nsion )
t
Mn ( Ill). Mn ( !V l 0 1 - S + n · m H z O u m orph
+
Fe OO H , m H z O u orp h
m

----> magnesium asbolane (Chukhrov et al. , 1987 ) . ( n � O ·S )

Birnessite
I Mn feroxyhyte I
There are small amounts of birnessite in the studied
crusts (sample 1-38-D- 124; Fig. 3b) with pre­
dominant contents of iron vernadite, manganese
feroxyhyte and lesser quantities of magnesium as­
bolane, mixed-layered asbolane-·buserite and
I
'
Fe-ver nudite

\
fl ::::. lite-I (7 ) 1-- M ixed layered
usbolun e -
buserite

goethite. \\ '
According to the supposition expressed earlier, I G o e t h i te I I B i r ness i te I I Asbolune I
the presence in this crust of mixed-layered asbolane ­
buserite, magnesium asbolane and goethite is the Fig. 9. Generalized scheme for transformation of
consequence of diagenetic transformations of iron manganese-iron oxyhydroxide minerals.
 Manganese- iron crusts, Bezymiannaya Seamount 640
Despite obvious differences in the environments
of formation of the crusts on the seamounts and the
sedimentary-diagenetic manganese- iron nodules
from the near-Equatorial Pacific Zone (Skorniakova,
1984) , common features are established in the
formation and transformation sequences of
manganese-iron oxyhydroxide phases.
Uspenskaya et al. ( 1987, 1988) have shown that
manganese- iron concretions deposited in the radio­
larian oozes of the sublatitudinal zone between the
Clarion - Clipperton Fractures are mostly concen­
trically layered with an alternation of layers of well­
crystallized dendrites and globules (MD layer 0·2 -
5 mm thick) and of layers of thin microlaminated
isotropic or weakly isotropic material with dendrites
and globules (TLD layer). The essentially manga­
nese MD layers have dominant amounts of buserite
(I) in the outer and middle parts of the concretions
and lesser quantities of asbolane- buserite. Nearer to
the nucleus of the concretion the relative amount of
birnessite and buserite(II) increases and that of
buserite(I) correspondingly decreases. The presence
of asbolane-buserite is also definitely established.
The TLD layers are represented mainly by asbolane­
buserite and by a somewhat lesser amount of buserite
(I). In order to understand this sequence of trans­
formations, it is essential to keep in mind that the
outer TLD layers contain perceptible quantities of
fine iron vernadite , which resembles iron vernadite
from hydrogenetic concretions and crusts.
Sorem & Fewkes ( 1 979) attempted to build up a
single pattern of the structural - textural features
of the concentric structure and the mineral composi­
tion and chemistry of the major components of
manganese- iron concretions from the Equatorial
Pacific Zone. It was established that the interlayers
equivalent to MD layers are composed of predomi­
nantly manganese oxyhydroxides or 10 A manga­
nates (average wt% Mn 35· 8 1 ; Fe 1 ·28 ; Ni 1 ·74; Cu
1 ·25; Co 0·07; Zn 0·23 ) , whereas the content of
poorly-crystallized and almost X-ray-amorphous
material of layers corresponding to TLD is made up
of mostly iron-manganese (average wt% Mn 19·42;
Fe 16· 94; Ni 0·27; Cu 0· 16; Co 0·31 ; Zn 0·01)
(Sorem & Fewkes, 1979). The alternation of M D
and TLD layers in the concretions from the Clarion­
Clipperton Fracture Zone also reflects the regional
variations of sedimentary conditions in this part of
the Pacific and, in particular, the alternation of
hiatus intervals in sedimentation with periods of
high biological productivity; this alternation of MD
and TLD layers is in good agreement with the
105
sediment section (Von Stackelberg, 1987). To obtain
a better insight into the formation of concretions
from the Clarion - Clipperton Zone and to compare
them with crusts , it seems necessary to analyse rep­
resentative examples of hydrogenetic- diagenetic
growth (Von Stackelberg, 1987 ) . The upper part of
a typical concretion is built up of layered and dense
material which looks black and optically amorphous
in the reflected light under the microscope. The
lower part near the base of the concretion has a less
structurally distinct fabric and is composed of light­
grey material with relatively higher reflectivity. The
boundary between these two parts of the concretion
coincides with the sediment-water interface . The
part of the concretion lying above this interface is
exposed to interaction with bottom seawater. I n
other words, this model concretion was formed a s a
result of accumulation of manganese - iron oxy­
hydroxide material on both sides. According to X­
ray diffraction data, there are essential differences:
the upper part is composed predominantly of 2·4 A
manganate (i.e. verandite) and the lower part of
10 A manganate. This information leads to the
conclusion that below the sediment-water interface
the diagenetic processes dominated and above it
hydrogenetic processes prevailed; the relationships
between them could have changed during the geo­
logical history of their formation. Despite distinct
differences in the modes of growth of these con­
cretions, the trend in the manganese-iron oxy­
hydroxide transformations is similar to the scheme
discussed earlier for crusts.
CONCLUSIONS
The Bezymiannaya 640 Seamount is a submeridi­
onally oriented block of oceanic crust covered with
moderately lithified limestone which dates from the
early Middle Eocene. From the middle parts to the
summit of the seamount the hydrothermal alter­
ation of limestones increases (mostly by phospha­
tization , calcitization, silicification) , together with
an increase in the intensity of growth of manganese­
iron oxyhydroxide crusts.
The crusts are composed of globular structures;
microlaminated accumulations of manganese - iron
oxyhydroxides which developed as the products of
substitution of the deeply phosphatized limestone
substrate. The association between the formation of
crust growths and patches of manganese-iron oxy­
hydroxides and the dissolution of limestones is
106 /. M. Varentsov, V . A. Drits and A.!. Gorschkov
evident also in the relatively high titanium and
aluminium contents which represent residual matter.
In their chemical composition , the manganese ­
iron oxyhydroxide crusts compose a relatively
homogeneous group between typical hydrothermal
and hydrogenetic deposits. In these crusts, the
hydrogenetic accumulation of heavy metals was
superimposed on manganese - iron oxyhydroxide
phases deposited under a strong influence of hydro­
thermal solutions, in particular at the early stages of
accumulation . This circumstance is clearly illustrated
by the features in the distribution of barium, which
is a hydrothermal component in these environments.
The Mn : Fe ratio values are rather low (0·885) for
the crusts from the middle parts of the slope, but
they increase for the crusts in the summit areas
(average 1 ·326) . Hydrothermal activity was particu­
larly intensive during the formation of the older
interlayers of manganese-iron oxyhydroxide crusts
at the time when this part of the Cape Verde Plate
was situated near the axial zone of the Mid-Atlantic
Ridge; as it moved further east, the role of hydro­
genetic factors increased.
The two major minerals composing the surficial
and the least altered crust interlayers are iron
vernadite and manganese feroxyhyte. The
manganese feroxyhytes are relatively unstable prod­
ucts which transformed into goethite. The mixed­
layered asbolane - buserite is usually found in the
lower interlayers of fairly thick crusts and in most of
the foot-wall crusts. The presence of this mineral is
interpreted as a result of postdepositional trans­
formations of iron vernadite and manganese fer­
oxyhyte. Magnesium asbolane was identified in
perceptible quantities in the upper thin (2- 15 mm)
crust from the middle part of the slope, and also
iron vernadite, manganese feroxyhyte , and mixed­
layered asbolane - buserite with admixtures of goe­
thite and birnessite. Crystallochemical data imply
that magnesium asbolane is the product of trans­
formations occurring in the following succession :
iron vernadite (manganese feroxyhyte) ---'> buserite(I )
--" mixed-layered asbolane- buserite ---'> magnesium
asbolane. Birnessite is interpreted as a product
of dehydration of once present but now absent
buserite(I). The suggested succession of postdepo­
sitional alterations of the oxyhydroxide material of
manganese - iron crusts is on the whole in agreement
with the trend in transformations of material in
hydrogenetic-diagenetic manganese- iron con­
cretions from the radiolarian zone of the East
Equatorial Pacific.
ACKNOWLEDGEMENTS
We are grateful to B . P . Zolotarev, V.A. Eroschev­
Shak and 1 . 1 . Bebeshev (Geological Institute of the
USSR Academy of Sciences) for preliminary de­
scription of the recovered samples.
For their assistance in analysing crust components
we thank our colleagues N.l. Kartoshkina and N. Yu.
Vlasova for their help in processing the data and
preparing the materials and N . D. Serebryannikova
for her assistance in scanning electron microscopy.
Constructive criticism of the anonymous reviewers
and editorial processing by J. Parnell (The Queen's
University of Belfast) were useful and improved the
work.
REFERENCES
APLIN, A.P. & CRONAN, D.S. (1985) Ferromanganese
oxide deposits from the Central Pacific Ocean. 1. En­
crustations from the Line Islands Archipelago. Geochim.
cosmochim. Acta 49, 427-436.
CARLO, E., McMuRrY, G. & KIM, K. (1987) Geochemistry
of ferromanganese crust from Hawaiian Archipelago. 1.
Northern survey areas. Deep Sea Res. 34, 441-467.
CHUKHROV, F.V., DRITS, V.A. & GORSHKOV, A.l. (1987)
Structural transformations of Mn-oxides in oceanic Fe­
Mn nodules. Izv. A N SSSR (ser. geol.) 1, 3-14 (in
Russian) .
CHUKHROV, F.V., Zv LAG tN , B . B . , GoRSHKOV, A.l. &
ERMILOVA, L.P. (1975) Delta-Fe hydroxides. In:
Hypergenetic Fe-oxides in Geological Processes (Ed.
by N.Y. Petrovskaya), pp . 70-84. Nauka, Moscow (in
Russian).
CHUKHROV, F.V . , ZVLAGIN , B . B . , GORSHKOV, A.l.,
ERMILOVA, L.P., KOROVUSHKJN , V.Y., R U D N ITSKAYA,
E.S., & YAKU BOVSKAYA, N. Yu . (1976) Feroxyhyte, a
new FeOOH modification. lzv. AN SSSR (ser. geol.), 5,
5-24 (in Russian).
CRAIG, H. (1974) A scavenging model for trace elements in
the deep sea. Earth Planet. Sci. Lett. 23, 149 - 159.
CRON A N , D.S. (1976) Manganese nodules and other ferro­
manganese oxide deposits . In: Chemical Oceanography
Vol. 5, 2nd edn. (Ed. by J.P. Riley & R . Chester),
pp. 2 17-265. Academic Press, London.
CRONAN , D.S. , GLASBY, G.P., MOORBY, S.A., THOMSON ,
J . , KNEDLER, K.E. & McD o u GALL, J.C. (1982) A sub­
marine hydrothermal manganese deposit from the
south-west Pacific Island Arc. Nature 298, 456-458.
DETRICK, R . S., HONNOREZ, J., ADAMSON, A.C. , BRASS ,
G . W . , GILLIS, K . M . , H U MPHERIS, S.E. , MEVEL, c . ,
MEYER, P . S . , PETERSEN, N., RAUTENSCHLEIN, M.,
SHIBATA, T. , STAUDIGEL, H., WOOLRIDGE, A. &
YAMAMOTO, K. ( 1986) Forages dans Ia dorsale media­
Atlantique: resultats preliminaires du Leg 106 du Joides­
Resolution (Ocean Drilling Program). C. R. Acad. Sci.
(ser. 2, 303) 7, 597-602.
HEtN, J.R. , Sc H WAB, W . C . & D Avts , A.S. ( 1988) Cobalt-
 Manganese- iron crusts, Bezymiannaya Seamount 640
and platinum-rich ferromanganese crusts and associated
substrate rocks from the Marshall Islands. Marine Ceo!.
78, 255-283.
LALO U , C., THOMPSON , G., RONA, P.A., BRICHET, E. &
JEHANNO, C. ( 1986) Chronology of selected hydrother­
mal Mn oxide deposits from the transatlantic geotraverse
'TAG' area, Mid-Atlantic Ridge 26°N. Geochim.
Cosmochim. Acta 50, 1737-1743.
M uRRAY, J.W. ( 1979) Iron oxides. In: Marine Minerals,
Course Notes, Vol. 6 (Ed. by R.G. Burns), pp . 47-98.
Mineralogical Society of America, Washington.
RIDOUT, P.S., CARPENTER, M.S.N. & MORRIS, R.J. ( 1984)
Analysis of metalliferous encrustation from a seamount
in the Gulf of Guinea. Chem. Ceo!. 42, 2 19-225 .
SHTERENBERG, L.E., ALEKSANDROVA, V.A., ILYICHEVA,
L.V., SivTsov, A.V. & STEPANOVA, K . L. ( 1986) Post­
depositional alterations in oceanic Fe-Mn concretions
and crusts. lzv. AN SSSR (Ser. Geol.) 1 , 80-88 (in
Russian).
SKORNIAKOVA, N .S. ( 1984) Morphogenetic types of Fe-Mn
concretions from the radiolarian belt of the Pacific.
Litho!. Min. Deposits 5, 67-83 (in Russian).
SoREM, R.K. & FEWKES, R.H. (1979) Manganese nodules.
Research Data and Methods ofInvestigation . IFI/Pienum
Data, New York, 723pp.
THOMPSON , G ., MOTfL, M . & RONA, P.A. ( 1985) Mor­
phology, mineralogy and chemistry of hydrothermal de­
posits from the 'TAG' area, 26°N Mid-Atlantic Ridge.
Chem. Ceo!. 49, 243-257.
ToTH, J.R. (1980) Deposition of submarine crusts rich in
manganese and iron. Ceo!. Soc. Am. Bull. 91, 44-54.
USPENSKAYA, T.Yu., GoRSHKov, A.l. & SJVrsov, A.V.
(1987) Mineral composition and inner structure of Fe­
Mn concretions from the Clarion-Clipperton fracture
zone. Izv. AN SSSR (Ser. Geol.) 3, 9 1 - 100 (in Russian).
UsPENSKAYA, T.Yu . , GoRSHKOv, A.I . & SJVrsov, A . V.
( 1988) Structure and mineral composition of oceanic
nodules Izv. AN SSSR (Ser. Geol.) 4, 88-97 (in
Russian) .
107
VARENTSOV, l.M., BAKOVA, N . Y . , DIKOV, Yu.P.,
GENDLER, T.S. & GIOVANOLI , R. (1979a) On the model
of Mn, Fe, Ni, Co ore formation in Recent Basins:
experiments with synthesis of Me-hydroxide phases on
Mn304. Min. Deposita 14, 281-296.
VARENTSOV, J.M., BAKOVA, N . Y . , DIKOV, Yu.P.,
GENDLER, T.S. & GIOVANOLI, R. ( 1979b) Synthesis of
Mn, Fe, Ni, Co oxide-hydroxide phases on manganese
oxides: on a model for transition metal ore formation in
Recent Basins. Acta Mineral. -Petrograph. (Szeged)
XXIV/I, 63-90.
VARENTsov, I . M ., D RITS, V.A., GoRSHKOv, A . !., Swrsov,
A.V. & SAKHAROV, B.A. ( 1989) Formation of Mn-Fe
crusts in the Atlantic: mineralogy, geochemistry of major
and trace elements, the Krylov Seamount. In: Genesis of
Sediments and Basic Problems of Lithology (Ed. by
V.N. Kholodov), pp. 58-78. Nauka, Moscow (in
Russian) .
VARENTSOV, I.M. & PRONINA, N . Y . (1973) On the study of
mechanisms of iron -manganese ore formation in Recent
Basins: the experimental data on nickel and cobalt. Min.
Deposita ( Berl. ) 8, 161-178.
VARENTSOV, J.M., SAKHAROV, B.A., D RITS, V.A.,
TSIPURSKY, S.l., CHOPOROV, D . YA. & ALEXANDROVA,
V.A. (1983) Hydrothermal deposits of the Galapagos
Rift Zone, Leg 70: mineralogy and geochemistry of
major components. In: Initial Reports of the Deep Sea
Drilling Project, Vol. 70 (Ed. by 1 . Honnorez, et a!. ) ,
pp. 235-268. U S Government Printing Office,
Washington.
VoN STACKELBERG, U. ( 1987) Growth history and variability
of manganese nodules of the Equatorial North Pacific .
In: Marine Minerals. Advances in Research and Resource
Assessment (NATO ASI Series, Series C. Mathematical
and Physical Sciences, Vol. 194) (Ed. by P.G. Teleki,
M .R. Dobson, J.R. Moore & U. von Stackelberg),
pp. 189-204. Reidel, Dordrecht.
Spec. Pubis int. Ass. Sediment. (1990) 11, 109-118

Microbiota from middle and late Proterozoic

iron and manganese ore deposits in China

L. Y I N
Nanjing Institute of Geology and Palaeontology, Academia Sinica, Chi-Ming-Ssu, Nanjing, People's Republic
of China

ABSTRACT

Abundant microfossils have been discovered in middle and late Proterozoic iron and manganese ore
deposits in eastern Guizhou Province, western Hunan Province, western Liaoning Province and Gansu
Province. On the basis of microfossil assemblages and radiometric dating, the age of the iron and
manganese ore deposits is considered to be in the range 1200-750 Ma.
A number of microfossils of Sphaerocongregus (or Bavlinella) have been found in rhodochrosite in
these deposits. Based on the different preservation of microfossils in relation to the iron and manganese
contents, it can be inferred that cyanobacteria are directly or indirectly implicated in the genesis of
these iron and manganese ore deposits.

INTRODUCTION

Late Proterozoic manganese ore deposits inter­
bedded with tillites are widely distributed in South
China. Some manganese ores in Sichuan, Guizhou,
Hunan, Hubei and Jiangxi Provinces have industrial
value. However, there are different views about the
geological age of these manganese ore deposits and
their genesis (see Ji, 1985; Xu, 1987). In order to
understand them better, the biostratigraphy of
manganese ore deposits in the Songtao district of
eastern Guizhou Province and the Huayuan district
of western Hunan Province has been studied with
the help of the 405 Geological Team of the Hunan
Geological Bureau and the 103 Geological Team
of the Guizhou Geological Bureau. A number of
organic-walled microfossils have been identified
from these sediments by means of palynological
maceration and thin section studies, and numerous
coccoid microfossils were photographed using the
scanning electron microscope (SEM). The results
not only strongly support the recognition of which
manganese ore deposits in eastern Guizhou Province
and western Hunan Province were formed during
the ' Nantuo glacial epoch' of the late Proterozoic,
but also provide important evidence for the genesis
of manganese ore deposits in South China.
In addition, organic-walled microfossils have been
obtained from iron and manganese ore deposits in
Wafangzi, Chaoyang County, Liaoning Province and
Jingtieshan, Jiuquan district and Gansu Province.
Middle and late Proterozoic iron and manganese
ore deposits in China occur as iron and manganese
carbonates interbedded with black shales formed
under anaerobic conditions. Important questions in
such environments, are which microorganisms could
live, and what effects could be attributable to micro­
organisms, such as transportation and enrichment of
iron and manganese. In this paper, this subject is not
discussed in depth. At the present level of knowl­
edge, the facts are presented for certain Chinese
deposits and their significance is suggested.
SEQUENCES OF IRON AND
MANGANESE ORE DEPOSITS, AND
THEIR MINERAL ASSOCIATIONS
A brief summary of the geology of the deposits
examined is given below.

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun

109
and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
l lO L. Yin
Songtao district of eastern Guizhou Province
The Datangpo Formation is 90-570 m thick; the
upper part consists of yellow-green mudrock inter­
bedded with fine sandstone, the middle part is
composed of yellow-green mudrock and silty mud­
stone and the lower part is grey-black shale, usually
containing manganese carbonate near the bottom.
This formation is underlain conformably by the
Liaoghekou Formation and overlain disconformably
by the Nantuo tillites.
Manganese ore deposits occur at the bottom of
the Datangpo Formation in this district. Ore bodies,
strata-bound and lenticular, extend laterally up to
400 m and are up to 7·65 m thick. Manganese
carbonate appears as dense, massive and striped
beds, containing 10-25% Mn. The ratio of Mn: Fe is
4·75-6·79 and the ratio of P: Mn is 0·0075-0·0163.
The manganese ore is characterized by a high con­
tent of phosphorus and a low content of iron. A
rhodochrosite-calcite series of manganese carbon­
ates is present, ranging through rhodochrosite,
calcium rhodochrosite, calcium-magnesium rho­
dochrosite, magnesium-manganese calcite and
manganese calcite.
Huayuan district of western Hunan Province
The Minle Formation is 218 m thick; the upper part
is made up of grey shales and dark-grey silty shales
and the lower part consists of dark-grey silty shales
interbedded with thin beds of black shale and grey­
black striped manganese carbonate (Fig. 2). Massive
manganese carbonate occurs at the bottom of this
formation with a thickness of 0·75 m. This formation
is underlain conformably by the Chunmu Formation
and overlain conformably by the Nantuo Formation.
Manganese ore deposits in this district are dated at
728 ± 27 Ma by means of a rubidium-strontium
whole-rock isochron (see Geological Team of
Hunan Geological Bureau, 1984).
The characters of the mineral deposit are similar
to those of the manganese ore deposits in eastern
Guizhou Province. The manganese carbonates are
mainly rhodochrosite, calcium rhodochrosite, mag­
nesium rhodochrosite, calcium-magnesium rhodo­
chrosite, magnesium-calcium rhodochrosite and
manganese dolomite.
Chaoyang district of western Liaoning Province
Manganese ore beds are situated in the Tieling For­
mation. The age of the manganese-bearing series is
about 1200 Ma.
The thickness of the Tieling Formation in this
district is about 70 m. The upper part is made up of
thick bedded siliceous limestone, the middle part
is a manganese-bearing series and the lower part
consists of laminated dolostone with lenticular
quartzose sandstone at the top. The underlying
Hongshuizhuang Formation, with a thickness of
130-170 m, consists of black carbonaceous shales
and is in conformable contact with the Tieling For­
mation. Lower Cambrian conglomerates overlap
the Tieling Formation with unconformity. The
manganese-bearing series is mainly composed of
mudrocks with some dolomitic conglomerates at the
bottom, and siliceous limestone at the top. In the
mudrock series, manganese ore occurs as stratiform
and lenticular ore bodies, associated with siltstone
and shales. The manganese ore belongs to the iron­
manganese class with Mn 16-33%, Fe 15-20% and
Mn: Fe ratio of 1-2. The phosphorus content in
primary carbonate ores is 0·004-0·006% and the
sulphur content is 0·5- 1%.
MICROBIAL FOSSILS
A number of sphaeromorphic microfossils, dis­
playing individuals, pairs or groups of cells with
more than three vesicles, have been obtained using
standard palynological techniques from iron and
manganese ore deposits of the Datangpo Formation
of eastern Guizhou Province, the Minle Formation
of western Hunan Province, the Tieling Formation
of western Liaoning Province and the strata of Gansu
Province. Most of them occur as bud-like forms or
forms with infillings (see Fig. 3). Some specimens
exhibit morphological features similar to forms
previously reported and are determined as Leio­
minuscula, Lophominuscula, Protosphaeridium,
Asperatopsophosphaera, Trachysphaeridium and
Bavlinella. These form-taxa usually occur in late
Riphean and Vendian strata in the USSR and North
Europe (see Timofeev, 1959, 1966, 1973; Vidal,
1976).
In addition, numerous coenobium-type fossils­
Sphaerocongregus valiabiris (or Bavlinella faveo­
lata) and their degradational remains were identified
from sections of manganese ore etched by HCl
(10-15%) before examination by SEM.
The organic-walled microfossils Sphaerocongregus
(or Bavlinella) have been mostly reported from late
Proterozoic strata, especially from glacial deposits,
in Scandinavia, Greenland, North America, China
 Microbiota from iron and manganese deposits 111

Fig. 1. Map showing the localities

of iron and manganese ore deposits
in China discussed in this paper. (A)
Huayuan manganese ore deposit,
western Hunan Province; (B)
Songtao manganese ore deposit,
eastern Guizhou Province; (C)
Wafangzi manganese ore deposit,
western Liaoning Province; (D)
Jingtieshan iron ore deposit, Gansu
Province. 0

A B c

E
lL
0
::J
-+-
c
0
z

u
1::-_:.::::1
Fig. 2. Stratigraphic sections of the
Minle Formation from Huayuan 0
ESC9 2
N
district of western Hunan Province 0
� 3

(A), the Datangpo Formation from L

Q) � 4
Songtao district of eastern Guizhou ......
Province (B) and the Tieling 0 I-:-..:.-:-:-I 5
L
Formation from the Chaoyang 0..
E ES::::j 6
district of western Liaoning u..
Province (C). (1) Sandy shale; (2) ::J � 7
E
sandy dolomite; (3) manganese ore c
::J
_c
.E5:9 8
beds; (4) black shale; (5) tillites; (6) u
dolomite; (7) shale; and (8)
limestone.

and elsewhere (Manum, 1968; Moorman, 1974;
Vidal, 1976; Knoll et al., 1981; Mansuy & Vidal,
1983; Yin, 1987).
Sphaerocongregus variabilis Moorman, 1974, the
type species of genus Sphaerocongregus Moorman,
1974, was recognized as the synonym of Bavlinella
faveolata Shepeleva, 1962, by Vidal (1976). How­
ever, Volkova (1974) concluded that Bavlinella
Shepeleva, 1962, is a junior synonym of Pyrito­
sphaera Love, 1958 and that Bavlinella forms, like
Pyritosph aera, arose as a result of the modifications
of acritarch tests, films or threads of organic matter,
and exines of spores (pollen) in the formation of
framboidal pyrite. Foster et al. (1985) reported
organic-walled microfossils Sphaerocongregus from
the early Cambrian Heatherdale Shale, on the
Fleurieu Peninsula, South Australia and they con­
cluded that members of Sphaerocongregus are dif­
ferent from Bavlinella in having a compound wall of
coccoid subunits and an extremely shallow negative
112
A D
F G
E
J and late Proterozoic iron and
reticulum between these subunits. It is recognized
here that the Bavlinella faveolata (Shepeleva, 1962)
Vidal, 1976 is the same as the Sphaerocongregus
variabilis Moorman, 1974 colonial microfossils. They
are both fossil representations of a particular bio­
logical form rather than secondary structures, due
to their restricted stratigraphic distribution and
relationship with a -particular environment. SEM
studies reveal that the fossils are coenobia and have
hollow, cell-like subunits (Fig. 4). They represent
certain biological forms with an affinity with living
coccoid cyanobacteria, such as Entophysalis (see
Cloud et al., 1975), Xenococcus and Dermocarpa
(see Knoll et al., 1981).
L. Yin
Fig. 3. Microfossils from middle
manganese sediments in China. All
photomicrographs are from organic­
walled microfossils obtained by
maceration. Scale in figure equals 15
f.tm in (A)-(H),(J),(K) and 10 f.tm
in (I),(L) and (M). (A),(E),(F),(G)
and (J) are from the Datangpo
Formation of eastern Guizhou
Province; (B) is from the Tieling
Formation of western Liaoning
Province; (C),(D),(H),(I) and (K)
are from the Minle Formation of
western Hunan Province; (L), (M)
are from the strata of Gansu
M
Province.
THE RELATIONSHIP BETWEEN
MICROBIOTA AND IRON AND
MANGANESE MINERALS
These studies have indicated that the morphological
features, quantity and distribution among the micro­
biota are related to the iron and manganese content
in iron and manganese ore deposits. In rocks con­
taining minimal iron-manganese contents, such as
black shale and carbonate, the microbiota is domi­
nated by larger forms, which can be considered to be
vegetative cells or cysts of eukaryotic alg�e. With
increasing iron and manganese content in the sedi­
ments, larger forms of microfossils decrease dis­
tinctly and a few forms display either infillings of
 Microbiota from iron and manganese deposits
Fig. 4. Scanning electron
micrograph of Sphaerocongregus
(or Bavlinella) from late
Proterozoic manganese ore,
Huayuan district, western Hunan
Province.
iron or manganese minerals, or exhibit irregular
shapes. In richer iron and manganese ores, cyano­
bacterial fossils ( Sphaerocongregus) rather than
eukaryotic microplankton are predominant.
It is well known that low-diversity microbiota
dominated by morphologically simple taxa appear to
be diagnostic for inshore coastal environments, while
higher diversity microbiota containing a hetero­
geneous array of morphologically complicated forms
indicate more open-shelf conditions (Vidal, 1981).
The sedimentary environments in the sequences
discussed in this paper would be inshore coastal
or lagoonal facies, because microbiotas in these
sequences are all characterized by low diversity.
Based on sulphur isotopic analysis, o34S for pyrite
in manganese ore in Huayuan, western Hunan Prov­
ince is 46·6-58·59% (Geological Team of Hunan
Geological Bureau, 1984). This high value of o34S
supports the suggestion that the manganese ore
deposits may have been deposited in a semi-enclosed
bay. In such an ecological environment, micro­
organisms were restricted by stressed physical and
chemical conditions, such as high concentrations of
nutrients or high salinity. Knoll et al. (1981) de­
scribed microfossils from the late Proterozoic min­
eral rock formation in North America and they
suggested that stressed conditions were caused by an
influx of glacial meltwater, thus allowing one organ­
ism (like Bavlinella faveolata) to proliferate and
dominate in such an environment. In the present
study, a number of Sphaerocongregus (or Bavlinella)
were found in manganese carbonate of a postglacial
epoch in eastern Guizhou Province and western
Hunan Province. The presence of a single genus of
microfossils in this particular environment is in
agreement with the finding of Knoll et al. (1981).
No glacial sediments have been seen in iron and
manganese deposits of either the Chaoyang district
113
of western Liaoning Province or the Jiuquan district
of Gansu Province. So, glacial activity was probably
not significant in these districts during the formation
of the iron and manganese ore deposits. However,
the diversity and the morphology of microfossils in
the iron and manganese deposits from rocks asso­
ciated with the ore beds in these districts are variable.
Possibly, stressed conditions not only resulted from
an anomalous salinity and temperature regime as­
sociated with the influx of glacial meltwater, but the
oxygen content in the water was also an important
control on both the diversity and the morphology of
the microorganisms.
It is considered that the normal balance between
oxygen and carbon dioxide in the basin only existed
when iron and manganese ions were in low ionic
concentrations. The photic zone, with more oxygen,
is more suitable for aerobic organisms. When iron
and manganese became more abundant, the oxi­
dation of these metal ions (Fe2+ and Mn2+) would
have depleted the oxygen available. Most original
aerobic organisms could not be sustained by such
anaerobic conditions and only a few forms of
cyanobacteria, characterized by facultative photo­
autotrophy (i.e. with capability in both aerobic and
anaerobic conditions), could continue development
because they are capable of anoxygenic photo­
synthesis. The interpretation discussed above is
shown in relation to the microorganisms in Fig. 5.
On the other hand, microorganisms may play an
important role in the iron and manganese cycles,
interacting with iron and manganese in several ways.
It is well known that the influence of microorganisms
on iron and manganese geochemistry is significant.
This is because fluctuations of conditions, such as
pH and Eh in water are paralleled by variations in
the nature of microbial populations (Edmunds et al.,
1982). In the material dealt with in this paper, it is
114 L. Yin
_J �z_! .
found that shales containing abundant microfossils
are always superjacent to the iron or manganese
ore beds (see Fig. 2). It is considered that the
biochemistry of microbial populations was an im­
portant influence on the solution, transport and
precipitation of the iron and manganese.
In previous studies, including both modern bio­
logical experiments and fossil records, it has been
shown that microorganisms play a significant role in
the precipitation of iron and manganese. However,
these organisms are commonly filamentous bacteria,
like Metallogenium (Nealson, 1983). No filamentous
bacteria have been seen in the present material.
There were two possible reasons for this. One is that
the ecological environment was not suitable for the
development of filamentous organisms. The other
reason may be that diagenesis, including the recrys­
tallization of iron-manganese carbonate, could
eliminate the filamentous organisms.
Although at present, we cannot say that there is a
definite relationship between cyanobacteria, like
Sphaerocongregus (or Bavlinella), and the genesis
of iron and manganese ore, it is certain that
their biochemical functions (i.e. photosynthesis,
respiration, adhesion, etc.) could alter the Eb and
pH of water and influence the oxidation and re­
duction of iron and manganese, as well as form
organic chelates of these metals. On the other hand,
Oz.-
Fig. 5. Schematic diagram showing
the distribution of microfossils in
B different environments.
it is well known that iron is readily cbelated by a
variety of organic molecules including oxalates,
citrates, burnie acids, tannins and siderophores, and
that the hydrous oxides of manganese are themselves
strong chelators of Mn2+ and other cations, and
adsorption/desorption processes play a major role in
the geochemistry of manganese (see Nealson, 1983).
So, the biochemjcal functions of microorgarusms
were closely concerned with the geochemistry of
iron and manganese during the formation of iron
and manganese ores.
Here we consider the manganese ore of western
Hunan Province and eastern Guizbou Province as
examples for interpretation of the relationship be­
tween microorganisms and manganese.
As discussed above, the sedimentary environment
was a semi-enclosed basin. Initially, there were
numerous but low-diversity planktonic micro­
organisms in the water, and their activities bad
increased the oxygen content and pH of the water.
When manganese ions entered the basin, mainly in
the form of manganese bicarbonate from the conti­
nent, volcanic eruption and hydrothermal solution,
their oxidation caused exhaustion of oxygen in the
water. In such an ecological environment, only cer­
tain cyanobacteria survived because they are capable
of anoxygenic photosynthesis. Manganese adhered
to mucilage, including carbohydrate polymers, on
 Microbiota from iron and manganese deposits
their walls, and organic chelates of metals could also
form. The chelates impregnated and mineralized the
cell walls of the cyanobacteria. In addition, the
enzymes enolase, superoxide dismutase and PEP
carboxykinase in organisms all require manganese
(see Nealson, 1983) although the question is open as
to whether or not cyanobacteria can obtain energy
for growth by the oxidation of manganese. Sub­
sequently, the manganese accumulated in the cells
of organisms. Such direct and indirect relationships
between the organisms and manganese allowed the
gradual deposition of manganese minerals in the
basin. Meanwhile, the water became more reduced
by both the oxidation and the accumulation of
manganese minerals, so that microorganisms like
cyanobacteria could not normally survive and dead
cells accumulated at the bottom of the basin. The
cell walls were degraded by sulphur-reducing bac­
teria and cells were partially or entirely replaced by
various manganese minerals, which caused further
manganese mineralization in the sediments. This
interpretation seems to be supported by the fact that
microfossils appear to be more abundant in the man­
ganese ore deposits with an increase in manganese
Fig. 6. Scanning electron
micrograph of Sphaerocongregus
(or Bavlinella) and their degraded
forms from late Proterozoic
manganese ore, Songtao district,
eastern Guizhou Province.
115
content, and the fossils are also more degraded in
manganese-rich sediments (Figs 6 and 7).
The colonial microfossils shown in Fig. 6A were
obtained from striped manganese carbonate. How­
ever, in dense, massive manganese-rich carbonate,
cell-like residues are as in Fig. 6C or in Fig. 7B. In
addition, organic components such as bitumen, satu­
rated hydrocarbons, aromatic hydrocarbons and
phenanthrenes, have been determined from massive
manganese-rich carbonate of western Hunan
Province (Geological Team of Hunan Geological
Bureau, 1984). The data also indicate organic ac­
tivity during the deposition of the manganese-rich
sediments.
Although all of the above speculations and inter­
pretations are mainly based on the morphology
of microfossils and textural features of iron and
manganese ores, it may be surmised that the bio­
logical and physiological functions of coccoid cyano­
bacteria directly or indirectly affected both the
transport and the deposition of iron and manganese
minerals. This only happened in suitable conditions,
characterized by low atmospheric oxygen level and
rich sources of iron and manganese ions, such as
116
Fig. 7. Scanning electron micrograph showing the
degraded forms of Sphaerocongregus? (A) From late
Proterozoic manganese ore of the Songtao district of
eastern Guizhou Province; (B) From late Proterozoic
manganese ore of the Huayuan district of western Hunan
Province.
develop in enclosed water basins. Previous reports
of microfossils from early Proterozoic banded iron
formations in China (Yin, 1979), late Proterozoic
banded manganese formations in China (Xu, 1987),
and a late Proterozoic manganese ore body in India
(Bandopadhyay, 1989) all seem to support the
L. Yin
genetic association between coccoid microorganisms
and iron and manganese minerals.
CONCLUSIONS
Based on the microfossil material available from
iron and manganese ore deposits, the following
conclusions were reached:
1 The diversity of microbiota in iron and manganese
deposits is relatively low and generally has little
biostratigraphic significance.
2 Sphaerocongregus (or Bavlinel/a) seems to have
been a cyanobacterium of facultative photoauto­
trophy, i.e. sustainable in both aerobic and anaer­
obic conditions, in that it not only occured in a
stressed environment controlled by anomalous sal­
inity and temperature associated with an influx of
glacial meltwater, but then also developed in
anaerobic conditions containing iron and manganese
minerals.
3 Coccoid cyanobacteria po�sibly play a role in the
genesis of iron and manganese ore deposits, by
direct or indirect biochemical effects.
ACKNOWLEDGEMENTS
I thank L. Wang, D. Cao and X. Zhan (Nanjing
Institute of Geology and Palaeontology, Academia
Sinica) for assistance in preparing the specimens,
producing the SEM micrographs and in drafting,
J. Ostwald (BHP Central Research Laboratories,
Australia) for critical review and J. Parnell (The
Queen's University of Belfast) for editorial help.
The costs of field studies and laboratory investi­
gations were covered by the National Nature Science
Foundation of China.
REFERENCES
BANDOI'ADHYAY, P.C. (1989) Proterozoic microfossils from
manganese orebody, India. Nature, 339, 376-378.
CLOUD, P., MooRMAN, M.A. & PIERCE D. (1975) Sporu­
,
lation and ultrastructure in a late Proterozoic cyano­
phyte: some implications for taxonomy and plant
phylogeny. Q. Rev. Bioi. SO, 131-149.
EDMUNDS, K.L.H., BRASSELL, S.C. & EGUNTON, G. (1982)
The organic geochemistry of benthic microbial eco­
systems. In: Mineral Deposits and the Evolution of the
Biosphere (Ed. by H.D. Holland & M. Schidlowski),
pp. 31-50. Dahlem Konferenzen, 1982, Berlin.
Springer, New York.
 Microbiota from iron and manganese deposits
FAN, D.L. (1959a) Wafangzi ferro-manganese ore deposits
in China. Geol. Rudn. Mestorozhd 4, 78-89 (in
Russian).
FAN, D.L. (1959b) The pyrosmalite in Wafangzi ore
deposit in China. Dokl. Akad. Nauk. USSR (ser. geol.
6) 126, 1338-1347 (in Russian).
FoGG, G.E., STEWART, W.D.P., FAY, P. & WALS BY, A.E.
(1973) The Blue-green Algae. Academic Press, New
York, 459pp.
FOSTER, C.B., CERNOVSKIS, A. & O'BRIEN, G.W. (1985)
Organic-walled microfossils from the Early Cambrian of
South Australia. Alcheringa 9, 259-268.
GEOLOGICAL TEAM OF HUNAN GEOLOGICAL BUREAU (1984)
Bulletin on geological characters and mineralogical pat­
tern of Minle manganese ore deposits in Huayuan region
of Hunan Province. Monograph of mineral deposit (18),
122pp. (in Chinese).
JI, J.F. (1985) Fossil cyanophytes from Early Sinian
manganese and iron-bearing moraine formation in
Southern China and their geological significance. In:
Selected papers from the 1st National Fossil Algal
Symposium, pp. 213-218. Geological Publishing House,
Beijing (in Chinese, with English abstract).
KNOLL, A.H. & AwRAMJK, S.M. (1983) Ancient microbial
ecosystems. In: Microbial Geochemistry (Ed. by
W.E. Krumbein), pp. 267-315. Blackwell Scientific
Publications, Oxford.
KNOLL, A.H., BucK, N. & AwRAMIK, S.M. (1981) Strati­
graphic and ecologic implications of late Precambrian
microfossils from Utah. Am. J. Sci. 281, 247-263.
MANSUY, C. & VIDAL, G. (1983) Late Proterozoic
Briaverian microfossils from France: taxonomic affinity
and implications of plankton productivity. Nature 302,
606-607.
MANUM, S. (1968) Microfossils from late Precambrian sedi­
ments around Lake Mjosa, Southern Norway. Norg.
Geol. Unders. 251, 45-52.
MooRMAN, M.A. (1974) Microbiota of the late Proterozoic
Hector Formation, Southwestern Alberta, Canada. J.
Paleontol. 48 , 524-539.
NEALSON, K.H. (1983) The microbial iron cycle. In:
117
Microbial Geochemistry (Ed. by W.E. Krumbein),
pp. 159-190. Blackwell Scientific Publications, Oxford.
TIMOFEEV, B.V. (1959) Ancient flora of the Baltic area and
its stratigraphic significance. Trudy VNJGRI 129,
Leningrad (in Russian) 320pp.
TiMOFEEV, B.V. (1966) Microphytological investigations of
ancient formations. Acad. Sci. USSR Lab. Precambr.
Geol. Geochronol. Nauka, Leningrad, 145pp. (in
Russian).
TIMOFEEV, B.V. (1973) Microphytofossils from the
Ukraine. Acad. Sci. USSR Jnst. Ceo!. Geochronol. Pre­
cambr. Nauka, Leningrad, 58pp. (in Russian).
VIDAL, G. (1976) Late Precambrian microfossils from the
Visingso Beds in southern Sweden. Fossils and Stra/a 9,
1-57.
VIDAL, G. (1981) Aspect of problematic acid resistant,
organic-walled microfossils (acritarchs) in the Upper
Proterozoic of the North Atlantic region. Precambr.
Res. 15, 9-23.
VOLKOVA, N.A. (1974) Types of damage to the body of
Precambrian and Cambrian acritarchs. Paleont. Zh. 4,
101-108 (in Russian).
Xu, Z.L. (1987) Algal fossils from late Precambrian
Banded Manganese Formation (BMF), Xianhtan,
Hunan Province of China. Acta Botanica Sinica 29,
104-110 (in Chinese, with English abstract).
YIN, L.M. (1979) Microflora from the Anshan Group and
the Liaohe Group in East Liaoning with its stratigraphic
significance. In: Selected works for a scientific symposium
on iron-geology of China, sponsored by Academia
Sinica, 1977. Stratigraphy and Palaeontology,
pp. 39-60. Science Press, Beijing (in Chinese, with
English abstract).
YIN, L.M. (1987) Microbiotas of latest Precambrian
sequences in China. In: Stratigraphy and Palaeontology
of Systemic Boundaries in China (Precambrian­
Cambrian Boundary) Vol. 1, pp. 415-522 (compiled by
Nanjing Institute of Geology and Palaeontology,
Academia Sinica). Nanjing University Publishing
House.
 Spec. Pubis in!. Ass. Sediment. (1990) ll, 119-138

Metal precipitation related to Lower Ordovician oceanic changes:

geochemical evidence from deep-water sedimentary sequences
in western Newfoundland

J. W . BOTSFORD* and D.F. SANGSTERt

*
centre for Earth Resources Research, Memorial University of Newfoundland, St. John's, Newfoundland
Canada, AlB 3X5; '"Geological Survey of Canada, 601 Booth St., Ottawa, Canada KIA 0£8

ABSTRACT

Lower Palaeozoic deep-water sedimentary sequences arc preserved within the Humber Arm Allochthon
in western Newfoundland, where they have been thrust westward and now structurally overlie coeval
shallow-water sequences. Of particular interest are the laterally equivalent Cow Head and Northern
Head Groups, base-of-slope shale-rich sediment apron deposits which span the latest Middle Cambrian
to late Early Ordovi cian.
A pronounced Early Ordovician change in oceanic conditions is particularly evident i n the Northern
Head Group, based upon: (1) a marked increase in bioturbation; (2) anomalously high manganese and
barium content; and (3) changes in carbon : sulphur ratios. All suggest a transition to a new depositional
regime characterized by ventilated depositional and early diagenetic conditions. This is much more
subtly reflected i n the Cow Head Group; the contrast is ascribed to alo ng-strike differences in original
margin morphology which the two groups embody. The contrast extends to sulphides within shales
through the section. I n the Northern Head Group, anomalous metal (zinc, copper and lead) concen­
trations (up to 300 ppm) occur within Lower Ordovician (Lower Arenigian) shales. Disseminated
sulphides within this horizon appear remobilized and rcplacive . On the other hand, localized metal
concentrations within the Cow Head Group are scattered throughout the entire stratigraphic interval
and are generally associated with organic carbon.
The sulphur isotopic profiles of early precipitated pyrite through the stratigraphic in terval in both
groups are also suggestive of a marked Lower Ordovician change from stratified to ventilated conditions
based upon a decrease in1'r'4S values in the Late Tremadocian. Immediately following this, o34S values
display a positive deflection suggestive of a temporary return to stratified conditions in the Arenigian.
These apparent circu lation changes may have controlled redox conditions, and in turn have governed
metal mobilization and precipitation.

REGIONAL GEOLOGY

The Humber Zone assemblage of western
Newfoundland (Williams, 1979) records : ( 1) the
establishment of a passive continental margin in the
Late Precambrian/Early Cambrian; (2) continental
* Present address: Newfoundland and Labrador Science
and Technology Advisory Council, 114 Empire Ave . , St
John's, Newfoundland, A l C 3G2.
Also at: t Derry Laboratory for Sedimentary Geochemistry
and Mineral Deposits, Ottawa-Carleton Geoscience
Centre, Ottawa, Canada.
Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun
and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
margin sedimentation spanning the Cambrian to
Middle Ordovician; (3) the destruction of the margin
during Middle Ordovician Taconic orogenesis; and
(4) subsequent deformation during Acadian oro­
genesis. The Early Cambrian Labrador Group is a
siliciclastic-carbonate sequence which represents
the basal part of the autochthonous sedimentary
sequence. This is overlain by a thick (approximately
1500 m) carbonate platform sequence (Port au Port
Group , St George Group) spanning the Middle
1 19
120 1. W. Botsford and D. F. Sangster

Cambrian to Early Ordovician (Fig. 1). The autoch­
thonous platform sequence was dominated by
shallow-water sedimentation, and is generally poor
in shale.
Equivalent deep-water strata are preserved in two
major allochthons, the Humber Arm Allochthon in
the south and the Hare Bay Allochthon in the north.
Block-faulting and foundering of the platform pre­
ceded emplacement of these allochthons, and is
recorded in the deposition of the Middle Ordovician
Table Head Group atop the platform sequence
( Klappa et a/., 1980; Stenzel & James, 1987).
The Humber Arm and Hare Bay Allochthons are
broadly similar in that they comprise thrust slices of
predominantly sedimentary lithologies in the lower
part, overlain by volcanic and igneous slices of
oceanic affinity, and capped by ophiolite complexes ;
all are separated by melange zones of variable
thickness. Both allochthons were emplaced west­
ward during the Middle Ordovician Taconic
Orogeny, now structurally overlie the autochthonous
platform sequence and are bounded by melange
(Figs 1 and 2). The internal stratigraphy is both
clearest and most complete in the Humber Arm
Allochthon, where the structural history is presently
better understood. The sedimentary succession here
is exposed in imbricate thrust slices, modified by
later (Acadian) compression.
Humber Arm Allochthon
The Humber Arm Allochthon is centred on the
Bay of Islands and extends from the Port au Port
Peninsula in the south to the Cow Head area in the
north (Fig. 2). A succession of deep-water sedi­
mentary units, time-equivalent to the platform
sequence outlined above, is exposed in the lower
part of the Humber Arm Allochthon (Fig. 3), and
termed the Humber Arm Supergroup (Stevens,
1970). At the base, red and green shale and sand­
stone of the ?Lower Cambrian Summerside
Formation occur. This passes upward into the

AUTOCHTHONOUS HUMBER ARM ALLOCHTHON

PLATFORMAL
SEQUENCE

ci GOOSE
a:
0 TICKLE
w FM.
..J
0
0 TABLE HD.

:i GROUP '-
LIgneous :J
Lvolcanlc]
ci
a:
0
ST. L Slices ::J
Melange
GEORGE
�
0 '-"'� 0-- "0'- <;)�
GROUP
..J

PORT
AU
z
.. PORT
�
CD z
::;
..
u
�"' ·._::.:·:-·.::--··.-
COW HEAD
:.� ;-_-.-·:- �-: ,· .
::; AREA
..
u

""''!,D 'V'
BAY OF ISLANDS
AREA

[2] Sandstone � Thin-bedded

limestone
,_ -J Siltstone Fig. 1. Schematic summary
� Dolostone
illustrating tectonostratigraphic
- Shale
Joo<:>J Carbonate relationships of Lower Palaeozoic
E:£2il Limestone conglomerate e lements in western Newfoundland.
 Metal-rich shales, Newfoundland 12 1

HARE BAY
ALLOCHTHON

HUMBER ARM
ALLOCHTHON

HUMBER ARM
SUPERGROUP
D
BAY OF ISLANDS �
OPHIOLITE SUITE
PORT A U PORT

PENINSULA A UTOCHTHONOUS CAMB R O

ORDOVICIAN PLATFORMAL
SEDIMENTS

POST-TACONIC SEDIMENT D
Fig. 2. Generalized geologic map of
the Humber Arm Allochthon. 25 50 75 100 km

Lower-Middle Ordovician Irishtown Formation
which contains quartzitic sandstone, conglomerate
and shale. These units are probably the deep-water
time-equivalents of the Labrador Group.
These are overlain by upper Middle Cambrian to
Lower Ordovician deep-water carbonate slope de­
posits derived from adjacent platform carbonates.
In the Bay of Islands area this sequence is termed
the Northern Head Group (Botsford, 1988), while
laterally equivalent and coeval strata to the north
are termed the Cow Head Group (James & Stevens ,
1986) (Fig. 3). The Northern Head Group comprises
the upper Middle Cambrian to Lower Ordovician
Cooks Brook Formation and the Lower Ordovician
(Arenigian) Middle Arm Point Formation (Fig. 3).
Both groups are conformably overlain by flysch
(Fig. 3), termed the Eagle Island Formation in the
Bay of Islands area (Botsford, 1988) and the Lower
Head Formation in the Cow Head area (Williams
et al., 1985). The Humber Arm Allochthon is struc­
turally thin at its northern and southern extremities,
so that only the Cow Head Group and Lower Head
Formation are preserved, in imbricate slices, in the
Cow Head area.
The Humber Arm Supergroup constitutes
the most complete and intact record of deep­
marine conditions through the late Middle
Cambrian to earliest Middle Ordovician in western
Newfoundland. Because of the stratigraphic control
available for the Northern Head and Cow Head
Groups, these two sequences are particularly useful
for documenting changes in deep-marine depo­
sitional conditions which may bear on the mobility
and precipitation of metals; discussion in ensuing
sections is directed toward this.
122
MELANGE
c:i
a:
0 their deposition under local palaeoceanographic
�t '"
COW HEAD AREA
�
MELANGE ��
.......____<::>
BAY OF ISLANDS AREA
Fig. 3. Schematic summary of the Humber Arm
Supergroup, in the Humber Arm Allochthon, illu strating
the relationship between the Bay of Islands and Cow Head
areas. Legend as per Fig. 1 .
Relationship o f the Northern Head and
Cow Head Groups
The Cow Head and Northern Head Groups are
laterally equivalent toe-of-slope sediment apron
deposits (James & Stevens, 1986; Botsford, 1988).
Both are roughly 400 m thick, and comprise car­
bonate conglomerates, bedded lime grainstone ,
chert and shale (Fig. 3). Shale occurs interbedded
with conglomerate, ribbon and parted limestone,
and dolostone.
A pronounced proximal (northwest) to distal
(southeast) transition is evident in the Cow Head
Group. Proximal Cow Head Group facies are domi­
nated by coarse carbonate conglomerate with minor
interbedded shale , while distal facies are dominated
by shale. A similar but more subtle depositional
polarity is evident in the Northern Head Group.
While both the Northern Head and Cow Head
J. W. Botsford and D. F. Sangster
Groups comprise carbonate gravity deposits and
shale, differences between them reflect an irregular
carbonate margin morphology which has controlled
conditions (Botsford, 1988) (see below).
SEDIMENTOLOGY
A marked change in sedimentological and ich­
nological character occurs within the deep-water
sequences of the Humber Arm Supergroup sugges­
0 <j MELANGE tive of a widespread change in depositional con­
��. ditions. This is pronounced in the Northern Head
Group and more subtly reflected in the Cow Head
Group. In general faunal communities in marine
environments decrease in diversity, size and numbers
of individuals with decreasing oxygen levels, from
0
�
commonly rich, diverse communities under aerobic
0
conditions, to a restricted (commonly vermiform)
infaunal community under dysaerobic conditions to
a complete lack of benthos under anaerobic con­
ditions (Rhoads & Morse, 197 1 ; Byers, 1977).
Within the Northern Head Group, shales of the
lrishtown and Cooks Brook Formations contain
abundant organic carbon and are very poorly bio­
turbated. This suggests deposition from the late
Middle Cambrian to the Late Tremadocian under
poorly oxygenated conditions. A marked change is
apparent at the (Late Tremadocian) base of the
Middle Arm Point Formation. Shales of the Middle
Arm Point and Eagle Island Formations are charac­
terized by ( 1) a marked increase in the diversity and
intensity of bioturbation (Botsford, 1988); (2) di­
minished organic carbon content; and (3) the
appearance of oxidized red (locally interbedded
with green) shales. This is suggestive of deposition
under better oxygenated conditions. Trace fossil
diversity in 'neritic' and 'flysch' facies remained
relatively constant through the Lower Palaeozoic
(Seilacher, 1978) and it is considered unlikely that
the increase in bioturbation level within the
Northern Head Group is the result of any marked
evolutionary change.
GEOCHEMISTRY
Coincident with the sedimentological contrast de­
scribed above are changes in geochemical aspects
including: (a) manganese content, (b) barium con­
tent and (c) sulphur-carbon relationships, which
 Metal-rich shales, Newfoundland
are reviewed here for shales through both the
Northern Head and Cow Head Groups.
Manganese
There is a contrast of manganese abundance between
the Northern Head and Cow Head Groups. The
manganese content of Northern Head Group shales
(Fig. 4) increases markedly from low 'background'
levels through the Cooks Brook Formation to
anomalously elevated levels, of up to 6·5 wt% MnO
within the Middle Arm Point and lowermost Eagle
Island Formations. Manganese in this enriched inter­
val occurs in three principal forms: ( 1) diagenetic
finely crystalline manganese carbonate disseminated
in red and green shale; (2) diagenetic manganese
carbonate bands, up to 3 em thick, in red and green
shale; and (3) manganese-iron carbonate which has
overgrown individual grains within dolomitic silt­
stones. Manganese is only present within carbonate
minerals.
Based on petrographic evidence and field relation­
ships this manganese carbonate precipitation oc­
curred very early in the diagenetic sequence, very
near the seafloor before compaction and prior to
extensive and protracted silica and carbonate cemen­
tation (Botsford, 1 988). This style of manganese
precipitation appears to be consistent with models of
early upward diffusion of reduced manganese under
shallow burial, and precipitation across a 'diagenetic
front' (e.g. Wilson et a/., 1986). This has been
described and modelled for an oxidative front and
Fig. 4. Stratigraphic distribution of
manganese within shales of the
Northern Head Group and adjacent
units. Elevated concentrations of
manganese above the Cooks
Brook-Middle Arm Point
boundary indicate the precipitation
of manganese carbonate resulting
from elevated Eh levels.
123
precipitation of manganese oxides (Lynn & Bonatti,
1965). We suggest that under somewhat lower Eh
and higher bicarbonate concentration this precipi­
tation has occurred not as oxides but manganese
carbonates. Recent analogues of this style of precipi­
tation have been described by Calvert & Price
( 1970a) and Pederson & Price ( 1982). Models of
early, shallow-burial diagenesis (reviewed in Hesse,
1 986) indicate that bottom-water conditions, such as
dissolved oxygen levels, can readily be responsible
for chemical gradients at shallow burial.
An analogous relationship between manganese
oxides and carbonates is illustrated in Cretaceous
and Tertiary shallow-water manganese ore deposits
(Frakes & Bolton, 1984; Bolton & Frakes, 1985).
Here manganese oxides have been precipitated in
the shallowest, best-oxygenated portions of the
basin, while laterally equivalent manganese carbon­
ates have been precipitated at greater water depths,
under apparently lower but still mildly positive Eh.
No manganese enrichment occurs in proximal Cow
Head shales, and only very subtle enrichment occurs
in distal shales from the Arenigian portion of the
section (Fig. 5).
Barium
The stratigraphic distribution of barium within shales
displays a pattern similar to that of manganese
within the Humber Arm Supergroup. A pronounced
enrichment of barium in shale (up to 8000 ppm) is
evident through the Arenigian part of the Northern
a
"' o
a a a
2 4 6
�
<wt.%)
..
.. MnO
E
124 J. W. Botsford and D. F. Sangster

Proximal setting Distal setting

Cow Head
Martin Pt.
m
�0
00
p
00
!§ 0
f- 11m
�� 0
p-
b 0
JjO 0

0
(-
�
�.:0�
.

m �0 0
0
0

0
r �
m 0 ill
�L

\ �
0
:=-
m

"' 0
!!-� wo
ill
0

II
i'!!ll£ jfl
0

0 .5 1.0
' 0 I I I I I I I I I
0 .5 1.0

MnO (wt.%) MnO (wt.%)

Fig. 5. Stratigraphic distribution of manganese in shales (black) of the Cow Head Group in proximal (Cow Head) and
distal (Martin Point) settings.

Head Group section (Fig. 6), but absent in the Cow
Head Group.
In the Middle Arm Point Formation (Northern
Head Group) barite occurs within shale as early
precipitated, euhedral crystals, generally fine crystal­
line but ranging up to 4 mm. Petrographic evidence
indicates that this authigenic barite was coprecipi­
tated with manganese carbonate, i.e. very early in
the diagenetic sequence, again prior to compaction
or any cementation.
Models of progressive sediment reduction under
shallow burial indicate that under anoxic bottom­
water conditions, active sulphate reduction will occur
at, or near, .the seafloor and the early diagenetic
precipitation or preservation of sulphate minerals is
highly unlikely. Such appears to be the case through
the Cambrian portion of the Northern Head Group.
Under more oxidizing conditions, an oxidizing zone
of variable thickness will exist at the top of the
sediment column, where sulphate is stable. The
principal source of sulphate in pore waters of this
zone will be: (1) diffusion from overlying seawater;
and (2) upward diffusion, from the underlying zone
of sulphate reduction, of reduced sulphur which is
reoxidized (Berner, 1980). Such a diagenetic en­
vironment clearly represents suitable conditions for
the precipitation of sulphate minerals (i.e. barite)
and the distribution of barite illustrated in Fig. 6 is
 Metal-rich shales, Newfoundland
·I
400
'�1,,,
i'"" lo
Fig. 6. Stratigraphic distribution of
barium within shales of the
Northern Head Group and adjacent
units. Enrichment within the Middle
Arm Point Formation indicates the
precipitation of authigenic barite
related to the preservation of
sulphate under elevated Eh levels.
consistent with a transitiOn to better oxygenated
seafloor conditions in the Lower Ordovician.
Two mechanisms may bear on the preservation of
authigenic barite and manganese carbonate during
ensuing burial:
1 Middle Arm Point shales which host these
authigenic minerals contain essentially no organic
carbon. The bacterially driven oxidation of organic
carbon is essentially the 'engine' which drives the
continuing reduction of sediment through progres­
sive burial. If contained carbon were consumed
early (i.e. at shallow levels) in the Middle Arm Point
diagenetic system, through a combination of dimin­
ished initial supply or extensive consumption in the
oxidation zone, then Eh may have stabilized until
lithification was essentially complete.
2 Silica occurs as an early and pervasive cement in
the Middle Arm Point and may locally have effected
the early closure of the diagenetic system, isolating
barite and manganese carbonate from subsequent
dissolution.
Sulphur-carbon relationships
Review
Studies of recent and ancient sediments indicate that
sulphur-carbon relationships are indicative of early
depositional conditions. Pertinent reviews may be
found in Berner (1970, 1984), Leventhal (1979, 1983,
1987) and Raiswell & Berner (1985). Under 'normal
marine' oxygenated bottom-water conditions, sul­
phur and carbon maintain a linear relationship in
125
�
" B
0
a
"
n 0
0
4 6 8
Ba (ppm x1000)
sediments due to S : C stoichiometry established
during progressive microbial sulphate reduction. The
S : C ratio in this case is 0·357 (Leventhal, 1983;
Raiswell & Berner, 1985). Under anoxic conditions,
sulphate reduction commences in the water column
above the seafloor, resulting in the precipitation of
'excess' sulphide (providing there is sufficient iron
present to precipitate pyrite). Hence 'anoxic' sedi­
ments display higher sulphur : carbon ratios (wt%
sulphur : wt% organic carbon).
Notwithstanding the complicating factors of:
( 1) addition of late pyrite, not related to early burial;
and (2) variations in sedimentation rate (cf.
Leventhal, 1 983) which may obscure these initial
ratios, this approach may allow the better discrimi­
nation of: ( 1) anoxic conditions which promoted the
early precipitation of sulphides in the ambient water
column; and (2) relatively oxygenated depositional
settings.
A further potential complication is the loss of
carbon during burial and thermal maturation. This
has most likely taken place in the Humber Arm
Supergroup and probably accounts for the high (rela­
tive to thermally immature sediments) sulphur :
carbon ratios presented below. A survey of illite
crystallinity and conodont alteration indices (CAl)
was conducted through the sequences sampled and
these parameters are consistent throughout (e.g.
CAl = 1 - 1· 5). (These data are not considered
directly relevant and are omitted for brevity, but
available upon request.) Hence the thermal
maturity of the sequences discussed is considered
consistent for the internal comparison presented
here.
126 J. W. Botsford and D. F. Sangster

Northern Head Group and adjacent units Cambrian and earliest Ordovician, but gave way to a
better oxygenated setting briefly through the Late
Because of temporal variations in depositional con­
Tremadocian. Poorly oxygenated conditions were
ditions the S : C ratio can be more meaningfully inter­
re-established in the Arenigian , and appear to have
preted when examined with stratigraphic control.
changed to better oxygenated conditions again in
Because the sulphur : carbon ratio gives a measure
the latest Arenigian, immediately preceding the
of oceanic bottom-water conditions the variation in
deposition of the Lower Head Sandstone. Data from
this ratio through a stratigraphic interval should
the proximal environment are sparser and more
indicate temporal variation in depositional environ­
scattered, but do not conflict with this interpretation.
ments. Figure 7 shows sulphur : carbon variations
through the Irishtown Formation, Northern Head
Group and lowermost Eagle Island Formation. Data Summary and discussion
reach a maximum at the Irishtown-Cooks Brook
An Early Ordovician change in oceanic conditions is
Formation boundary, and although somewhat scat­
recorded in the deep-water sediments of the Humber
tered are generally greater than values for normal
Arm Supergroup, but the response to this change
marine sediments and suggestive therefore of anoxic
was different in the laterally equivalent Northern
or poorly oxygenated bottom-water conditions,
Head and Cow Head Groups.
through deposition of the uppermost Irishtown and
In the Northern Head Group this change occurred
Cooks Brook Formations. A marked decrease in
at the Cooks Brook-Middle Arm Point Formation
ratios , indicative of the transition to oxygenated
boundary. Evidence for a change in oceanic con­
'normal marine conditions' occurs in the (Arenigian)
ditions includes :
Middle Arm Point Formation.
1 A marked increase in bioturbation at the forma­
tion boundary;
2 The establishment of a new early diagenetic regime
Cow Head Group
represented by (a) hematite, (b) authigenic manga­
Sulphur: carbon ratios indicate that temporal vari­ nese carbonate, and (c) authigenic barite;
ations in depositional conditions also occurred in the 3 A marked decrease in S : C ratios indicating a
Cow Head Group (Fig. 8). In the distal environment, transition to better oxygenated conditions in the
locally elevated S : C values suggest that poorly Middle Arm Point.
oxygenated conditions occurred during the Late Considered together, this evidence is consistent

500

400 elevated S within

authigenic sulphate

a�
Fig. 7. Stratigraphic distribution of
sulphur : organic carbon ratio within
0 shales of the Northern Head Group
and adjacent units. High ratios
0 0 indicative of poorly oxygenated
q, depositional conditions span the
uppermost Irishtown and Cooks
D
Brook Formations. The decrease in
S : C ratios, beginning at the (Upper
Tremadoc) Cooks Brook- Middle
Arm Point (MAP) boundary and
continuing into the MAP Formation,
marine conditions suggests a marked transition to
better oxygenated conditions. The
two samples which do not fit this
10 12 14 16 18 20
pattern contain e xcess sulphur within
sulphur/organic carbon authigenic sulphate (barite) .
 Metal-rich shales, Newfoundland 127

Cow Head
PROXIMAL Martin Pt. DISTAL
ljO
lOO

�0 0 0
l50 0

0 �0 I
0

�
JjO
JOO

JOO
150

I
100
JjO
�
\
&
10
200 oo
150 0
c
�

i5
�
<.) m
� 100
s:
"

100 34·5-

oo
"' Normal marine conditions
j0

"' Normal marine conditions

0 2 4 6 8 10
o�--l--,1--,l,-,lr--,-l-,-l-,-l-,-1-,-1-1
0 2 4 6 8 10

sulphur/organic carbon
Fig. 8. Sulphur : organic carbon ratios for shales of the Cow Head Group. Low values within the Tremadocian suggest an
episode of better oxygenated conditions, which contrasts with the preceding Cambrian and subsequent Arenigian
depositional and early diagenetic settings.

with an Early Ordovician 'ventilation event' which
persisted from the Late Tremadocian through the
Late Arenigian in the Northern Head Group.
While this Early Ordovician transition to more
oxidizing deep-water conditions is dramatic in the
Northern Head Group, the change is much more
subdued and temporary in the Cow Head Group. In
the Cow Head Group S : C ratios suggest that weakly
oxygenated conditions were established in the Late
Cambrian, to be temporarily replaced by more oxy­
genated conditions during the latter part of the
Tremadocian. Poorly oxygenated conditions were
again re-established at the Tremadocian-Arenigian
boundary, particularly in the proximal environment.
The absence of abundant authigenic manganese car­
bonate and barite suggests that pronounced changes
in early diagenetic conditions related to a sudden
change in redox conditions did not occur in the Cow
Head Group. This contrast between the Northern
Head and Cow Head Groups has been ascribed to
variability in the carbonate margin and slope mor­
phology, which influenced local palaeoceanographic
conditions and resulted in the more extensive and
continuous deposition of biogenic debris in the Cow
Head area (Botsford, 1988).
Notwithstanding these lateral and facies vari­
ations, the abundance of organic carbon in Middle
Cambrian to Early Ordovician sediments is con­
sistent with an episode of extensive black shale de­
position, suggestive of poorly aerated deep-marine
bottom water, worldwide (cf. Leggett et a/., 1981).
The appearance of more oxidizing conditions in the
128 J. W. Botsford and D. F. Sangster
Late Tremadocian of the Northern Head and Cow
Head Groups is approximately coincident with an
Early Ordovician interval sparse in black shale
worldwide, suggesting that this oxygenated episode
may reflect global oceanic conditions.
BASE METALS
Introd uction
Localized enrichments of base metals (zinc, lead,
copper and nickel) are apparent in shales of the
Humber Arm Allochthon, but in detail differ in
magnitude and mode of occurrence between the
Northern Head and Cow Head Groups. Individual
enrichments in the following order of magnitude
occur in the Northern Head Group: zinc-400 ppm,
lead-300 ppm, copper-350 ppm and nickel-
130 ppm. Lead occurs at these anomalous concen­
trations only in the Northern Head Group and
enrichments of the other metals do occur in the Cow
Head Group but are not as profound.
Anomalously high nickel contents can be at­
tributed to two contrasting styles of occurrence.
First, nickel is associated with disseminated sulphides
in shales (see discussion below). Second, nickel oc­
curs in detrital silicate grains in ophiolite-derived
flysch (Lower Head, Eagle Island Formations) cap­
ping both allochthonous sequences.
Northern Head Group
Abundant pyrite occurs in an approximately 10 m
interval at the base of the Northern Head Group,
near the Irishtown -Cooks Brook Formation bound­
ary. Here, several beds of carbonate pebble con­
glomerate, ranging in thickness from 20 to 400 mm,
are partially to completely replaced by pyrite (Fig.
9a). The only lithology which is never replaced is
black, phosphatic shale, which comprises up to 10%
of individual beds. In some instances, where replace­
ment is complete, field textures are suggestive of
detrital pyrite, but petrographic examination indi­
cates that this is a relatively fine crystalline (30 �J.m),
pebble-by-pebble replacement of an original carbon­
ate conglomerate, with interstitial ferroan carbonate
cement.
This unit overlies a 40 m thick black shale sequence
at the top of the Irishtown Formation and occurs
within the most intensely anoxic interval developed
in the Humber Arm Supergroup. No base metal
sulphides have so far been observed.
The stratigraphic distributions of lead, zinc,
copper and nickel within the Northern Head Group
(Fig. 10) show a pronounced enrichment in
Arenigian shales at the top of the Middle Arm Point
and base of the Eagle Island Formation. Petro­
graphic and SEM/EDX (scanning electron
microscopy/energy diverted X-ray analysis) examin­
ation revealed the presence of chalcopyrite, galena,
sphalerite and locally pentlandite all occurring as
highly disseminated blebs and grains, 10-50 �tm in
size, and within very thin veinlets.
Sulphide blebs are commonly irregular, inter­
grown and locally replacive with the clay matrix.
Where sulphides have been noted within adjacent
thin sandstones, they occur as late pore fillings, sur­
rounding detrital grains and locally replacing inter­
stitial matrix and cement (Fig. 9b). Intergrown
galena-sphalerite (Fig. 9c) and galena-chalcopyrite
also occur in cubic habit.
Veinlets of galena or chalcopyrite up to 0.25 mm
in width occur intergrown with vein-filling potassium
fieldspar and quartz (Fig. 9d).
All metal anomalies in the Northern Head Group
and adjacent units occur in bedded sediment. Sam­
pling of associated melange units has yielded only
background concentrations of zinc, lead, copper and
nickel.
Cow Head Group
Figures 11 and 12 illustrate the stratigraphic distri­
bution of zinc, lead, copper and nickel within proxi­
mal and distal facies shales of the Cow Head Group.
In contrast to the Northern Head Group, zinc and
copper anomalies within Cow Head Group shales
are not concentrated at one stratigraphic horizon,
but are scattered from the Upper Cambrian to the
Lower Ordovician. Compared to Northern Head
Group shales, concentrations of lead, nickel, zinc
and copper are consistently lower.
While the stratigraphic distribution of metal en­
richments is scattered, it is interesting to note that
all but one (85-20; Fig. 12) occur within parts of the
section characterized by poorly oxygenated depo­
sitional conditions. Detailed SEM/EDX examin­
ation indicates that most enriched metal occurrences
are related to the presence of organic carbon. In
some cases, sphalerite, chalcopyrite and ?pyrrhotite
replace delicate framboidal pyrite (Fig. 13a), which
is locally associated with organic matter. In other
cases, blebs of sphalerite, with minor pyrite, sur­
round (Fig. 13b) or occur directly within (Fig. 13c)
 Metal-rich shales, Newfoundland 129

Fig. 9. Sulphide occurrences in the Northern Head Group. (a) Thin beds of carbonate conglomerate completely replaced
by pyrite (py) within laminated black shale (sh); base of the Cooks Brook Formation (late Middle Cambrian), Seal Cove,
Middle Arm, Bay of Islands. (b) SEM/EDX photomicrograph (backscatter mode) illustrating pore-filling chalcopyrite
blebs (arrows), with small inclusions of galena (bright areas), within thin sandstone bed at base of Eagle Island Sandstone.
Surrounding silicate grains are opaque in backscatter mode but adjacent detrital chromite grain (Ch) can be seen; Eagle
Island Formation, Bay of Islands area; magnification and scale in micrometres at lower right. (c) SEM/EDX
photomicrograph (backscatter mode) illustrating intergrowth galena (gal)- sphalerite (sph) grain within (opaque) shale
matrix; Middle Arm Point Formation, Bay of Islands area; magnification and scale in micrometres at lower right. (d) SEMI
EDX photomicrograph (scanning mode) of veinlet within Middle Arm Point Formation shale illustrating intergrown
chalcopyrite (Cp) and potassium feldspar (fsp) cross-cutting shale (sh); magnification and scale in micrometres at lower
right.

flattened fragments of organic material (which can compaction or any cementation.

frequently be identified as graptolite fragments). All It is of further interest to note that the style of
of these sulphides have precipitated relatively early sulphide occurrence is different in sample 85-20
in the diagenetic history of the shales, prior to within Tremadocian 'normal marine' sediments.
 ......
VJ
0

ill' 'a

,�

"'
�
' \:!:)
' 0
1:;
"'
' �
'm �
ag "'
;::;
' P...
i
'cl'
t:J
:->J
�
200 300 0 20 40 60 80 100 120 140
�;:;.
0 100 200 300 400 0 100 200 300 0 100
"'
...
Zn !ppm) Pb !ppm! Cu !ppm) Nl !ppm!

Fig. 10. Stratigraphic distribution of zinc, lead, copper and nickel within shales of the Northern Head Group and adjacent units. The stratigraphic i nterval
spans (1) the Irishtown Formation, at the base, through (2) the Cooks Brook and Middle Arm Point Formations (Northern Head Group) and (3) the
o verlying Eagle Island Formation. This displays the anomalous concentration of these elements in sulphides localized within the Arenigian part of the
section .
 Cow Head

100 � � �
0 0 � o0 �

0
• oO
B �
B � •0
� 0� 0 [\) 800 0
� 0
0 0 00
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�
Oo
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0 0 "'

0 0 0 0 12:.
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I
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i
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0 ' 0 o,

100 100 � 100 • ro �� rw � � � m 100 � lOO 10 w 100 120 liO

!ppml Cu (ppm)
Zn (ppm) Nl !ppml
Pb

Fig. II. Stratigraphic distribution of zinc, lead, copper and nickel in shales of the Cow Head Gro up deposited in a proximal setting.

......
w
 ......
w
N

Cow Head Group: Distal setting

Mart1n Pt
4� 6� �� ��
0
f g

"'�-�
0� 0 0 0 �0
0 0 0 �0
0 0 0 0
100 100 o 100 0 100 0
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·c: 0 0 O 0
.. 0 0 00 rn
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< 0 0 0 0
J� 0 J� 0 J� 0 i� 0
z
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0 0 0 0
�
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-JOO JOO lOO •JOO
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0 Sample 85-20 tl;)
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a: 0 0 0 C)
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I'll t:Bdl I'll � c] 0 �0 �
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f
!00 0 0 � 100 �0 100 g 0 100 0 0
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0 0 0 0
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:;;
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E
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u
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0 I I I I

100 100 JOO 100 W ro 110 100 100 liD 111J J10 100 100 JOO 10 � 00 I� I� 110

Pb (ppm) Cu (ppm) Nl (ppml

Zn (ppm)

Fig. 12. Stratigraphic distribution of zinc, lead, copper and nickel in shales of the Cow Head Group deposited in a distal setting.
 Metal-rich shales, Newfoundland 133

{C)
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-·
_,. __
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Fig. 13. Sulphide occurrences in the Cow Head Group. (a) SEM/EDX photomicrograph (scanning mode) illustrating
framboids comprising finel y intergrown chalcopyrite and pyrrhotite within Cow Head Group shale; Western Brook Pond;
magnification and scale in micrometres at lower right. (b) SEM/EDX photomicrograph (backscatter mode) illustrating the
association of sphalerite (and minor pyrite) blebs (bright areas) with flattened fragments of organic material ( flattened
black area ) . This style dominates sulphide occurrences in the Cow Head Group; magnification and scale in micrometres at
lower right. (c) SEM/EDX photomicrograph (backscatter mode); detail of above illustrating the presence of sphalerite
(bright areas) within flake of organic material; magnification and scale in micrometres at lower right. (d) Chalcopyrite (Cp)
replacing detrital chert grain in sample 85-20 from Tremadocian shale of the Cow Head Group; magnification and scale in
m icrometres at lower right.

Here chalcopyrite occurs replacing chert and other
grains (Fig. 13d) reminiscent of the replacive style of
precipitation described for sulphides in the Northern
Head Group.
Discussion
Metal enrichments in shales of the Northern Head
Group and Cow Head Group appear to have oc­
curred at different times and by contrasting pro­
cesses. In the first case, precipitation of zinc, copper,
lead and nickel sulphides appears to have been
a stratigraphically confined, relatively late event,
through vein and pore filling and replacement, not
directly related to the presence of organic carbon.
By contrast, sulphides in the Cow Head Group
appear to have been relatively early and only in one
example have been extensively remobilized. This
contrast in sulphide occurrence may be related to
several factors.
While transition metals are generally mobile in
the divalent (reduced) form, precipitation as sul­
phides will occur under reducing conditions in the
presence ofH2S (Jacobs & Emerson, 1982; Maynard,
134 J. W. Botsford and D. F. Sangster
1983). Transport mechanisms may include the forma­
tion of complexes involving chloride or organic
matter. Concentration of metals in organic material
may commence during the life-cycle of organisms,
and combined with the behaviour of these metals
outlined above, is thought to account for the common
association of sulphide mineralization with (organic­
rich) black shale (Vine & Tourtelot, 1970; Calvert &
Price, 1970b; Maynard, 1983).
Preliminary evidence suggests that these processes
of metal enrichment, related to the presence of
organic carbon, controlled localized sulphide precipi­
tation in Cow Head Group shales. This does not,
however, appear to be the principal factor controlling
anomalous occurrences of lead , zinc , copper and
nickel in the Northern Head Group, since this en­
richment occurs in an interval which represents the
highest levels of dissolved oxygen in the depositional
and early diagenetic environment.
Factors responsible for this localized enrichment
may include: ( 1) the transport of metals , within
detrital grains or as complexes, during deposition of
the Eagle Island Sandstone ; (2) the in situ mobiliz­
ation of metals under a redox gradient during early
diagenesis (cf. Klinkhammer et al. , 1982); or (3)
contrasting burial and deep diagenetic history. As
previously discussed, comparable illite crystallinity
indices and conodont alteration indices in the two
groups suggest that the last alternative is not likely.
SUL P HU R ISOTOPES
Introd uction
To assess further the relationship of sulphide precipi­
tation and postulated changes in oceanic conditions
sulphur isotopic values in pyrite have been deter­
mined in shale from the Northern Head and Cow
Head Groups. Pyrites selected for isotope determi­
nation are of known or readily inferred age and
span the entire stratigraphic sequence under
consideration.
Secular trends in sulphur isotopic values may be
used to identify episodes of oceanic stagnation, and
associated widespread reducing conditions , and ven­
tilated, relatively oxidizing conditions, which may
have been a factor in controlling base metal mobility
(cf. Goodfellow & Jonasson, 1984; Goodfellow,
1987). In the Cambrian-Devonian sedimentary se­
quence of the Selwyn Basin, for example (ibid. ) ,
anoxic events related to oceanic stratification are
characterized by isotopically heavy pyrite sulphur,
where 634S is roughly +30%o. Ventilated episodes
are defined by less positive isotopic values, where
()34S approaches roughly +5%o.
The nature of the sulphur reservoir present in
bottom water at any given time is indicated most
directly by early diagenetic pyrite (or its metastable
precursor), precipitated at the onset of bacterial
sulphate reduction during shallow burial. Ensuing
generations of pyrite tend to be coarser crystalline
and more euhedral and may incorporate sulphur of
uncertain isotopic history. In general, it appears that
pyrite precipitated first in the diagenetic sequence
incorporates the isotopically lightest sulphur , and
that ensuing pyrite generations become progressively
isotopically heavier (e.g. Raiswell, 1982).
A chemical technique recently developed at the
Geological Survey of Canada (Hall et al. , 1988)
facilitates the extraction, separation and sulphur
isotope determination of this highly disseminated,
fine-crystalline, early precipitated pyrite which com­
monly occurs in the shale samples of this study. The
majority of sulphur isotopic analyses reported in this
study are of this type of sulphide occurrence. The
sulphur isotopic signatures for 1 1 samples of burrow­
filling and fine nodular pyrite from the Cow Head
Group have also been determined. Four samples
from the Northern Head and Cow Head Groups
have yielded sufficient authigenic barite to establish
the sulphur isotopic signature in this sulphate.
Chemical separation of pyritic and baritic sulphur
was performed using the techniques of Hall et al.
(1988). Sulphur isotopic determinations were then
performed at Geochron Laboratories, Cambridge ,
Massachusetts, on a contract basis.
Temporal changes in sulphur isotopic signature
A pattern of temporal change in 634S values is most
clearly displayed by the Northern Head Group
(Fig. 1 4), in part because of sampling density, and
is confirmed by data from the Cow Head Group
(Fig. 15). Based upon the principles briefly outlined
above , this temporal variation is remarkably consis­
tent with the postulated Lower Ordovician ventil­
ation event discussed in previous sections.
Northern Head Group
Sulphur isotopic signatures in the Northern Head
Group are heaviest near the (uppermost Middle
Cambrian) Cooks Brook -Irishtown Formation
 Metal-rich shales, Newfoundland 135

.
•
E -:"l -10 10 30

D e p o s i t i o n a l /e a r l y d i a g e n e t i c c o n d i t i o n s S u l p h u r I s o t o p i c s i g n a t ure o r :

I n d i c a t e d b y o t h e r p a r a m e t e r s (se d i m e n t o l o g y ,
s h a l e g e o c h e m . , S IC r e l a t i o n s h i p s ) 0 f i n e l y d i s s e m i n a t e d p y r i te

Fig. 1 4 . Sulphur isotopic signature

B
In shale

(%o) of finely disseminated pyrite in v e n t i l a t ed c o n d i t i o n s

shales of the Northern Head Group i a u t h i g e n i c b a rite I n s h a l e

and adjacent units. The � po o r l y o x y g e n a t e d c o nditions

sulphur isotopic signature of
authigenic barite in three shale
samples is also shown. • A n o m a r o u s m e t a l c o n c e n tra t i o n s

boundary, where b34S values close to + 30%o
occur (Fig. 14). This coincides with the most pro­
nounced anoxic conditions , as indicated by sulphur ­
carbon relationships discussed previously (see Fig.
7). A progressive upward change to lighter-pyrite
sulphur in the Early Ordovician is evident, and is
most pronounced in the Middle Arm Point Forma­
tion, where o34S values approaching 30%o occur.
- setting is not presently available.
Here again sulphur isotope data mirror other evi­
dence in suggesting the onset of ventilated conditions
in the Early Ordovician. Of particular i nterest is the
return, in the Arenigian, to a heavier isotopic signa­
ture, ranging from roughly 0 to +22%o. This
stratigraphic interval coincides with the anomalous
concentrations of zinc , lead, copper and nickel within
the uppermost Middle Arm Point Formation (see
Fig. 10). The significance of this relationship is un­
clear. It may be that the sulphur isotope signature is
indicating a subtle return, not otherwise apparent,
to more stratified conditions conducive to the pre­
cipitation of sulphides.
Cow Head Group
The transition from isotopically heavy pyrite sui-
phur in the Cambrian to a lighter signature in the
Ordovician is also evident in the Cow Head Group.
Furthermore the presence of isotopically heavier
sulphur in the Arenigian is evident in the proximal
setting (Fig. 15) , coincident with the return to poorly
oxygenated conditions described in previous sec­
tions. Isotopic data for the same interval in the distal
Sulphur isotopic signature of barite in the Northern
Head and Cow Head Groups
The sulphur isotopic signature of authigenic barite
in the Northern Head Group (Fig. 14) and Cow
Head Group (Fig. 15) falls within the range of b34S
values established for pyrite sulphur in surrounding
samples. This is surprising since fractionation associ­
ated with sulphate reduction normally results in a
considerable separation of sulphide and sulphate
signatures. Only one (Northern Head Group) sample
could be interpreted as distinct from the pyrite
sulphur field, and falls within the o34S range of
+30%o in dicated for Cambro-Ordovician sulphate
by Claypool et a!. ( 1980). The reason for this conver­
gence of pyrite and barite isotopic signatures is not
 P R OX I M A L DI STAL -
Cow Head 00
0\
SULPHUR ISOTOAC SIGNATURE Martin Pt. SULPHUR ISOTOPIC SIGNATURE

400

350
I 0
Do
0I
� 0
z � 300
"'
[j
>
0
0
a:
0
=- 150

I/ �
100 I
0
�
�- �

1
�
· ·· · ·

ISO 0 1:<:1
•
�
0 <::>
"'
�;; 0 �
...,

!
.,_
•.;
1 00
�
- ;:::
D � .,_

50 �
:>l
ill I �
0
�
;:::
OQ
"'
-40 "'
-10 10 ...,

o3•s
-40 -� 20 40

o HS
D e p o si t i o n a l /early d i a g e n e t i c c o n d i t i o n s S u l p h u r I s o t o p i c s i g n a t u re o r :

Indicated b y ot h e r p a ra m e t e r s <s e d i m e n t o l o g y ,
s h a l e g e o c h e m . , S iC r e l a t i o n s h i p s ) 0 f i n e l y d i s s e m i n a t ed p y r i te I n s h a l e

i a u t h i g e n i c b a ri t e I n s h a l e

I
v e n t i l a t ed c o n d i t i o n s • b u rrow-f i l l i n g o r l i n e n o d u l a r p y ri t e

Fig. 15. Sulphur isotopic signature (%o) of: (a) finely disseminated pyrite (open
poorly ox ygenated c o n d it i o n s

squares); (b) burrow-filling or fine nodular pyrite (filled squares); and (c)
• A n o m a l o us m e t a l c oncentra t i o n s authigenic barite (si ngle sample) in shales of the Cow Head Group.
 Metal-rich shales, Newfoundland
clear. It may be related, however, to the model
outlined by Berner (1980) of upward diffusion of
reduced sulphur from a zone of bacterially driven
sulphate reduction (where it was fractionated) and
the subsequent reoxidation of this sulphur and incor­
poration in authigenic sulphate. Barite is only found
in 'ventilated' samples.
SUMMARY AND DISCUSSION
Localized enrichments of metals (300+ ppm) in
shales occur in two princip al styles and settings in
the allochthonous Lower Palaeozoic sequences of
western Newfoundland. The contrasting nature of
these occurrences appears to be related to fundamen­
tal differences in depositional and early diagenetic
conditions.
In the Northern Head Group, anomalous metals
in Arenigian shales are found in sphalerite, galena,
chalcopyrite and locally pentlandite which occur as
highly disseminated replacements and pore and vein
fiUings. In contrast, zinc, copper and nickel sul­
phides scattered throughout Cambrian-Ordovician
shales of the Cow Head Group are associated with
organic matter and show only localized evidence of
subsequent remobilization.
The sedimentology, shale geochemistry, sulphur­
carbon relationships and sulphur isotopes indicate
a significant change in the marine environment,
from Cambrian- Early Ordovician anoxic conditions
to a ventilation event commencing in the Late
Tremadocian. These conditions appear to have con­
tinued through the Arenigian in the Northern Head
Group, while S : C profiles suggest a return to more
reducing conditions in the Cow Head Group.
The occurrence of sulphides outlined above ap­
pears to be related to these temporal variations in
oceanic conditions. The most profound buildup of
sulphides consists of pyrite at the (Upper Middle
Cambrian) base of the Cooks Brook Formation in
the Northern Head Group.
The replacive and vein-filling style of sulphide
occurrence in the Northern Head Group (and locally
within the Cow Head Group) may reflect a redox­
related mobilization of metals within sediments de­
posited during the Lower Ordovician ventilation
episode. It is possible that the precipitation of these
sulphides may be related to a return to more stratified
conditions during the Arenigian. In the Northern
Head Group this is subtly suggested by the o34S
profile which briefly returns to more positive values
137
and may indicate an episode of stratified, reducing
conditions conducive to H2S formation and sulphide
precipitation.
It is interesting to note that most of the platform­
hosted base metal occurrences in western
Newfoundland are localized in the Lower Ordovician
St George Group. It is not clear what the relation­
ship is between this mineralization and the Lower
Ordovician 'ventilation event' postulated in this
study. Unknown is the timing of metal mobility (in
deep-marine shales) and the dewatering of this sedi­
mentary sequence. Dewatering during collisional
orogenesis may have commenced as early as the
Middle Ordovician Taconic orogeny, but regional
geologic considerations suggest that the most signifi­
cant compression occurred later, during the Acadian.
ACKNOWLEDGEMENTS
This study forms part of a collaborative project
undertaken through the Canada-Newfoundland
Mineral Development Agreement ( 1984-89), DSS
Contract 23233-7-0223/0 1 -ST. Many of the results
are also based upon fieldwork, sampling and analysis
supported by the Natural Science and Engineering
Research Council funding to N.P. James, whose
advice regarding sedimentological and regional
geological aspects is gratefully acknowledged.
The cooperation and technical support of the
Newfoundland Department of Mines and Geological
Survey of Canada are also acknowledged. Reviews
by E. Cameron, W. Goodfellow and R. Raiswell
substantially improved the manuscript.
REFERENCES
BERNER, R . A . ( 1970) Sedimentary pyrite formation. A m .
J. Sci. 268 , 1-23.
BERNER, R.A. ( 1980) Early Diagenesis: a Theoretical
Approach . Princeton U niversity Press , Princeton,
241pp.
BERNER, R . A . ( 1984) Sedimentary pyrite formation: an
update. Geochim. cosmochim. A cta 48, 605 - 6 15 .
BoLTON , B . R . & FRAKES, L . A . ( 1985) Geology and genesis
of manganese oolite, Chiatara, Georgia , USSR. Geol.
Soc. Am. Bull. 96, 1398- 1406.
BoTSFORD, J . W . ( 1988) Depositional history of Middle
Cambrian to Lower Ordovician deep- water sediments,
Bay of Islands, western Newfoundland. Unpublished
PhD Thesis, Memorial University of Newfoundland,
509pp.
BOUVIER, J . L . & A BB EY , S. ( 1980) Simultaneous determi­
nation of water, carbon dioxide and sulfur i n rocks by
138 J. W. Botsford and D. F. Sangster
volatization and non-dispersive infrared absorptiometry.
Can. J. Spectros. 25, 126- 132.
BYERS, C.W. ( 1977) B iofacies patterns in euxinic basins: a
general model. I n : Deep Water Carbonate Environments
(Ed. by H . E . Cook and P. Enos), pp . 5 - 18. Spec.
Publ . Soc. Econ. Paleont. Miner. 25.
CALVERT, S.E. & PRICE , N .B. ( 1970a) Composition of
manganese nodules and manganese carbonates from
Loch Tyre, Scotland . Contrib. Min. Petrol. 29, 2 1 5 - 233.
CALVERT, S . E . & PRtCE, N . B . ( 1 970b) Minor metal contents
of recent organic-rich sediments off southwest Africa .
Nature 227 , 593-595.
CLAYPOOL, G . E . , HOLSER, W . T . , SAKI, l . R. & ZAK, I .
( 1980) The age curves for sulfur and oxygen isotopes i n
marine sulfate a n d their mutual interpretation. Chem.
Ceo!. 28 , 199-260.
FRAKES, L . A . & BOLTON , B . R . ( 1984) Origin of manganese
giants: sea-level rise and oxic-anoxic history. Geology
12, 83-86.
GooDFELLOW , W. (1987) Anoxic stratified oceans as a
source of sulphur in sediment-hosted stratiform Zn- Pb
deposits (Selwyn Basin, Yukon, Canada). Chem. Geol.
65, 359-382.
GoODFELLOW, W . & JoNASSO N , I. ( 1 984) Ocean stagnation
and ventilation defined by o34S secular trends in pyrite
and barite, Selwyn Basin, Yukon. Geology 12 , 583-586.
HALL, G . E . M . , PELCHAT, J. & LOOP, J. (1988) Separation
and recovery of various sulphur species in sedimentary
rocks for stable sulphur isotope determination. Chem.
Geol. 67, 34-45.
HESSE, R . ( 1 986) Early diagenetic pore water/sediment
interaction: modern offshore basins. Geosci. Can. 13,
165- 196.
JACOBS, L . & EMERSON , S. (1982) Trace metal solubility in
an anoxic fjord. Earth Planet. Sci. Lett. 60, 237-252.
JAMES, N . P . & STEVEN S , R . K . ( 1 986) Stratigraphy and
Correlation ofthe Cambro-Ordovician Cow Head Group,
Western Newfoundland. Geological Survey of Canada,
Bulletin 366.
KLAPPA , C . F . , 0PALINSKl, P . R . & JAMES, N . P . (1980)
Middle Ordovician Table Head Group of Western
Newfoundland: a revised stratigraphy. Can. J. Earth Sci.
17, 1007- 1019.
KLINKHAMMER, G., HEGGIE, D .T. & GRAHAM, D.W. ( 1 982)
Metal diagenesis in oxic marine sediments. Earth Planet.
Sci. Lett. 6 1 , 2 1 1 -219.
KRAUSKOPF, K.B. (1967) Introduction t o Geochemistry.
McGraw-Hill, New York, 72 lpp.
LEGGErr, J . K . , McKERRow, W . S . , CocKs, L . R . M . &
RICHARDS, R . B . ( 1981) Periodicity in the early Palaeozoic
marine realm. J. Geol. Soc. Lond. 138, 1 67 - 176.
LEVENTHAL, J . ( 1979) The relationship between organic
carbon and sulfide sulfur in recent and ancient marine
and euxinic sediments. EOS 60, 283.
LEVENTHAL, J. ( 1983) An i nterpretation of carbon and
sulfur relationships i n Black Sea sediments as indicators
of environments of deposition. Geochim. cosmochim.
A cta 47, 133 - 137 .
LEVENTHAL, J . ( 1987) Carbon and sulfur relationships in
Devonian shales from the Appalachian Basin as an
indicator of environment of deposition. Am. J. Sci. 287,
33-49.
LYNN , D . C . & BoNATTl, E. ( 1965) Mobility of manganese
in diagenesis of deep-sea sediments. Marine Ceo!. 3,
457-474.
MAYNARD, J . B . ( 1 980) Sulfur isotopes of iron sulfides
in Devonian-Mississippian shales of the Appalachian
Basin: control by rates of sedimentation. Am. J. Sci.
280, 772-786.
MAYNARD, J . B . ( 1983) Geochemistry of Sedimentary Ore
Deposits. Springer, New York, 305pp.
PEDERSEN, T.F. & PRICE , N . B . ( 1982) The geochemistry
of manganese carbonate in Panama Basin sediments.
Geochim. Cosmochim. Acta 46, 59-68.
RAISWELL, R . (1982) Pyrite texture, isotopic composition
and the availability of iron. Am. J. Sci. 282, 1244- 1263.
RAISWELL, R . & BERNER, R . A . ( 1985) Pyrite formation in
euxinic and semi-euxinic sediments. Am. J. Sci. 285 ,
710-724.
RHOADS, D . C . & MoRSE, J . W . ( 1971 ) Evolution and eco­
logic significance of oxygen-deficient marine basins.
Lethaia 4, 413 -428.
SEtLACHER, A. ( 1978) Use of trace fossils for recognizing
depositional environments. In: Trace Fossil Concepts
(Ed. by P . B . Basan) , pp. 1 67 - 18 1 , SEPM Short Course
No. 5 .
STENZEL, S . R . & JAMES, N . P . (1987) Death and destruction
of an early Paleozoic carbonate platform, western
Newfoundland. Program with Abstracts, Society of
Economic Paleontologists and Mineralogists Mid-Year
Meeting, AustilL
STEVENS, R . K . ( 1970) Cambro-Ordovician flysch sedimen­
tation and tectonics in west Newfoundland and their
bearing on a proto-Atlantic Ocean . Geological Associ­
ation of Canada, Special Paper No . 7 , pp. 165- 177.
VtNE, J . D . & TouRTELOT, E . B . ( 1970) Geochemistry of
black shale deposi ts - a summary report. Econ. Geol.
85, 253-272.
WtLLIAMS, H. ( 1979) Appalachian Orogen in Canada. Can.
J. Earth Sci. 16, 792-807.
WILLIAMS, H . , JAMES, N . P . & STEVENS, R . K . ( 1985)
Humber Arm Allochthon and nearby groups between
Bonne Bay and Portland Creek, western Newfoundland.
In: Current Research , Part A. Geological Survey of
Canada, Paper 85 - 1 A , pp. 399-406.
WILSO N , T . R . S . , THOMSON , 1 . , HYDES, D . J . , COLLEY, S . ,
CALKIN, F . & SORENSEN , J . ( 1986) Oxidation fronts in
pelagic sediments: diagenetic formation of metal-rich
layers. Science 232, 972-975.
Spec. Pubis inl. Ass. Sediment. (1990) 11, 139-146

Origin of iron carbonate layers in Tertiary coastal sediments

of Central Kalimantan Province (Borneo), Indonesia

G .R . SIEFFERMANN

ORSTOM-UGM Cooperation, Sekip K 3, Yogyakarta, Indonesia

ABSTR ACT

Siderite layers, brown coals and quartzitic sands are an important part of the Tertiary section of the
Rungan River Basin in Central Kalimantan Province, Indonesia. The siderite layers consist of grey, fine­
grained, indurated rocks.
The depositional setting in Borneo during the Upper Tertiary was that of a large coastal lowland area
with peat swamps and tropical giant podzols, much like the modern landscape. This environment seems
to have been favourable for the formation of siderite. A relationship can be suggested between iron
carbonate sedimentation and deferrification of onshore sedimentary continental formations through a
pedological podzolization process. The iron was probably removed from the soils by 'black' waters
which were rich in iron-complexing organic compounds. The iron carbonate was probably formed in
tidal lagoons, in a brackish environment under reducing conditions.
The depositional setting shows that the origin of the iron in siderite layers must be sought laterally,
probably hundreds of kilometres away, in bleached siliceous formations, associated with coal beds which
are the former peat deposits. This mode of occurrence may have application to other sequences where
such distinct lateral relationships are less obvious.

INTRODUCTION

Since 1979, Indonesian and ORSTOM scientists,

within the framework of scientific cooperation be­
tween Indonesia and France, have produced soil
maps covering large parts of Central Kalimantan
Province (Brabant & Muller, 1981; ORSTOM &
Dept Transmigrasi, 1981). Numerous observations
and analyses are available for the post-Miocene
sediments of the Central Kalimantan Coastal Plain
(Sumartadipura, 1976).
The outcrops of these sediments reveal sandy
layers, sometimes intercalated with gravels and
clayey horizons, siderite, and coal beds. An analysis
of the modern depositional setting of the coastal
plain was carried out as a basis for interpreting the
nature and formation of these outcrops. This paper
outlines the characteristics of the main outcrops
along the Rungan River (Fig. 1) and describes the
present coastal landscape and geochemistry of units
within it.
DESCRIPTION OF THE OUTCROPS
Siderite
The most conspicuous outcrops of bedded siderite
are located on the Rungan River, between its conflu­
ence with the Manuhing River and the town of
Tumbang Jutuh (Fig. 1). On this stretch, the Rungan
River cuts its valley through post-Miocene sedi­
ments. Three main siderite outcrops can be ob­
served within the river channel between July and
November, when the water level of the river is low.
The siderite consists of a very hard rock, forming
nearly continuous layers between 200 and 300 mm in
thickness. The layers are so hard that they form
small rapids in the river (Fig. 2). The rock has a very
pale yellowish-grey colour which changes gradually
into dark reddish-violet, especially after a week of
air exposure. This change in colour is not just super-

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun

139
and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
140 C. R. Sieffermann

10 20 30

Fig. 1. Coal and siderite outcrops

c::::? SIDERITE /COAL �LIMESTONE along the Rungan River, Borneo,
Indonesia.

Fig. 2. Outcrop of siderite layers in

the Rungan River, in Central
Kalimantan (Borneo).
 Iron carbonate layers in coastal sediments, Borneo 141

ficial; after two weeks a depth of 20 mm is affected,

and after two months a 100 mm thick block becomes
completely dark red up to the centre. This change in
colour undoubtedly corresponds to an oxidation
process. Submerged under the river water the sider­
ite acquires only a very superficial yellow crust.

Clay beds

The indurated siderite layers are mainly underlain

by fine soft bluish-grey clay. Frequently, organic
matter in the form of leaves and other plant frag­
ments can be observed in these clay layers. The
overlying sediments above the siderite are silty with
an upwards increasing amount of sand, and a minor
amount of quartz gravels.

Coal beds

Between the second and third outcrop of siderite

(Fig. 1), five coal beds can be observed. Coals have
not been observed to directly overlie the siderite.
The rank of the coal is brown coal and the total
thickness reaches 800 mm (Fig. 3). Perfectly pre­
served tree trunks can be found within the coal
layers, indicating a depositional environment of
forest peat, similar to that described by Cecil et al.
(1985) for the Central Appalachian Basin during the Fig. 3. Outcrop of Miocene coal on the Rungan River, in
Carboniferous and comparable to the current peat Central Kalimantan (Borneo).
belt in Kalimantan to the south (Fig. 4).

instead appears to be more like that of coastal

ANALYTICAL DATA
In its X-ray diffraction pattern, the siderite has all
the characteristic reflections of iron carbonate (3·58,
2·79, 2·34 and 2·13 A). Associated with the siderite
is an interstratifi.ed montmorillonite-chlorite. In a
normal state, the main peak for this phase is 12·8 A,
shifting after· heating to 11·8 A, and after glycerol
treatment to )4·7 A. Fine quartz, illite and dis­
ordered kaolinite are often associated with these
minerals. The bluish-grey clay underlying the siderite
contains the same montmorillonite-chlorite min­
eral, associated with disordered kaolinite, illite, and
a small amount of quartz.
The rivers are transporting a different mineral
suite today. In order of abundance, disordered kao­
linite, quartz, illite and goethite dominate the river­
ine clay fraction in accordance with the dominant
oxisol and ultisol cover of the island's interior. The
clay mineral mixture associated with the siderite
sedimentation under a periodic marine influence,
mainly because of its montmorillonite-chlorite
content, its bluish colour and reducing character­
istics, and the absence of goethite and hematite.
An explanation for the genesis of the siderite is
more problematic. A good approach to understand
its deposition is to look at geochemical mechan­
isms of the modern coastal plain of the Indonesian
Central Kalimantan Province.
THE MODERN COASTAL LANDSCAPE
Millions of hectares of poorly drained coastal plains
of the Indonesian Islands are covered with peat. The
peat zone of Kalimantan is situated in relation to the
other landscape units in a well-defined sequence
(Fig. 4): upslope from the peat is a wide zone of
deferrified tropical giant podzols; further inland is a
zone including coal and siderite; and at the centre of
142 G.R. Sieffermann

}
0 50 100Km

Igneous, volcanic and

m�tamorphic rocks with Oxisols
and Ultisols

� Post Mioc�n� s�dim�nts

with coal and Sid�rit� lay�rs
covn

� D�f�rrifi�d PODZOL 5
L...:.J
;Jtf;,'fJ; Thick ombrog�nous PEAT

§ Coastal PEAT on brackish wat�r s� dim�nts Fig. 4. Succession of soil types in

Central Kalimantan Province.

The oxisols
the island is a vast oxisol landscape developed on
crystalline and volcanic rocks. Towards the coastal In the upstream units, the oxisol formation is con­
area, thinner peats overlie predominantly clayey, trolled by two mechanisms: weathering and erosion.
brackish water sediments contammg pyrite, 1 Weathering destroys completely the minerals of
montmorillonite-chlorite and sometimes siderite. the crystalline and volcanic rocks through a hydroly­
sis process. The less-soluble elements remain and
form the characteristic minerals of the oxisols; mainly
GEOCHEMISTRY OF MODERN kaolinites, iron and aluminium oxides and hydrox­
COASTAL LANDSCAPE ides. Such processes have been well studied during
the last30 years by Bonifas (1959), Millot (1964),
The geochemistry of each of the landscape zones Delvigne ( 1965), Lelong ( 1967), Tardy (1969) and
represented in Fig. 4 is different. Sieffermann (1973). These authors have shown that
 Iron carbonate layers in coastal sediments, Borneo 143

during hydrolysis, nearly two-thirds of the weathered
rock is removed in soluble, ionic form. It is easy to
forget this because the process is invisible. The
hydrolysis of 3 parts of andesite gives only 1 part of
soil and the remaining 2 parts disappear. Half of the
dissolved rock is silica. In other words, for each
quantity of soil we can see in Borneo, on the Matto
Grosso Shield in Brazil, or in the Congo Basin, an
equal amount of silica has been transported to the
coastal zone of sedimentation.
2 Erosion affects all soils and removes the soil
minerals formed during the weathering process in
the form of suspensions in the rivers. In equatorial
regions, the soils represent an equilibrium between
the weathering and the erosion processes. This re­
moval of 'soil minerals' can be seen and measured: it
is the solid transport. These two mechanisms are
represented on the right-hand side of Fig. 5.
The giant podzols
This unit occurs over thousands of square kilometres
and forms a very flat landscape. The giant podzols
can be morphologically compared with those of tem­
perate climates, but differ from temperate podzols
by the greater thickness of their horizons. They are
characterized by a white quartz sand horizon, often
more than 5 m thick, overlying an iron and alu­
minium hardpan, frequently more than 2 m thick.
The hardpan forms a nearly permanent water table
with only lateral outflow.
Such podzols have been extensively reported dur­
ing the last 30 years by Viera & Oliveira-Filho
( 1962),
Altenmuller & Klinge ( 1964), Klinge (1967, 1969),
Andriesse ( 1969, 1970), Turenne (1970, 1975),
Flexor et al. ( 1975) and Thompson ( 1986). The
normal, undisturbed vegetation on such soils is
forest.
At its southern limit, the giant podzols are overlain
by ombrogenous thick peats as represented in Fig. 5.
The great contrast in these soils, between the white
quartz sand horizon and the iron and organic hard­
pan, is not caused by a change in depositional source
materials or by facies changes resulting in different
parent materials, but by thousands of years of clay
mineral breakdown through rainwater percolation
The giant podzols have been formed from fluviatile
sedimentary clayey sands, similar to those deposited
by modern rivers, and composed mainly of quartz
gravels and sands, kaolinites and iron hydroxides.
The percolation of the equatorial rainwater through
such sediments created the bleached horizon in which
only quartz remains. If the past rainfall was compar­
able to the modern rainfall, a column of 50 km of
rainwater has percolated slowly through these soils
during the last 30 000 years.
The removal of the iron and aluminium through
organic compounds has been described by Bruckert

SOUTH r----- About 200 Kilom<ttrs ------- NORTH

I I
PODZOLS ---
.J4VA SEA [ OXISOLS and
f---- PEAT -----11-
I 1 w��
SOOm-
I
200m-
100m -
35m-
--�--=-""- �----_,...-- •'

Coastal Peat accumulation area Lateritic

sedimentation weathering area
area
De- ferrificatioo md
de- aluminization area

I
Soluble Al and Fe
organic compounds Soluble
Neoformat ions
fr action
( �__,/' .

�
Pyrite
Siderite
Fe- Chlorite
2:1 Clay minerals
C
(� lSi 04r--
tons:
Ca++, Mg++, K•, Na• etc ...
in river water
J+ Soil minerals:
Fig. 5. Transfer of elements during + . Ka olinite

weathering and genesis of new Soil minerals River transport .,__..--

�
Er o s Goethite
Hematite
minerals in the coastal landscape of Gibbsite
Kalimantan.
144 G.R. Sieffermann

(1970), Razzaghe-Karimi (1974), and Turenne to the genesis of the siderite and pyrite. Siderite
(1975). Tancredi et a!. (1975) proposed that the iron may be the dominant mineral in reducing freshwaters
removed from the soils was later available to make (Postma, 1982; Giresse, 1987), whereas pyrite may
siderite and iron chlorite in Quaternary sediments be more frequent in seawater environments
of the Amazon Delta. Tancredi et al. therefore (Casagrande et a!., 1977; Postma, 1982).
suggested a relationship between siderite formation The clays surrounding the siderite layers of the
and deferrification of white kaolin deposits, pro­ Rungan River suggest brackish water sedimentation,
cesses that fit the situation in Indonesia. A similar even though the salt has been washed away since the
mechanism was proposed by Bubenicek (1970) for Tertiary. More field investigations have to be under­
the iron chlorites and siderite of the important iron taken in order to understand the genesis of the
ore deposit of Lorraine (France). These processes siderite and pyrite.
are shown in the central part of Fig. 5. There is little data available for iron carried by
inland groundwater to the coastal area. However,
the heavy clayey texture of the sediments, their
The coastal sedimentation zone
topographic position which is less than 1 m above
The coastal sedimentation zone is characterized by the mean sea level, the presence of salt which induces
its clay mineral suites. dispersion of clays and consequently the impervious­
1 Inherited clays and minerals arrive detritally from ness of the clay layers, suggest that groundwater
the inland environment; these are mainly disordered iron discharge may play a role only in short distance
kaolinites, small amounts of quartz, and minor transport.
amounts of mica.
2 Clay mineral of 2: 1 type; mainly interstratified
montmorillonite-chlorite and iron-bearing clay min­
erals with chlorite X-ray characteristics. These 2: 1 CONCLUSION
minerals can represent up to 30% of the clays of the
coastal unit. In the coastal area of Central Kalimantan Province,
It should be emphasized that such 2: 1 minerals the fine sediments are a mixture of inherited detrital
are almost absent in the solid load of rivers draining components and newly formed aggradational clays
tropical oxisol areas. A similar absence of such incorporating cations from the seawater. Within this
minerals was observed in South America in the solid clay mineral mixture, neoformed minerals such as
transport of the tropical Xingu River (Gibbs, 1967). siderite and pyrite are being produced.
The most plausible explanation is that these 2: 1 This modern depositional setting can be directly
minerals of the coastal sedimentation zone are applied to post-Miocene sediments in Central
formed by aggradation of degraded clay particles Kalimantan, in which indurated siderite layers are
coming from the inland units. The river water carries underlain by clays having a mineralogical compo­
soluble silica derived from the inland soils where sition much like those of the modern analogue.
equatorial weathering occurs. This silica could con­ Deferrification of onshore sedimentary continental
tribute to the growth of small clay crystals in the formations through the agency of pedological
sedimentation area, with incorporation of potassium podzolization processes can be inferred from such
and magnesium ions from seawater in the new struc­ features as bleached quartz sands and organic
ture. Such transformations by the aggradation of hardpans.
inherited clays related to the environment have been
extensively reported by Dietz (1941), Grim et a!.
(1949), Grim & Johns (1954), Powers(1957, 1959),
Nelson ( 1960) and Pinsak & Murray (1960). ACKNOWLEDGEMENTS
3 Neoformed siderite and pyrite. The iron in these
two minerals is undoubtedly derived from inland, The author wishes to express his deepest gratitude
either in the form of soluble iron-organic compounds to J. Parnell (The Queen's University of Belfast),
or from the destruction of detrital goethite and E.I. Robbins (US Geological Survey, Reston) and
hematite. Goethite and hematite disappear in the M.J. McFarlane (University of Reading), for their
reducing brackish water environment of the coastal invaluable suggestions and their great contribution
sedimentation zone, and their iron may contribute to the correction of this text.
 Iron carbonate layers in coastal sediments, Bomeo 145

REFERENCES rivers in Amazonia. In: Atas do Simposio s6bre a biota

amazonica. Limnologia, 117-125.
KLINGE, H. (1969) Climatic conditions in lowland tropical
ALTE � MULLER, H . J. & KLINGE, H. (1964) Micromorpho­
logical lllvestigations on the development of podzols in podzol areas. Trop. Ecol. 10, 222-239.
LELONG, G.F. (1967) Nature et genese des produits
the Amazon Basin. Soil micromorphology Proc. 2nd.
d'alteration de roches cristallines sous clima/ lropical
Int. Wk. Mtg. Soil Micromorph. Arnhem, pp. 295-305.
ANDRIESSE, J.P. (1969) A study of the environment and
hunude (Guyane Fram;aise). These Sci. Univ. Nancy,
characteristic of tropical podzols in Sarawak. Geoderma 182pp.
2, 201-207. MILLOT, G. (1964) Geologie des Argiles. Masson, Paris,
ANDRIESSE, J.P. (1970) The development of podzol mor­
499pp.
phology in the Tropical Lowlands of Sarawak (Malaysia). NELSON, B.W. (1960) Clay mineralogy of the bottom sedi­
Geoderma 3, 261-279.
ments, Rappahannock River, Virginia. Clays Clay Min.
BoNIFAS, M. (1959) Contribution c) !'etude geochimique de
(7th Nat!. Conf. 1958), 135-148.
!'alteration laterique. These Doc. es Sciences, Strasbourg.
ORSTOM & DEPT. TRANSMIGRASI (1981) Reconnaissance
survey in Central Kalimantan. Phase I Maps. 21 maps
Mem. Serv. Carte Geol. Als. Lorr. 17, 159pp.
BRABANT, P. & MuLLER, D. (1981) Reconnaissance Survey
11250 000. ORSTOM-Transmigrasi Project PTA-44.
in Central Kalimantan. Soil and Land Suitability.
Dept of Transmigration, Jakarta.
PINSAK, A.P. & MURRAY, H.H. (1960) Regional clay min­
Indonesia-ORSTOM Transmigration Project PTA-44,
136pp. Dept of Transmigration, Jakarta. eral patterns in the Gulf of Mexico. Clays Clay Min. (7th
BRUCKERT, S. (1970) Influence des composes organiques
Nat! Conf. 1958), 162-178.
PoSTMA, D. (1982) Pyrite and siderite formation in brackish
solubles sur Ia pedogenese en milieu acide. These Sci.
Univ. Nancy, 250pp. and fresh water swamp sediments. Am. J. Sci. 282,
BuBENICEK, L. (1970) Geologie des gisements de fer de
1151-1183.
Lorraine. These Sci. Univ. Nancy. Pub!. IRSID 48,
PowERS, M.C. (1957) Adjustment of land derived clays to
146pp. the environment. J. Sedim. Petrol. 27, 355-372.
PowERS, M.C. (1959) Adjustment of clays to chemical
CASAGRANDE, D.J., SIEFFERT, K., BERSCHINSKJ, C. &
SuLTON, N. (1977) Sulfur in peat forming systems of the
change and the concept of the equivalence level. Clays
Clay Min. (6th Nat!. Conf. 1957), 309-326.
Okefenokee Swamp and Florida Everglades: origin of
RAZZAGHE-KARIMI, M. (1974) Evolution geochimique et
sulfur 111 coal. Geochim. Cosmochim. Acta 41, 161-167.
mineralogique des micas et phyllosilicates en presence
CECIL, C.B., STANTON, R.W., NEUZIL, S.G., DULONG,
F.T., RuPPERT, L.F. & PIERCE, B.S. (1985) Paleoclimate d'acides organiques.These Univ. Paris VI, 96pp.
controls on late Paleozoic sedimentation and peat forma­ SIEFFERMANN, G. (1973) Les sols de quelques regions vol­
caniques du Cameroun. These Sci, Strasbourg. Mem.
tion 1n the Central Appalachian Basin (USA). Int. J.
ORSTOM 66, 183pp.
Coal Geol. 5, 195-230.
SuMARTADIPURA, A.S. (1976) Geologic map of Tewah
DELVIGNE, J. (1965) Pedogenese en zone tropicale. La
quadrangle, Central Kalimantan, 1: 100 000 scale. Geol.
formation des mineraux secondaires en milieu ferral­
litique. Mem. ORSTOM 13, 177pp. Survey of Indonesia, Bandung.
TANCREDI, A., SIEFFERMANN, G., BESNUS, Y., FUSIL, G. &
DIETZ, R.S. (1941) Clay minerals in recent marine sedi­
DELIBRIAS, G. (1975) Presence et formation de niveaux
ments. Thesis, Univ. illinois. Summary in Am. Min. 27.
FLEXOR, J.M., OLIVEIRA, J.J., RAPAIRE, J.L. & de siderite dans les sediments recents du delta
StEFFERMANN, G. (1975) La degradation des illites en
Amazonien. Bull. Groupe fram;. Argiles XXVII, 13-29.
TARDY, Y. (1969) Geochimie des alteralions. Eludes des
montmorillonite dans I' Alios de podzols tropicaux humo­
arenes et des eaux de quelques massif�· criswllins
ferrugineux du Reconcavo Bahianais et du Para (Bresil).
Cah. ORSTOM (ser. Pedol.) Xill, 41-48.
d'Europe et d'Afrique. These Sci. Strasbourg. Mem.
Serv. Carte. Geol. AIs. Lorr., 270pp.
GIBBS, R.J. (1967) Geochemistry of the Amazon River
THOMPSON, C.H . (1986) Giant podzols on Pleistocene dunes
system. Geol. Soc. Am. Bull. 78, 1203-1232.
GJRESSE, P. (1987) Les depots Quaternaires du lac
in eastern Australia. XIII Congr. Int. Soc. Soil Science,
Hamburg ill, 1295-1296.
Barombi-Mbo (Ouest Cameroun). Geodynamique 2,
TuRENNE, J.F. (1970) Influence de Ia saison des pluies sur
132-133.
GRIM, R.E., DIETZ, R.S. & BRADLEY, W.F. (1949) Clay
Ia dynamique des acides humiques dans les profils ferral­
mineral composition of some sediments from the Pacific htiques et podzoliques sous savane en Guyane Fran�aise.
Cah. ORSTOM, Pedol. Vill, 419-450.
Ocean of the California Coast and the Gulf of California.
TuRENNE, J.F. (1975) Mode d'humification et differentiation
Bull. Geol. Soc. Am. 60, 1785-1808.
podzolique dans deux toposequences guyanaises. These,
GRIM, R.E. & JoHNS, W.O. (1954) Clay mineral investi­
gations of sediments in the Northern Gulf of Mexico. Univ. Nancy, 175pp.
VIERA, L.S. & OLIVEIRA-FILHO, J.P.S. (1962) As caatingas
Clays Clay Min. (2nd Nat!. Conf. 1953), 81-103.
KLINGE, H. (1967) Podzol soils: a source of blackwater
do Rio Negro. Bol. Tee. lnst. Agron. Norte 42, 1-42.
Spec. Pubis int. Ass. Sediment. (1990) 11, 147-156

Mineral deposits in Miocene lacustrine and

Devonian shallow-marine facies in Yugoslavia

J. OBR AD O V I C and N. V A SIC

Faculty of Mining and Geology, University of Beograd, Djusina 7, I 1000 Beograd, Yugoslavia

ABSTRACT

Miocene lacustrine facies in Serbia, Yugoslavia, contain sedimentary zeolites, bentonites, oil shales with
authigenic minerals, magnesites and borates. Some of these mineral deposits are of diagenetic origin,
including the alteration of volcanic glass. In some cases hot waters of volcanic origin migrated through
serpentines that underlie the lake basins, bringing magnesium to the lake water. Boron was derived by
the leaching of volcanic and pyroclastic rocks by meteoric waters.
Devonian marine shallow-water facies in western Macedonia include oolitic ironstone deposits.
Oolitic ironstones (mostly chamositic clays) were deposited within a clastic sequence composed of clays,
silts and sands which were subsequently metamorphosed. All primary structures were destroyed by
metamorphism and/or tectonic activity. The internal fabrics of the chamosite ooids are mostly tangential,
although in some cases they are radial. The iron had a multiple origin, including streams which drained
weathered terrains and possibly upwelling deep basin waters.

INTRODUCTION

In Yugoslavia, especially in Serbia, many non­
metallic mineral deposits occur in lacustrine facies
of Tertiary age including sedimentary zeolites
(Obradovic, 1988), bentonites, oil shales (Obradovic
& Jovanovic, 1987), borates and sedimentary
magnesites (Obradovic et al., 1984). Their formation
is related to the diagenetic alteration of volcanic
glass (bentonites, zeolites), or to other processes
(sedimentary magnesites, borates and others) m
alkaline-saline lakes.
A Devonian ironstone formation is mined in
western Macedonia. Many geologists (Page, 1958;
Harder, 1966; Kleut, 1966, 1968; Obradovic &
Karamata, 1982; Karamata, et al., 1982, 1988) have
investigated the Tajmiste ironstone deposit, but
some problems remain unresolved. The oolitic
ironstone ores from Tajmiste are a shallow-marine
facies, within a sequence of clastic sediments. Re­
crystallized limestones occur only at the top of the
series. Although the ironstone formation has experi­
enced metamorphism and/or tectonic deformation,
chamosite ooids with both tangential and radial­
concentric fabric are recognizable.
LACUSTRINE FACIES
Many lake basins existed in Serbia in Neogene
times. The lakes became established in the Palae­
ogene, and lasted until the Upper Miocene or
Pliocene. All of them were freshwater lakes (Fig. 1),
situated in graben-like intermontane basins near the
marginal part of the Pannonian Sea.
Under the influence of contemporaneous vol­
canism (heating of water), vertical movements of
fault blocks (shallowing and deepening in different
parts of the lake) and a dry, arid climate, the lake
water changed from fresh to alkaline and saline
(Obradovic, 1983). This occurred at a certain stage
of lake development and often only in some parts of
the lake. Because of subsequent subsidence and
water inft.ow, all lakes reverted to freshwater en­
vironments. According to Pantie & Mihajlovic

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun 147

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
148 1. Obradovic and N. Vasic
- - ·.._ r,\
- ·--···: .;-
c-·, � .
(�)
/
)
'·
)
( 1977), a comparison between fossil floras collected
over a wide area in Central and Southern Europe
shows that the dry climatic zone shifted from the
north, southwards throughout the Miocene.
Zeolites
In Serbia, a dry period occurred in the Middle
Miocene (Table 1). At that time sedimentary zeolites
(the product of the diagenetic alteration of volcanic
glass) were formed in many lake basins. These
zeolites are mostly referrable to clinoptilolite, as in
the Slanci Basin and the Vranje Basin at Zlatokop
(Obradovic & Dimitrijevic, 1987).
At Zlatokop in the Vranje Basin, zeolitized
quartz-latitic tuffs are interbedded with marly sedi­
ments of Middle Miocene age (Fig. 2). The tuffs are
separated from the marly sediments by layers of
laminated silicified tuffs containing analcime and
lenses of black chert. The tuffs are predominantly
fine-grained volcanic ash and rare crystals of quartz,
plagioclase (30-35% An) and biotite. The tuffs are
on average about 80% zeolitized, and constitute up
to 90% of the rock volume. The zeolite corresponds
to calcium clinoptilolite.
In some lake basins, including the Slanci Basin,
lacustrine sediments overlie a fluvial floodplain and
swamp succession. Clay, dolomitic and tuffaceous
Fig. 1. Palaeogeographic
reconstruction of Miocene
environments in Yugoslavia. After
Grubic (1980). (1) Land, (2) lakes,
(3) sea, (4) land-sea boundary, (5)
islands, (6) volcanic centres
(dacite-andesite), (7) Slanci Basin,
(8) Valjevo-Mionica Basin, (9)
Jarandol Basin, (10) Vranje Basin. I,
Adriatic Basin; II, Pannonian
Basin; III, Dacian Basin; IV, land
with lakes.
marl and tuff were deposited in the lake. The prod­
ucts of the diagenetic alteration of the tuffs were
bentonite, clinoptilolite and analcime.
Oil shales
The lacustrine facies includes two types of oil shale.
The first is carbonate-rich and the second is silici­
clastic. The first type, in the Valjevo-Mionica Basin,
includes dolostones and rarely dolomitic marlstones
with laminae of kerogen. Moulds of gypsum crystals
are very common in the carbonate rocks. It is possible
to distinguish three series. The lower series contains
varved and laminated pelites (mostly marlstones)
and laminae of kerogen and rare beds of searlesite.
The middle series contains tuffaceous material and
varved pelites (tuffaceous dolostones and dolomitic
marlstones) with laminae of kerogen and beds of
searlesite in association with analcime and potassium
feldspar crystals. The upper series consists of
carbonate rocks with rare laminae of kerogen. A
younger siliciclastic formation lies transgressively
upon them (Obradovic & Jovanovic, 1987).
In another type of oil shale, in the Vranje Basin of
Oligo-Miocene age, laminae of kerogen alternate
with laminae of shale or clay, but the authigenic
minerals mentioned above have not been discovered
in them.
Table 1. Lacustrine facies and their characteristics

Slanci Basin Vranje Basin Zlatokop Jarandol Basin Valjevo-Mionica Basin

Age Lower-Upper Miocene Lower Miocene-Pliocene Lower- Upper Miocene Late Lower-Late Upper
Miocene

Character of the Freshwater with coal Freshwater with floral Freshwater with coal and Freshwater with oil shales
lake water remains floral remains
2;::
Saline-alkaline (volcanic Saline-alkaline (volcanic Saline-alkaline
s·
Saline-alkaline "'
.,
glass-bentonite- glass-clinoptilolite- (magnesites with the (searlesite, analcime and !:?..
clinoptilolite-analcime) analcime) moulds of borate, K feldspar) with oil shales !:>..
phosphate and sulphate �
0
minerals; early diagenetic "'
:::;:
dolomitization of CaC03 -"'
mud)
�
Freshwater fossil remains Freshwater floral remains Freshwater fossil remains Freshwater floral remains, CrQ
0
oil shales "'
1:)
"'
Contemporaneous Tuffs and tuffites Volcanic rocks, tuffs and Volcanic rocks, tuffs and Tuffs and tuffites ;::;·
volcanic products tuffites tuffites

Tectonic activity Strong Strong Strong Strong

Climate Wet Wet Wet Wet

Dry (Middle Miocene) Dry (Middle Miocene) Dry (Middle Miocene) Dry (Middle Miocene)
Wet Wet Wet Wet

�
\C
 LITHOSTRATIGRAP HIC
COLUMN FROM ZLATOKOP - VRANJE
LACUSTRINE BASIN

0
44

2 MAR LSTONE
+
2 "

�
a.
2 ::E TUFFACEOUS MARLSTONE
a: 0
w <.>
2 i+ MARLY TUFFITE

2
+ TUFFACEOUS

�+ MARLSTONE

-' ' '- 2 e:

"" w
I
�
:
SILICIFIED TUFF WITH ANALCIME
z
w 2 0
"
SILICIFIED TUFF WITH ANALCIME
a:
z I "' AND WITH LENSES OF BLACK
w
(.) 2 <.>
CHERT

0 +
E
�
g v v
v v v v w ffi TUFF WITH

'I v v v
z �
3:
"'
�
v v v v CUNOPTILOUTE

w �
...J
v v "'
c v v v v
c
v v
� ;::
v v v v g
..
...J
SILICIFIED TUFF WITH ANALCIME
J:
v <J)
v TUFF WITH

v v
w
z CL!NOPTILOLITE
�
v v v v
"'
"

v v v v

MAALSTONE
2

G N 0

1----_1 MARLSTONE
�- MARLY TUFFITE

'
[2Z] TUFF
In }I TUFFACEOUS MARLSTONE

�- SILICIFIED TUFF
I� I BLACK CHERT

PARALLEL
2 LAMINATION 't FLORA REMAINS

Fig. 2. Lithostratigraphic column for Zlatokop, Vranje Lacustrine Basin.

 Mineral deposits, Yugoslavia
Sedimentary magnesites and borates
In the tectonically active Jarandol Basin, several
subenvironments can be distinguished. In one of
them, in a shallow-water dolomitic carbonate com­
plex, deposits of sedimentary magnesite (Bela Stena
=white rock) occur (Obradovic et al., 1984). Ultra­
mafic and volcanic rocks and locally Triassic dolo­
mites underlie these lake sediments. The Bela Stena
deposit is a lens-shaped body that once contained
about four million tons of magnesite. The magnesites
are bedded in layers of different thickness, mostly
400-500 mm, which were more or less destroyed by
diagenetic modification, slumping and tectonic ac­
tivity. The characteristics of the magnesite deposits
are given in Table 2. Electron microprobe analyses
show that the content of MgO varies from 38·72 to
46·19% . The highest content is characteristic of the
massive type of magnesite.
The source of magnesium was the ultramafic rocks;
hot waters of volcanic origin migrated through them,
bringing magnesium to the lake. Also, magnesium
may have been derived by leaching of the ultramafic
rocks by meteoric waters. At the time of most
intense faulting hydrothermal solutions precipitated
magnesium and other components as a nodular and
porous type of magnesite deposit along the fault
zones. Bedded massive and laminated magnesite
pass laterally into dolomitic and magnesitic marl­
stones. Due to vertical fault movements some parts
of the magnesite deposits were exposed to subaerial
conditions. The magnesite became dried and frag­
mented to produce what is known as the brecciated
type (Obradovic et al., 1990). Desiccation cracks
commonly occur in this deposit. In magnesite, es­
pecially in the porous type, moulds of gypsum and
lueneburgite [Mg3B2(0H)6(P0)4 ·6H20] crystals
occur. Crystals of lueneburgite up to 3 mm in size
were found.
In the same lake basin (Fig. 3), a deposit of boron
Table 2. Characteristics of magnesites from the Bela Stena deposit
Sedimentary features Types
Bedding Laminated
Lamination Massive
Desiccation cracks Cavernous
Kerogen of sapropelic type Brecciated
Floral remains Nodular
Algal structure
Tufa
151
minerals was discovered in fine-grained clastic sedi­
ments, representing a very shallow-water environ­
ment. In the outer part of the basin, colemanite
(2[Ca2B60u·5H20]) and howlite (Ca2B5Si09(0H)5)
occur in association with bitumen, calcite and
gypsum, forming the lens-shaped body. In the
central part of the basin, in the same fine­
grained siliciclastic subenvironment, ulexite
(2[NaCaB506(0H)6-5H20]), colemanite and tinca­
lonite (Na2B405(0H}4-3H20) were found. All these
boron minerals are typical of playa lake deposits.
The boron was probably derived by the leaching of
volcanic and pyroclastic rocks by meteoric waters.
DEVONIAN SHALLOW-MARINE
CHAMOSITIC IRONSTONE
In western Macedonia a Devonian shallow-marine
sequence contains oolitic ironstone deposits. Fossils
found in limestones from the area surrounding the
mine indicate a late Lower Devonian to Middle
Devonian age.
The oolitic ironstones, primarily chamosite clays,
in the Tajmiste deposit, western Macedonia, were
deposited within a clastic series of claystones, shales
and sandstones, which were subsequently metamor­
phosed into quartzites, phyllites and schists. There
are several important beds of ironstone.
It is possible to distinguish three stratigraphic
units: a lower unit under the ores, the unit containing
the ores and an upper unit above the ores. The first
unit is composed of fine-grained sediments with rare
sandstones (metamorphosed to phyllite and quart­
zites), the second unit includes the ores within sand­
stones and shales (quartzites, slates and phyllites),
and the third unit is metamorphosed sandstones,
shales and claystones (quartzites and phyllites) with
limestones at the top. Coarsening-upward sequences
are characteristic for the lower and middle units.
Environment
Lake basin, shallow water with temporary
·
subaerial conditions
pH= 8-10
Alkaline-saline water (moulds of sulphate, borate
and phosphate minerals; occurrences of
lueneburgite)
Contemporaneous volcanism
 LITHOSTRATIGRAPHIC
COLUMN FROM A PART OF JARANDOL

LACUSTRINE BASIN

..

OELUVIUM
ALLUVIUM

DOLOMITE AND
9' DOLOMITIC MARL
2

BORON
MINERALIZATION
2

2 MAGNESITE

LUTITE:
2 TUFF, TUFFITE, MARL, CLAY

ARENITE:
SANDSTONE 1 TUFF 1 TUFFITE

2
� RUDITE:
���C
� CONGLOMERATE, VOLCANOC

2 ANDESITE

2 PARALLEL L AMINATION

2 WAVY L AMINATION

GRADED BEOOING

CONVOLUTION

FLORA REMAINS

- COAL

Fig. 3. Lithostratigraphic column from a part of Jarandol Lacustrine Basin.

 LITHOSTRATIGRAPHIC
COLUMN OF IRONSTONE FORMATION

FROM TAJMISTE

RECRYSTALLIZED
LIMESTONE

Co SCHIST

Co PHYLLITE

C.a SCHIST

RECRYSTALLIZED
LIMESTONE

METASANDSTONE

z PHYLLITE
:'! 2
z
0
> METASHALE
w
c 2 PHYLLITE

METASANDSTONE
PHYLLITE
METASANDSTONE "'
w
2 Ca-Se "­
"­
�
Co
w
-
PHYLLITE
..J -
Se-Ca
c -
2
c - Ca-se-Co

� METASHALE

Sd-Co-Mt ORE

METASANDSTONE "'
w
Co- Sd ORE "'
0
METASANDSTONE

Sd-Co ORE �
i
METASANDSTONE
z
Sd-Co ORE
2
�
RECRYSTALLIZED
METASANDSrONE ii' LIMESTONE

�
a::
�
METASHALE
- PHYLLITE
w
w

� .
�
Co-Mt-Sd ORE c

�
c METACL ASTIC
ROCK
;;
METASHALE
Sd-Co ORE

z
- ORE

Set-Co PHYLLITE
2 Co CHLORI TE -CHAMOSI TE
METASANDSTONE ii'
!E Co CALCITE

PHYLliTE "' Se SERICITE

� Sd SIDERITE
METASHALE g Mt MAGNETITE

2 PARALLEl
L AMINATION

Fig. 4. Lithostratigraphic column of ironstone formation from Tajmiste.

154 J. Obradovic and N. Vasic

Most primary structures were destroyed by meta­ Table 4. Spectrochemical trace element analyses of iron
morphism and/or tectonic activity. Only in a few ores (ppm)

cases can parallel lamination be distinguished

2 3 4
(Fig. 4).
According to Harder ( 1966, 1989), the different Pb 15 15 50 *

iron ores can be distinguished by using the chemical Zn 500 600 500 111·52
compositions of the ores. The Minette type of iron Cu 150 500 700 61·03
Mn 5000 3000 500 2100
ore is geochemically characterized by high contents Co *
80 10 5
of Ti02 (more than 0·15% ), P205 (more than 1% ), Ni 100 30 50 27-44
V205 (about 0· 1% ) and Al203 (more than 4% ). Cr 100 *
150 274·54
These contents are lower in exhalative iron ores v 200 200 50 152·03
Ba * *
(Lahn-Dill type) than in the ores of the Minette 300 178·52
* * *
Nb 3·50
type. According to these data, ironstones from the Zr * * *
124·09
Tajmiste deposit correspond more closely to the y * * *
38·18
Sr * * *
Minette type than to the exhalative type. Chemical 129·09
analyses (Tables 3 and 4) show that ironstone ores *
Not determined. Analyst for samples 1, 2, 3,
show some differentiation in their chemical compo­ B. Milanovic, Beograd; for sample 4, D. Opper, Koln.
sition, but they do correspond to the Minette type.
Although some pyroclastic rocks are found in the
Tajmiste deposit, basic volcanic rocks occur 50 km the nuclei of the ooids are visible, but usually this is
distant from it, and are covered by thick deposits of not the case. Siderite commonly replaced chamosite,
Palaeozoic rocks, so there is unlikely to be a genetic but the magnetite is of metamorphic origin. The
connection between them and the Tajmiste ooids were deformed by metamorphism. In some
ironstones. cases two or three ooids have coalesced with a
The fabric of the ores is oolitic, rarely pisolitic. common outer cortex.
The ooids are mostly less than 0·5 mm, and rarely The tangential fabric in the ooids suggests that
from 0·5 to 0·8 mm in size. The ooids are composed besides ooids similar to lateritic ooids (radial­
of chamosite with tangential and radial structure, concentric fabric) there are others. The tangential
and rarely of siderite and magnetite. In some cases fabric is probably produced by the mechanical ac­
cretion of detrital clay (kaolinite) and hydrated iron
oxide minerals (Bhattacharyya & Kakimoto, 1982).
Table 3. Chemical analysis of iron ores Ooids with radial fabrics, resembling lateritic pisoids,
are also composed of chamosite, which was partly
2 3
replaced by siderite at the late diagenetic stage. In
Si02 7·73% 19·68% 7·14% the region surrounding the deposit there is no ex­
Ti02 0·36 0-48 0·39 posed weathering crust or occurrence of laterites.
AI203 3·00 3·92 7·23 Because of this the origin of this kind of ooid is
F�03 22·22 8·53 5·32 questionable, but it is believed that they correspond
FeO 35-45 43·88 43-97
MnO 0·15 0·16 0-48 to a weathering crust.
MgO 0·50 0·99 1·98 Until now there has been no satisfactory general
CaO 2·42 1·04 3·05 model for the interpretation of the origin of these
Na20 0·09 0·09 0·12 ironstones. We did not find any evidence that the
K20 0·11 0·11 0·80
investigated ooids represent the diagenetic ferru­
P20s 2·80 1·13 2·58
s 1·04 1·03 0·69 ginization of calcareous ooids. The tangential fabric
Org.mat. 0·38 1-49 0·64 of the ferruginous ooids originated, according to
H20 1000° 23·75 17·50 25-43 Bhattacharyya & Kakimoto (1982), by the mechan­
H20 110° 0·18
ical accretion of suspended hydrated iron oxides and
100·00% 100·03% 100·00% detrital clay minerals, especially kaolinite, around
the nucleus, in water with some degree of agitation.
(1) Chamosite-siderite ore; (2) chamosite-siderite ore;
(3) siderite-chamosite ore
The chamosite formed from the kaolinite during
Classical gravimetric methods were employed for oxides the early stages of diagenesis in an iron-rich
and water (analyst: D. Nikolic). environment.
 Mineral deposits, Yugoslavia
The ongm of the iron is probably polygenetic.
The chemical composition of the Tajmiste ironstones
shows a similarity between them and the Minette
type of ironstones, indicating that the iron originated
from weathered terrains. Some differences between
the Minette type and the Tajmiste ironstones, like
the occurrences of goethite in the Minette type,
indicate that iron was not only supplied by streams
which drained weathered terrains but that the up­
welling of deep basinal waters may also have been
an important source of iron.
CONCLUSIONS
Miocene lacustrine rocks in Serbia contain authigenic
zeolites, bentonites, magnesites and borate deposits.
Climate and contemporaneous volcanic activity had
a strong influence on the diagenetic processes and
alteration of the lacustrine facies. A dry, semi-arid
to arid climate and vertical movements of fault
blocks with contemporaneous dacitic-andesitic vol­
canism influenced the chemistry of the lake water,
changing it, generally in the Middle Miocene, to
alkaline and saline. These conditions made possible
the alteration of volcanic glass to bentonites and
zeolites, the deposition of magnesite and the occur­
rence of borate, silicoborate, phosphate and sulphate
minerals. They also influenced the diagenetic forma­
tion of authigenic minerals (searlesite, analcime,
potassium feldspar) in oil shale.
Devonian shallow-marine rocks in western
Macedonia are characterized by the occurrence of
oolitic ironstone deposits composed of chamosite
and siderite, with magnetite, pyrite, chlorite­
thuringite, ankerite, apatite, stilpnomelane, min­
nesotaite, quartz and rare calcite. The ironstone
deposits occur within clastic sediments, which were
metamorphosed to quartzites, slates and phyllites.
In a shallow subtidal environment, rich in organic
substances and in mildly agitated waters, ooids were
formed by the mechanical accretion of suspended
hydrated iron oxides and detrital clay minerals
around the nucleus (ooids with tangential fabric).
During early diagenesis chamosite was formed, and
later the chamosite was replaced by siderite. Ooids
are cemented by fine-grained siderite, rarely with
chamosite or dark amorphous chamositic masses.
Ooids with radial fabrics, resembling lateritic
pisoids, are also composed of chamosite, which
was partly replaced by siderite at the late diagenetic
stage. In the region surrounding the deposit now
155
there is no exposed weathering crust or occurrence
of laterites. The origin of this kind of ooid is therefore
questionable, but it is believed that they correspond
to a weathering crust.
The origin of the iron is probably polygenetic.
The data indicate that iron was not simply supplied
by streams which drained weathered terrains,
although this source was important. We cannot
exclude the upwelling of deep basinal waters as an
important source of iron.
ACKNOWLEDGEMENTS
We gratefully acknowledge the help of S. Karamata
who offered helpful suggestions. We would like to
thank J. Parnell for his editing of the manuscript and
suggestions for its improvement. 0. Mudronja
assisted in the preparation of the figures.
REFERENCES
BHAlTACHARYYA, P.D. & KAKIMOTO, K.P. (1982) Origin of
ferriferous ooids: an SEM study of ironstone ooids
and bauxite pisoids. J. Sediment. Petrol. 52, 849-859.
GRUBIC, A. (1980) Yugoslavia -an Outline of Geology of
Yugoslavia, Excursion 201A -202c (Ed. by A. Grubic),
26th Int. Geol. Congress, Paris, 5-92.
HARDER, H. (1966) Kiinnen die Mazedonischen Eisenerze
aus Verwitterungsliisungen gebildet worden sein. Ref.
VI Savetovanja geol. Jugoslav., Ohrid II, 659-673.
HARDER, H. (1989) Mineral genesis in ironstones: a model
based upon laboratory experiments and petrographic
observations. In: Phanerozoic Ironstones, Vol. 46 (Ed.
by T.P. Young & W.E.G. Taylor), pp. 9-18. Spec.
Publ. Geol. Soc.
KARAMATA, s., 0BRADOVIC, J. & NIKOLIC, D. (1982)
Study of the characteristics of Fe ores from Western
Macedonia-on the example of the Mine Tajmiste. Part
II. Unpubl. studies (in Serbo-Croatian).
KARAMATA, S., 0BRADOVIC, J. & NIKOLIC, D. (1988)
Study of the characteristics of Fe ores from Western
Macedonia-on the example of the Mine Tajmiste. Part
111. Unpubl. studies (in Serbo-Croatian).
KLEUT, D. (1966) Mineral composition of Tajmiste Mine.
Ref VI Save10vanja geol. Jugoslav. Ohrid. II, 506-514
(English summary).
KLEUT, D. (1968) Phosphorus in the Tajmiste iron ore
deposit. Rad. Ins/. za geol. rud. islr. i isp. nukl. i dr. min.
sir., Beograd 4, 125-139.
0BRADOVIC, J. (1983) Some aspects of sedimentation in
Neogene Lake Basins in Serbia, Yugoslavia. 4th !AS
Regional Meeting, 18-20 April 1983, Abstracts,
120-121.
0BRADOVIC, 1. (1988) Occurrences and genesis of sedi­
mentary zeolites in Serbia, Yugoslavia. In: Occurrences,
Properties and Ulilization of Natural Zeolites (Ed. by
D. Kallo & H.S. Sherry), pp. 59-69. Academiai Kiado.
156 J. Obradovic and N. Vasic
Budapest.
0BRADOVIC, J. & DtMITRJJEVIC, R. (1987) Klinoptilolizirani
tuf Zlatokopa kod Vranja (Ciinoptilolized tuffs from
Zlatokop, Vranje Lake Basin). Glas SA N U 51, 7-19
(English summary).
0BRADOVIC, J. & JovANOVIC, 0. (1987) Neke karakteristike
sedimentacije u neogenom Valjevsko-Mionickom
Basenu (Some characteristics of Neogene sedimentation,
Valjevo-Mionica lake basin). Glas SA N U 51, 53-63
(English summary).
0BRADOVIC, J. & KARAMATA, S. (1982) Study of character­
istics of Fe ores Western Macedonia-on the example of
the Mine Tajmiste. Part I. Unpubl. studies (in Serbo­
Croatian).
0BRADOVIC, J., KARAMATA, S. & VAS IC , N. (1984) Sedi­
mentary magnesite from 'Bela Stena' deposit and its
origin. 5th !AS European Regional Meeting on Sedi­
mentology, 9-11 April 1984, Marseille, France,
Abstracts, 330-331.
OBRADOVIC, J., KARAMATA, S., KELTS, K., 0BERHAENSLI, H.
& VASIC, N. (1990) Lake sedimentation and occurrence of
sedimentary magnesite (in press).
PAGE, B.M. (1958) Chamosite iron-ore deposit near
Tajmiste, Western Macedonia, Yugoslav. Econ. Geology
53 (1), 1-21.
PANTie, N. & MIHAJLOVIC, D.J. (1977) Neogene flore
Balkanskog kopna i njihov znacaj za paleoklimatologiju,
paleobiogeografiju i biostratigrafiju (Flores Neogenes
provenant du Continent Balkanique et leur importance
au point de vue de Ia Paleoclimatologic, Paleobio­
geographic et Biostratigraphie). Geol. Anali Balk. Pol.
XL, 103-125.
 Copper Deposits

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
Spec. Pubis int. Ass. Sediment. (1990) 11, 159-172

Syngenetic and paleokarstic copper mineralization

in the Palaeozoic platform sediments of
West Central Sinai, Egypt

M. A . E L S H A R K A WI*, M. M. E L A RE Ft an d A . A B DEL M O TE LI Bt
*Geology Depar tmen t, Facul ty of Science, Kuwai t Universi ty , Kuwai t; tceology Depar tmen t, Facul ty of
Science, Cairo Universi ty, Egyp t

ABSTRACT

Copper in the form of carbonate, chloride, silicate, sulphate and phosphate minerals is encountered
within the Palaeozoic sediments of the Urn Bogma region, West Central Sinai, Egypt. They are
classified into two contrasting genetic types: ( 1 ) strata-bound to stratiform malachite confined within a
certain stratigraphic level of Cambro-Ordovician clastic sediments; and (2) strata-bound copper carbon­
ate, chloride, silicate, sulphate and phosphate confined within a buried Carboniferous karst profile.
The geometric distribution patterns of the malachite of the first type represent a high degree of
congruence with the primary, deformational and biogenic sedimentary structures of the enclosing rocks .
The malachite was formed syngenetically during the accumulation of the host sediments in fluviodeltaic
environments.
In the second type, the geometric distributions of the copper minerals and the chemistry and mineral
composition of the host karst products reveal that these copper minerals are of pedogenic origin,
deposited from solutions in a paleosol developed during the Carboniferous karst event. The variation in
the pH and Eh conditions of the paleosol environment and the related biogenic processes are suggested
to be the main factors controlling the leaching of the copper and its migration and redeposition within
the subsoil and topsoil horizons of the paleokarst profile.

INTRODUCTION

The copper minerals of the Urn Bogma region at­
tracted the attention of the ancient Egyptians (5000
BC or even earlier). They were used throughout
the Predynastic periods of Ancient Egypt. Ancient
workings for copper of Pharaonic time occur in West
Central Sinai at many localities in the Urn Bogma
region ( Lucas & Harris, 1962). The region is occu­
pied mainly by upper Proterozoic basement rocks
followed unconformably by sedimentary successions
of Cambro-Ordovician and Carboniferous ages
( Fig. 1).
The present work is concerned with the distri­
bution, mode of occurrence and possible genesis of
the copper minerals occurring in the Palaeozoic
succession of this area. The copper occurs in the
form of carbonate, chloride, phosphate, silicate and
sulphate minerals and is confined within a certain
stratigraphic level of the Cambro-Ordovician sedi­
ments and in a Carboniferous buried paleokarst
profile. The work is based on detailed field and
megascopic investigations supported by stratigraphic
and sedimentologic observations, geometric in­
terpretation and identification of organic matter.
The identity of the copper and clay minerals was
verified by X-ray diffraction (XRD) and the chemical
analysis of the paleokarst profile was carried out by
X-ray fluorescence (XRF).
The mechanisms of formation of the Palaeozoic
copper minerals involve fluvial (Cambro­
Ordovician), karst and pedogenetic processes
(Carboniferous) with an overprint from diagenetic
processes. Certain palaeoclimatic and palaeoen­
vironmental conditions are postulated as a result of
the present study.

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun

159
and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
 �
,.....
(]',
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Copper minerals

Organic remains
c;

-:-v.-
Simple flaser str.

Trace fossils

Ball & pillow otr.

CJ-

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Detailed profiles ---v- Mud cracks

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,. of the cuprife�ous
sed. AT: Abu Thbra F.
Loose clayey to UB : Um Bogma F.
E53 Siltstone
� sandy materials u Cross bedding A : Adedia F.

CJ Sandstone G Ferricr·ete <C:> Lenticular bedding

N.: Nasib F.
AH : Abu Hamata F.
r::-;;::-]
� Conglomerate I j Alunite & gypsum
'\v
v
v
=!? Convolute bedding SK: Sarabit El Khadim•F;

Fig. 1. Palaeozoic sections of Urn Bogma region and detailed lithostratigraphy of the cupriferous sediments.
 Copper mineraliza tion, Sinai 161

An epigenetic hydrothermal origin as a result of
Tertiary volcanicity was proposed by most of the
authors who have studied the copper minerals of this
area, including Barron (1907), Ball (19 16), Davey
( 1948), Soliman ( 1961), Gindy (1961) and Hilmy &
Mohsen ( 1965). Segev ( 1984) postulated a hydro­
thermal hypogene origin for associated gibbsite in
Urn Bogma. El Shazly et a t. ( 1963) considered the
copper minerals as oxidation and leaching products
of primary copper sulphides present in the basement
rocks of West Central Sinai. Magaritz & Brenner
(1979) attributed the copper and manganese associ­
ation of Urn Bogma to copper and manganese
migration during marine diagenesis.
LITHOSTRATIGRAPHY OF THE
PALAEOZOIC SEDIMENTS
The Cambro-Ordovician sediments
The Cambro-Ordovician sediments are represented
by a clastic sequence underlying the Carboniferous
dolomitic rocks in the Urn Bogma region. Litho­
stratigraphic details are included in Fig. 1. Weissbrod
( 1969) assigned them to the Cambrian, then Issawi
& Jux ( 1982) used trace fossils to extend their age to
cover the Cambro-Ordovician. Soliman & El Fetouh
( 1969) subdivided these sediments into three forma­
tions; the Sarabit El Khadim Formation, Abu
Hamata Formation and Adedia Formation. The
Abu Hamata Formation is equivalent to the Timna
Formation of Israel (Weissbrod, 1969). Kora ( 1984)
introduced the Nasib Formation to include the upper
part of the Abu Hamata Formation as shown in
Table 1.
The Carboniferous sediments
The Carboniferous sediments are dominated by
carbonates and divided into a lower Urn Bogrna
Formation and a conformably overlying Abu Thora
Formation (Kora, 1984). The modified lithostrati­
graphic succession is shown in Table 2.
El Sharkawi et a/. ( 1990) proved that the Lower
Dolostone 'Ore Member' and the overlying Marly
Dolostone-Siltstone Member of Kora ( 1984) rep­
resent a typical soil profile of a paleokarst surface.
This profile was buried by the rocks of the Upper
Dolostone Member. This is manifested by: (1) de­
velopment of dissolution features of different forms;
(2) formation of intrakarstic sediments; (3) wall­
rock alterations of the parent carbonate rocks;
(4) formation of calcrete; and (5) development of
paleosol sediments covering the karstified rocks and
filling the dissolution features.
The Urn Bogma Formation (the lower karstified
carbonates and the Upper Dolostone) was subjected
to another episode of karstification during the
Quaternary (EI Sharkawi eta/., 1990). This is mani­
fested by the formation of stepped terraced escarp­
ments, favouring the retreat of the slopes of the

Table 1. Lithostratigraphic succession of the Cambro-Ordovician sediments

Formation Main lithology and environment

Adedia Sandstone with minor siltstone and shale

(25-55 m) Occasional conglomerates at base
Fluviomarine environment
Nasib Deltaic sediments differentiated into:
(=45m)
Upper variegated member (=25m), subdivided into:
(a) Upper laminated siltstone and shale
(b) Middle green, 3 .5 m thick cupriferous beds, micaceous
siltstone and shales, subordinate sandstone
(c) Lower alternating beds of shales and siltstone
2 Lower white member consisting of conglomerate and
sandstone, manganiferous (=20 m)
Abu Hamata Sandstone, siltstone, shale, glauconitic and algal subarkoses
(12-36 m) Neritic environment
Sarabit El Khadim Basal conglomerate, alternations of sandstone and siltstone
(7- 17 m) Continental shelf, very calm shore
Basement rocks
162 M.A. El Shar ka wi, M. M. El Arefand A. A bdel Moteli b
Table 2. Lithostratigraphic succession of the Carboniferous sediments
Formation Member
Abu Thora
(>100 m)
Upper Dolostone
Unconformity
Urn Bogma Marly Dolostone­
( =41 m) Siltstone
Lower Dolostone
Unconformity
Basement rocks and Cambro-Ordovician sediments
main wadis of the area and development of karren
morphogenetic karst features. The uppermost sur­
faces of these karstified rocks are encrusted by
surficial calcareous and siliceous duricrusts (calcrete
and silcrete). The ultimate result of this younger
karstification is the complete denudation of the
Upper Dolostone Member and subsequent destruc­
tion of the underlying paleokarst profile.
The distribution of copper minerals in the
Palaeozoic sediments is indicated on the individual
stratigraphic successions in the six studied sites in
'
the Urn Bogma region (Fig. 1).
STRATA-BOUND TO STRATIFORM
MALACHITE IN THE CAMBRO­
ORDOVICIAN SEDIMENTS
Malachite is found in the clastic rocks of the Nasib
Formation. It is mostly confined to the middle green
part of the variegated member of this unit. In the
overlying Adedia Formation and underlying Abu
Hamata Formation, no malachite or other copper
minerals are observed. No traces of copper sulphides
or any other sulphide minerals are detected in
polished sections. Malachite occurs as small col­
loform globules, up to 4 mm in diameter, usually
associated with kaolinite. The cupriferous sediments
consist of rhythmic alternations of laminated shale,
micaceous siltstone and very fine-grained sandstone
Main lithology and environment
Sandstone with shale intercalations
Coal in the upper part, with
Lepidodendron sp. and Sigillaria sp.
Yellow to pink dolostone with
occasional yellow shales
Warm shallow-marine environment
Karstified member, siltstone
representing soil cover, cupriferous
Extensively karstified dolomitic
rocks with intrakarstic product
housing manganese ores and caliche
nodules.
(Fig. 1). The shale layers are of green colour and
some layers are stained by a violet colouration. The
clay minerals constituting the shale layers are kao­
linite, illite and chlorite. The uppermost surfaces of
·the shale layers are dominated by shrinkage features
and scour-and-fill structures. The interlayered silt­
stones and sandstones exhibit well-defined sedimen­
tary structures including horizontal and undulating
lamination, cross-lamination, ftaser bedding, graded
bedding, ripple marks, load casts, load balls and
pillows. Biogenic structures are also recorded and
include tracks and vertical burrows. The sandstones
are subarkosic, composed mainly of subangular to
subrounded quartz grains with subordinate alkali
feldspar and opaques. The matrix is made up of
green kaolinite together with less abundant illite.
The grains are usually cemented by calcite and
malachite.
Both in the field and on a hand specimen scale,
the geometric forms of the malachite and the associ­
ated green kaolinite exhibit a high degree of congru­
ence with the primary, depositional, deformational
and biogenic structures of the enclosed rocks. The
geometrical classification of the various forms of the
malachite and the associated kaolinite, detected
under the binocular microscope, is subdivided into
14 types, illustrated in Fig. 2.
The close congruence of the geometric patterns of
the malachite with the sedimentary structures suggests
that the malachite was deposited during the accumu­
lation and dewatering of the host clay sediments.
 Copper mineralization, Sinai
STRATA-BOUND COPPER MINERALS
IN THE CARBONIFEROUS BURIED
KARST PROFILE
The Carboniferous karst profile is subdivided into
three distinctive horizons corresponding to the typi­
cal paleosol profile (EI Sharkawi et al., 1 990). These
are the parent carbonate horizon, the subsoil
horizon and the topsoil horizon.
The parent carbonate horizon includes the fresh
or slightly weathered dolostone, which still exhibits
the original textures and mineral compositions. The
subsoil horizon constitutes the upper parts of the
parent carbonate. It is characterized by: (1) abun­
dant distribution of solution features with structural
modification, pulverization and brecciation of the
parent carbonate; (2) advanced degree of dedolo­
mitization and formation of dedolomite and concen­
tration of sesquioxides of iron and manganese with
clays; and (3) development of crustified calcareous
nodules (calcrete).
The topsoil horizon constitutes the uppermost
erosion surface of the paleokarst profile and consists
mainly of alternating multicoloured layers of kaoli­
nitic shales, ochres and nodules of alunite and
gypsum together with copper minerals. These sedi­
ments merge gradually downwards into the altered
dolostones and the associated weathering products
of the underlying subsoil horizon. Organic remains
were recognized in the topsoil section (Fig. 3) within
the green, black and red shales. The plant remains
are dominated by palynomorphs, woody particles
and insoluble opaque organic detritus. The paly­
nomorphs are differentiated into spores and pollen
grains. The spores include Tr i lete sp., Denso5porites
sp., Dictytr i letes sp. and Mutticellaesporites sp. as­
sociated with a few badly preserved unidentified
microspores. The pollen grains are dominated
by small land-derived forms related to the genus
Sp heripollen i tes.
The occurrence of land-derived pollen grains and
spores and the absence of marine dinoflagellate cysts
and acritarchs indicate a continental origin for
the studied sediments. Therefore, the sediments
of the topsoil horizon are of continental origin de­
posited under subaerial pedogenetic conditions
during the karstification of the Lower Dolostone
Member of the Urn Bogma Formation.
Different associations of megascopic copper
minerals including carbonate, chloride, silicate, sul­
phate and phosphate minerals are intimately associ­
ated with this Carboniferous karst profile. These
163
copper minerals are mainly distributed within the
red kaolinitic layers of the topsoil horizon. The close
association between these copper minerals and the
buried soil profile reflects the role of subaerial
weathering in the concentration of the copper during
the Carboniferous karstification event. The copper
minerals of this type are highly altered and leached
in the localities of Gebel Sarabit El Khadim and
Gebel Adedia. This alteration is attributed to the
effect of subsequent Quaternary karstification (EI
Sharkawi et al., 1990).
The identified copper minerals include malachite
(Cu2C03(0H)z), atacamite (Cu2C1(0Hh),
paratacamite (Cu2(0HhCI), pseudomalachite
(Cu5(P04h(OH)4-H20), turquoise (CuAir,
(P04)4(0H)s-4H20) and chrysocolla (CuSi03· H20).
Other minerals including lungite (Cu4(S04)
(OH),;H20), spangolite (CunAl(S04)-
(0H)12CI·3H20), bultgenbachite (Cu10(N03)-
(0HbCidH20), connellite (Cul'1(S04)C14-
(0Hb·3H20), antlerite (Cu3(S04)(0H)4) and
chalcanthite (CuS04·5H20) were also recorded by
Hilmy & Mohsen (1965). According to Hilmy &
Mohsen, copper sulphate minerals occur as fissure
fillings in the ferruginous shales overlying the
manganese ore at Gebel Sid El Banat, which cor­
respond to the topsoil horizon of the present work.
Malachite occurs as aggregates of globules up to
1 mm in diameter displaying a colloform structure.
It is usually associated with other copper minerals
and widely distributed among the topsoil and subsoil
horizons. The atacamite has a blackish-green colour
and a green streak. It occurs as aggregates of mas­
sive grains of sand size and is commonly associated
with malachite in the topsoil horizon. Widespread
veinlets of atacamite and gypsum occur cutting across
the rock of the underlying subsoil horizon. Para­
tacamite, the dimorph of atacamite, is green and
usually occurs as thin crusts associated with the
gypsum and alunite nodules of the topsoil horizon.
Pseudomalachite has a green to blackish-green
colour and occurs as thin colloform crusts within the
red kaolinitic and ochreous layers of the topsoil
horizon. It is always associated with black plant
remains. Turquoise has sky blue to bluish-green
colours and a green streak. It is commonly present
in the subsoil horizon. In some instances, turquoise
fills strata-bound veinlets within the topsoil horizon
The geometrical forms of these copper minerals
and their relationship with the host karst sediments
are classified as follows:
1 Geometrical forms of copper minerals in the top-
 ., ..
2 3

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: :-:·.· : : : ::::.:-:-: · : ·
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 Copper m ineralization, Sinai 165

LITHOLOGY LITHOLOGIC DESCRIPTION

Unconformity
and gypsum capped
rich crust.
Stratified alunite and gypsum nodules
intercalated with organic matter.

Intercalated ochreous, cupriferous

. . . . . . . . .
green clays, shales and siltstones.
· . ·. · . · . · . ·. · . ·-· . · .· Isolated manganese nodules occur
• • • • • • • • 0 • •

.
.
.
.
.
.
. .
. .
.
.
.
.
.
.. . . .
. parallel to the shale laminae. Organic
matter present.

Deep brown indurated iron pisolites

Green shale with yellow ochre.

Stratified alunite and gypsum nodules

embedded in loose sands.

IOcm Cupriferous green and red shales and

clays with gypsum and organic matter.

Fig. 3. Fine stratigraphy of the

topsoil horizon in Abu Hamata
area. Encircled numbers indicate 0
samples analysed in Tables 3 and
Stylolitic dolomitic calcarenite bed rock.
4.

Fig. 2. [opposite] Geometric distribution patterns of the malachite in the copper-bearing sediments of the Nasib Formation.
(1) Stratiform malachite arranged parallel to the lamination of the enclosing shale, siltstone or sandstone. (2) Strata-bound
malachite randomly distributed within the host sediment. (3) Strata-bound malachite distributed along the top surfaces of
the ripple marks. (4) Fine stratiform discontinuous streaks of malachite and kaolinite conformable with the original
lamination of the host sediments . (5) Strata-bound discontinuous streaks forming a planar non-parallel flaser structure.
(6) Strata-bound to stratiform concave-upward streaks corresponding to a !laser structure produced by oscillation ripples .
(7) Strata-bound discontinuous streaks filling, together with shale laminae, small scale grooves. These grooves are
developed along the uppermost surfaces of coarser material and represent a scour-and-fill structure. (8) Fine discontinuous
streaks filling shallow burrow pipes. In some instances , the streaks are confined with the upper convex relief capping the
burrows which characterize the bottom surfaces of the overlying shale layers. (9) Strata-bound discontinuous and branched
streaks of malachite and kaolinite forming a bifurcated flaser structure . ( 10) Stratiform laminae parallel to the internal
lamination of the host sediment. ( 11) Stratiform undulated laminae developed along the horizontal bedding planes of the
host sediment. ( 12) Stratiform distributed spots or streaks arranged parallel to the cross-lamination of the host sandstone.
( 13) Stratiform interrupted concave-upward streaks developed along the top surfaces of the shale layers , indicating buried
mud cracks. Some of these streaks are loaded by gravel and sand grains. ( 14) Strata-bound veinlets of malachite cutting
across some layers of the host sediment.
166 M.A . El Shar ka wi, M.M. El Arefand A . A bdel Moteli b
soil horizon. The details of the topsoil horizon are
illustrated in Figs 1 and 3. The geometric forms
encountered in this horizon are:
(a) Stratiform lenticular masses, up to 400 mm
long and 100 mm thick, encountered within the
red and green shales. The laminae of the host red
shales follow the outer boundaries of these lenses.
The lenses consist of pseudomalachite, malachite
and atacamite with kaolinite.
(b) Strata-bound discrete pockets, up to 200 mm
in diameter, of pseudomalachite randomly dis­
tributed within the green and kaolinitic shales.
The cupriferous bodies exhibit lamination.
(c) Stratiform fine lamination of malachite and
chrysocolla intercalated with the green, red
and blackish-red shales. The copper laminae are
closely congruent with the primary lamination of
the host sediment. The intercalated shale laminae
include abundant plant remains.
(d) Stratiform fine streaks of malachite with or
without atacamite, up to 40 mm long. They are
enclosed within the siltstone layers.
(e) Strata-bound minute spots of malachite, up to
0.5 mm in diameter, distributed within the red
kaolinitic shales.
(f) Strata-bound veinlets cutting across the red
kaolinitic shales. These veinlets consist of one of
the following associations: malachite, atacamite
and gypsum with or without malachite, turquoise
and paratacamite, and chrysocolla, atacamite and
gypsum.
(g) Strata-bound veinlets of atacamite cutting
across the iron pisolites.
(h) Strata-bound thin crusts of paratacamite
encountered within the gypsum and alunite
nodules.
2 Geometrical forms of copper minerals in the
subsoil horizon:
(a) Strata-bound pockets of turquoise, up to
30 mm in diameter, encountered within the shaly
materials of the intrakarstic sediments.
(b) Strata-bound veinlets of atacamite, malachite
and gypsum cutting across the manganese nodules
and crusts which fill the subsurface solution
cavities.
3 Copper minerals in exposed and altered Carbon­
iferous karst. In the exposed and altered Carbon­
iferous karst terrains, only turquoise and malachite
are recorded. This type of karst is represented by an
accumulation of terrigenous sediments mixed with
manganese oxides. The turquoise and malachite
occur as fine detrital grains embedded within the
residual accumulations. Other copper minerals seem
to have been leached and removed during the mech­
anical and chemical weathering which accompanied
the Quaternary karstification event.
GEOCHEMISTRY OF THE
CARBONIFEROUS PALEOKARST
PROFILE AND THE FORMATION OF
ASSOCIATED COPPER MINERALS
The paleokarst profile of Abu Hamata (Fig. 3) was
sampled and analysed for major and trace elements
(Tables 3 and 4). Two samples (samples 1 and 2)
represent the parent stylolitic dedolomitized calca­
renite and the overlying dedolomite of the subsoil
horizon respectively. The other five samples are
from the topsoil sediments collected from different
levels. The intercalated layers of gypsum and alunite
of the topsoil and the highly manganiferous varieties
of the subsoil horizon are not represented. The
analysed samples were carefully selected to avoid
any megascopic gypsum, alunite, copper and
manganese minerals. Each spot sample weighed
about 1 kg, and was crushed, quartered and analysed
by XRF against relevant clay and dolomite
standards.
The frequency of the major elements throughout
the soil profile (Table 3) shows that:
1 the overall trend of the analysed samples of the
topsoil horizon is characterized by high values of
Si02, Al203 and Fe203, a low value of MgO and a
depletion of CaO. In contrast, the samples of the
subsoil and parent carbonate rocks are characterized
by high values of CaO, MgO, a low value of Fe203
and very low values of Si02 and Al203;
2 the content of MgO decreases, and CaO increases,
from the parent rock towards the subsoil;
3 the K20 content reaches up to 5·43% in the
topsoil samples but is only a fraction of 1% in the
underlying subsoil and bed rock;
4 Na20 is mostly depleted in the subsoil and bed
rock samples and ranges from 0·1 to 1·01% in the
topsoil samples;
5 P205 fluctuates between 0·09 and 0·42% in the
topsoil sediments and is represented by much lower
values in the underlying subsoil and parent carbonate
rocks;
6 Ti02 content is relatively high in the topsoil
samples reaching up to 1·48% in comparison to its
content in the subsoil and bed rock samples;
7 MnO is represented by fractions of 1% up to
2·63% in the analysed samples.
 •

Table 3. Major element content (%) of the paleokarst profile of Abu Hamata

Si02 Ti02 AI203 F�o3t MnO MgO CaO K20 Na20 P20s Loi* Total

7* 57·44 1·18 15·00 6·99 0·02 0·79 0·25 3·17 0·10 0·09 14·21 99·24
6 49·96 0·82 12·82 12·04 2·63 8·68 0·82 2·64 0-42 0·17 6·76 97·76
5 50·27 0·90 13·38 23·34 0·07 1-70 0·10 2·78 0·35 0·10 3-81 96·80
4 47·37 1-48 19·76 8·87 0-45 4·38 0-45 5-43 1·01 0·09 7·30 96·59
3 55·69 1·09 18·19 11·93 0·05 2·31 0·58 3·96 0-45 0-42 5·08 99·75
2 7·36 0·17 0·36 2·93 2-19 14·05 31·81 0·35 0·01 0·01 40·35 99·59
1 2·77 0·08 0·24 1·31 0·14 19·75 29·92 0·19 0·01 0·01 45·06 99-48

Code:
1 Stylolitic calcarenite (bed rock);
2 ·Dedolomite (subsoil); �
3 "'"'""''" l �"'
4 Green shale; ...,
5 Ferruginous shale; Topsoil �
6 Green shale, cupriferous; s·
"'
7 Green shale. ...,
:::,
* See Fig. 3. :::-:
N
t Total iron oxide. :::,
* Loss on ignition to 1000°C ::::-.
0
?
v,
s·
�.
Table 4. Trace element content of Abu Hamata paleokarst profile (in ppm)

Rb Ba Pb Sr La Ce Nd y Th Zr Nb Zn Cu Co Ni Sc v Cr Ga

7* 49 74 135 143 92 155 66 68 29 524 72 58 151 7 17 15 350 346 26

6 83 1282 69 192 84 176 75 72 16 412 so 423 476 35 97 13 555 614 20
5 89 76 146 200 108 220 102 69 12 431 so 498 438 44 58 16 1480 1310 19
4 171 105 221 126 155 241 133 82 27 715 84 1020 178 42 328 16 1430 1140 29
3 128 93 31 179 127 242 162 1 15 21 524 69 446 470 23 93 17 193 625 28
2 22 1610 172 88 259 207 342 231 1 110 15 567 74 61 291 14 286 544 9
- -
1 125 101 35 61 110 10 9

* As in Table 3.

......
0\
-...]
168 M.A . El Shar ka wi, M.M. El Arefand A. Abdel Moteli b

ln the subsoil horizon, the analysed sample is factors controlling the leaching, migration and rede­
relatively enriched in barium, lanthanum, neo­ position of these elements. The rhythmic strati­
dymium, yttrium, cobalt and nickel (Table 4) when graphic distributions of the redeposited iron- and
compared with the topsoil samples while rubidium, aluminium-bearing minerals, e.g. goethite and alu­
strontium, thallium, zirconium, niobium, copper nite, within the topsoil sediments indicate seasonal
and gallium are relatively depleted. ln the topsoil changes in the Eh and pH conditions of the soil
there is a pronounced increase in the content of environment, which in turn clepenclecl on variations
thallium, zirconium and copper. The increase in in the palaeoclimate or the soil moisture regime.
thallium and zirconium is attributed to the detrital The close relation between the alunite and gypsum
components of the pedogenetic paleokarstic sedi­ suggests that alunite was deposited during the
ments while copper is attributed to the deposition of periods of evaporation. Potassium in the topsoil
copper minerals from solution in the topsoil. sediments may have been derived by leaching from
The chemical composition of the analysed topsoil allochthonous potassium-bearing minerals, e.g.
samples reflects their lithological characters and is feldspar, mica and illite, or during the diagenesis of
similar to that of ferruginous laterites or latosols the residual clays in an acidic medium.
(Bear, 1967). Kaolinite and sesquioxicles of iron and Manganese is mobile in the relatively acidic parts
manganese are the most abundant mineral constitu­ of the soil profiles and may be carried in solution to
ents of all the studied topsoil sections. The kaolinitic the lower parts, where the pH is higher (Lelong et
and iron layers are intercalated with thin layers of al., 1976). This may explain the general scarcity of
gypsum and alunite and indurated iron pisolites. MnO in the present topsoil horizon and the concen­
Kaolinite is a good indicator of a former wetter tration of the manganese ore in the karst solution
climate. It is favoured by a high-leaching acidic features of the subsoil horizon by an eluviation
environment but also remains stable for long time process during soil formation.
intervals in neutral and alkaline environments Silicon is one of the main constituents of the
(Birkland, 1984). Because of the high solubility of kaoLinite and chrysocolla. Under very humid
K+, Ca2 +, Si032- and o- ions in weathering con­ leaching conditions, silicon is leached easily as bases.
ditions, the salt accumulations in the soil profiles It tends to form SiOl- ions which remain soluble
reflect a diminishing in soil moisture under ariel over a large pH range.
conditions or clue to seasonal oscillations of the The occurrence of phosphorus in the present top­
water table level (Birkland, 1984). soil sediments is attributed to the abundance of the
The depletion of CaO in the topsoil was the result organic matter distributed in this horizon. The or­
of the complete dissolution of dolomite in the humid ganic matter is responsible for leaching, absorption
regime, i.e. during the eluviation process. Calcium and accumulation of phosphorus as organic phos­
tends to migrate to lower horizons, forming redepo­ phate complexes and/or phosphoric acid (Bear,
sited CaC03 (ancient caliche and freshwater calcite 1967). The phosphorus is the main constituent of
cement), under suitable alkaline conditions and a the pseuclomalachite as well as turquoise.
low C02 content.
The main forms of iron in the studied topsoil
sections are residual ochres, indurated pisolites of DISCUSSION
goethite (ferricrete) and hematite associated with
kaolinite. Aluminium is the main constituent of the Two modes of occurrence of cupriferous sediments
residual kaolinite, turquoise and alunite. Iron can are recognized in the platform Palaeozoic sediments
migrate in the acidic medium of the exposed soil of Sinai. Copper mineralization in Cambro­
waters and is converted to ferric ions in a more Ordovician sediments is represented by strata-bound
alkaline medium (Hem, 1963). In the bicarbonic to stratiform malachite in clastic sediments while the •
moderately acid medium, iron becomes relatively younger Carboniferous copper mineralization en­
soluble, while aluminium remains immobile (Lelong compasses a variety of strata-bound copper minerals
et al., 1976; Krauskopf, 1979). Aluminium is soluble confined within a fossilized karst profile. The
when the environment is sufficiently oxidizing and is Cambro-Ordovician occurrence is similar to the
deposited owing to small increases of pH (Lelong e t Cambrian cupriferous sediments of Timna (Bartura
a l., 1976). Thus the relative mobility o f the iron and & Wurtzburger, 1974) in Israel and Wadi Dana
aluminium and Eh-pH conditions, are the essential (Bender, 1974) in Jordan.
 Copper mineralization, Sinai
The copper in the Cambro-Ordovician and Car­
boniferous clastic sediments can be envisaged as a
surface leaching product of copper sulphide minerals
from the Precambrian rocks of the Arabo-Nubian
Shield. These sediments surround the border of the
copper-mineralized Precambrian rocks in Jordan
(Burgath et al., 1984) and in Egypt (El Shazly et al.,
1955). It is debatable whether copper was present
in the Lower Dolostone Member or brought into
solution during the pedogenetic evolution of the
karst profile. Nevertheless, Soliman (1961) recorded
0·5% copper in the large dolomite crystals of the
Lower Dolostone. The bed rock and subsoil are
depleted in copper relative to the topsoil at the Abu
Hamata site (Table 4). The intimate association of
copper mineralization with faults and volcanism in
the Cretaceous to Neogene sedimentary rocks of
Israel (II ani et a/., 1987) could not be extended to
explain the studied Palaeozoic sediments in Sinai
where copper mineralization is never recorded con­
centrated in the vicinity of faults or tied to the
Tertiary basalts.
The syngenetic Cambro-Ordovician malachite is
intimately associated with clay minerals and displays
a strong congruence with the sedimentary structures.
It is believed that malachite was probably formed
from a bicarbonate solution saturated in copper and
was deposited under severe arid conditions.
The copper-mineralized karstified Carboniferous
sediments have no counterpart in neighbouring
countries. The karstified nature of the enclosing
sediments was overlooked by previous investigators
who erroneously described it as a normal strati­
graphic succession. The dolomitic (mainly ferroan
dolomite) and dedolomitized subsoil of the karst
profile is intimately developed with extensive
manganese mineralization (El Sharkawi eta!., 1990).
The clayey topsoil is admixed with strata-bound
copper carbonate, chloride, silicate, sulphate and
phosphate minerals, and hence mineralogically dis­
tinguished from the copper mineralization of the
Cambro-Ordovician sediments. The fate of leached
copper during karstification depends on many factors
as reflected in the diverse mineralogical composition.
The stratified arrangement of the copper minerals
within the kaolinitic shales of the topsoil horizon
and their close relation with gypsum and alunite
indicate that these copper minerals were deposited
from a pore soil solution containing Cu2+, Cl-,
SOi- C032-, POl-, SiOl- and AlH ions and
were entrapped within the shale laminae. The for­
mation of copper minerals prevailed during low
169
moisture regimes or periods of evaporation and
under neutral to alkaline conditions. The fact that in
some instances the copper minerals form strata-bound
veinlets cutting through certain karst or karst alter­
ation products may be related to the mobilization of
the above-mentioned ions during subsequent acidic
leaching and their redeposition.
Copper is comparatively soluble in the acidic
environment of the weathering processes. The
changes in physico-chemical conditions of the sol­
ution during pedogenesis can precipitate metals such
as c0pper as stable minerals (Lelong et a!., 1976).
The neutralization of acidic waters by reactive wall
rocks such as carbonates causes dissolved copper to
precipitate (Guilbert & Park, 1986). Eh and pH
changes and the formation of complex chlorides
dominate the geochemical behaviour of copper
at low temperature (White, 1968; Rose, 1976;
Maynard, 1983) and there is a large field of copper
solubility under oxidizing conditions at moderate to
low pH. Iron is less soluble under these conditions.
In their passage through a carbonate formation the
dilute copper solutions will precipitate brochantite
and atacamite. The stability field of these minerals is
similar and their formation depends only on the
concentration of so/- and Cl- anions in the sol­
ution (Kern & Weissbrod, 1967). According to
Barton & Bethke (1960), the relevant reaction for
the formation of atacamite is:
The cupric solution reacts with C02 derived from
the carbonate or the carbonic acid to form malachite
by the following reactions:
2Cu 2+ + Col- + 20H- --> CuzC03 (0Hh
According to Guilbert & Park (1986), malachite is
favoured in more dilute cupriferous water or by a
lower Pco2, although the stability field of malachite
(Kern & Weissbrod, 1967) in terms of the pH and
copper concentration in the solution at various partial
pressures of C02 shows that the malachite crystal­
lization is only slightly_ dependent on the Pco2.
According to Kern & Weissbrod (1967), brochantite
or atacamite will be precipitated if the Cu 2+ con­
centration is high enough. On the other hand, at a
very low Cu 2+ concentration, azurite, malachite or
tenorite can precipitate and in such circumstances
the C02 content of the atmosphere above the sol­
ution has scarcely any influence on the stability of
these minerals. Chrysocolla has to be formed from a
cupric solution containing available soluble silica. In
170 M . A . El S har ka wi , M. M. El Arefan d A. Abde l Mo te li b
supergene processes, the soluble silica may combine
with copper to form chrysocolla as follows:
4Cu 2 + + 4Si0/- + 6H2 0 � Cu4H4Si40w(OH)s
The occurrence of pseudomalachite in the organic­
rich layers of the topsoil may indicate the reaction of
the cupric solution with organic phosphorus and/or
phosphoric acids to form this mineral when leaching
was not strong enough to remove phosphorus. On
the other hand, the presence of turquoise in the
form of strata-bound veinlets or pockets within the
sediments of the subsoil horizon suggests th€ mi­
3
/
gration of Cu2+, AJ + and PO - from the upper
acid-leached parts of the soil into the lower horizon
and their redeposition.
CONCLUSIONS
Workable copper deposits are known to occur in the
Palaeozoic platform sediments surrounding the
northeast margin of the Arabian Shield. In the Urn
Bogma region, two modes of copper occurrence
were recognized: (1) strata-bound to stratiform
malachite in the Cambro-Ordovician ftuviodeltaic
sediments; and (2) strata-bound copper carbonate,
chloride, silicate, sulphate and phosphate minerals
in a buried Carboniferous karst profile.
The Cambro-Ordovician occurrence is similar to
the copper deposits in Timna and Wadi Dana in
neighbouring countries. It is anticipated that
Cambro-Ordovician malachite at Urn Bogma was
syngenetically deposited under a ftuvi odeltaic en­
vironment. The Carboniferous paleokarstic copper
deposit has no counterpart in the neighbouring
countries and the copper minerals are of supergene
origin deposited during the pedogenic evolution of
the paleokarst surface.
The recognition of paleokarst in the Carbon­
iferous, the intimate development of copper
minerals within the topsoil horizon capping the
Lower Dolostone Member of the karst profile and
the unconformable cap of the Upper Dolostone
Member could be used as a prospecting guide for
workable copper deposits in the region.
ACKNOWLEDGEMENTS
We thank N.A. El Ella for the identification of the
spores and pollen grains in the topsoil and J. Parnell
for correcting the English.
REFERENCES
BALL, J. (1916) The Geography and Geology of West
Central Sinai- Egypt. Surv. Dept . , Cairo, 219pp.
BARRON , T. (1907) The Topography and Geology of the
Peninsula of Sinai (Western Portion) . Surv. Dept. ,
Cairo, 241pp.
BARTON , P . B . & BETHKE, P . M . (1960) Thermodynamical
properties of some synthetic zinc and copper minerals.
Am. J. Sci. (A) 258, 21 -34.
BARTURA, Y. & WURTZBURGER, U. (1974) The Timna
Copper Deposit, pp. 277-285. Centenaire de Ia Soc.
Geol. de Belgique. Gisement Stratiformes et Provinces
Cupriferes, Liege.
BEAR, F . E . (1967) Chemistry of the Soil. American Chemi­
cal Society Monography Series. Reinhold, New York,
512pp.
BENDER, F. ( 1974) Geology of Jordan . Contribution to the
Regional Geology of the Earth. Gebruder Borntraeger,
Berlin, 196pp.
BIRKLAND, P . W . ( 1984) Soils and Geomorphology. Oxford
University Press, New York, 372pp .
B u RGATH, K . P . , HAGEN, D. & SIEWERS, V. ( 1984) Geo­
chemistry, geology and primary copper mineralization in
wadi Araba, Jordan. Geol. Jb (B) 53, 3-53.
.
DAVEY , J.C. (1948) Report on Southern Sinai. Mining
Mag. 78, 44-152 and 212-214.
E L SHARKAWI, M . A . , E L AREF, M.M & ABDEL MoTELIB,
A. (1990) Manganese deposits in a Carboniferous
paleokarst profile, Urn Bogma region, west-central Sinai ,
Egypt. Min Deposita 25 , 34-43.
EL SHAZLY, E . M . , AsDEL NASER, S . & SHUKRI, B . ( 1955)
Contributions to the mineralogy of copper deposits in
Sinai . Geol. Surv. Egypt, Bull. 1 , 13pp.
EL SHAZLY, E . M . , SHUKRI, N . M . & SALEEB, G.S. (1963)
Geological studies of Oleikat, Marahil and Urn Sakran
manganese-iron deposits, West Central Sinai. J. Geol.
UAR 7, 1 -27.
GINDY, A.R. ( 1961) The origin of copper mineralizations
in Central Sinai , UAR. Proc. 4th Arab Sci. Congr. ,
Cairo , 607-634.
GuiLBERT, J . M . & PARK, G . F . (1986) The Geology of Ore
Deposits . Freeman, New York , 985pp.
HEM , J . D. (1963) Chemical equilibria and rate of manga­
nese oxidation. US Geol. Surv., Water Supply Bull.
(A) 1667, 64pp.
HILMY, E. & Mo HSEN , L. (1965) Secondary copper minerals
from West Central Sinai. J. Ceo!. UAR 9, 1 - 12.
ILANI, S., FLEXER, A. & KRONFELD , J. (1987) Copper
mineralization in sedimentary cover associated with
tectonic elements and volcanism in Israel. Min. Deposita
22, 269-277.
IssAWI, B. & Jux, U. (1982) Contributions to the strati­
graphy of the Paleozoic rocks in Egypt. Ceo!. Surv.
Egypt, Bull. 64, 28pp.
KERN, P. & WEISSBROD, A. (1967) Thermodynamics
for Geologists. Freeman, Cooper and Company, San
Francisco, 304pp .
KORA, M. ( 1 984) The Paleozoic outcrops in Urn Bogma
area, Sinai. PhD Thesis , Mansoura Univ . , Egypt , 280pp.
KRAUSKOPF, K . B . (1979) Introduction to Geochemistry .
McGraw-Hill, New York, 817pp.
LELONG , F. , TARDY , Y., GRANDIN, G . , TRESCASES, J . J . &
 Copper m iner alization , Sin ai
BouLANGE, B. (1976) Pedogenesis, chemical weath­
ering and processes of formation of some supergene
ore deposits. In: Handbook of Strata-bound and Strati­
form Ore Deposits , Vol. 3 (Ed. by K.H. Wolf) , pp.
93 - 173. Elsevier, Austerdam.
LucAS, A. & HARRIS, J.R. ( 1962) Ancient Egyptian Ma­
terials and Industries , 4th edn. Edward Arnold, London,
523pp.
MAGARITZ, M. & BRENNER, L B . (1979) The geochemistry
of a lenticular manganese ore deposit (Urn Bogma ) .
Min. Deposita 14, 1 - 13.
MAYNARD, J . B . ( 1983) Geochemistry of Sedimentary Ore
Deposits. Springer, New York, 305pp.
RosE, A.W. (1976) The effect of cuprous chloride com­
plexes in the origin of red-bed and related deposits.
Econ. Geol. 72, 1036- 1048.
171
SEGEV, A. (1984) Gibbsite mineralization and its genetic
implication for the Urn Bogrna manganese deposits,
Southwestern Sinai. Min. Deposita 19, 54-62.
SoLIMAN, S . M . (1961) Geology of the manganese deposits
of Urn Bogma, Sinai and its position in the African
manganese production. 1st Iron and Steel Congr. Proc.,
Min. Ind., Cairo , 1 - 2 1 .
S OLIMAN, S . M . & EL FETOUH, M . ( 1969) Petrology o f the ·
Carboniferous sandstones in West Central Sinai. J. Geol.
UAR 13, 6 1 - 143.
WEISSBROD, T. ( 1969) The Paleozoic of Israel and adjacent
countries (part 2), the Paleozoic outcrops of South­
western Sinai and their correlation with those of Southern
Israel. Geol. Surv. Israel, Bull. 48, 32pp.
WHITE, D .E. (1968) Environment of generation of some
base-metal ore deposits. Econ. Geol. , 63 301 -335.
Spec. Pubis int. Ass. Sediment. (1990) 11, 173-180

Geochemical data for the Dongchuan- Yimen

strata-bound copper deposits, China

C. R A N
Department o f Geology, Kunming Institute of Technology, Kunming, Yunnan Province, China

ABSTRACT

Trace element, organic carbon, stable isotope and fluid inclusion data are reported for the Dongchuan­
Yimen type strata-bound copper deposits Yunnan, China. The trace element data show that the ore
materials were derived from the host rocks and underlying beds, and that bismuth, lead and zinc were
additionally introduced through deep fractures. The ore-forming fluid was a hot connate brine. The
sulphur was derived from sulphate-reducing bacteria, and carbon was derived from marine carbonate.
Organic carbon played an important part in the metallogenesis. In the Kangdian Axis, two deep
fractures controlled the sedimentation of a cupriferous algal reef limestone. Copper was subsequently
mobilized into vein deposits.

INTRODUCTION

The Dongchuan-Yimen copper deposits are large
(economically mineable) and occur in an algal reef
carbonate development in the Proterozoic Kunyang
Group in the South Kandian Axis (Fig. 1, Table 1).
The ore bodies include stratiform and vein types.
The main horizons which contain the stratiform ores
are: (1) the lower algal dolomite of the Luoxue
Formation and a transitional bed underlying it; and
(2) the black bed of the Shishan Member of the
Luzhijiang Formation and a transitional bed under­
lying it. They are the products of two transgressive
cycles, and are tidal flat-bay-lagoon facies. Purple
beds underlie both of these beds. The stratiform
ores are of diagenetic origin, and were remobilized
into vein deposits (Fig. 2; Ran, 1983).
GEOCHEMICAL DATA
Trace element geochemistry
Trace element data for beds and ore deposits of the
mining area are recorded in Table 2. The coefficients
of trace element enrichment were evaluated using
the ratio of the analysed value of the elements to the
Clarke value of elements in the crust (Li, 1981). The
elements with a coefficient of greater than 2 are
enriched elements, coefficients in the range 2-0·5
are elements at levels close to the Clarke value, and
coefficients less than 0·5 are deficient elements.
Silver, copper, tin, molybdenum and boron are
enriched in strata of the Luoxue and Yinmin For­
mations, barium and lead are at normal levels
and other elements are deficient. Silver, copper, tin,
molybdenum, barium, lead and bismuth are enriched
in the ore deposits. The silver contents in the strata
are 0·26 to 12 ppm (average 2·3 ppm), but in bornites
they exceed 100 ppm and in chalcopyrites the values
range from 5·2 to 50 ppm. Bismuth is absent in the
Yinmin purple bed, the Luoxue dolomite and dia­
genetic deposit, and is occasionally present in the
transitional beds, but ranges from 56·3 to 195 ppm in
remobilized deposits; so bismuth is probably not
derived from the host sequence. Gallium is generally
in the range 2-8 ppm in the host rocks, but at
12-30 ppm in chalcopyrite. In the Shishan Member,
Yimen, silver, copper, lead, molybdenum, gallium,
tin, boron and barium are mostly enriched elements,
lanthanum, titanium, vanadium, nickel, cobalt and
yttrium are normal and the others are deficient. In
the Shishan-Fengshan ore deposit, copper, silver,

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun 173

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
174 C. Ran

I
Proterozoic
( Kunyang Subgroup)

Proterozoic
z
(Sinian)

Mz Mesozoic

I Major fault

Fig. 1. Geological sketch map of

the south of the Kangdian Axis,
highlighting the Kunyang Group.

tin and molybdenum are enriched elements, prob­
ably derived from the host rocks. In summary,
the lithophile elements titanium, chromium, stron­
tium, yttrium, niobium, lanthanum and vanadium
are mostly deficient, except barium and boron; the
Organic geochemistry
The contents of organic carbon in the Dongchuan­
Yimen copper mine are recorded in Table 3. The
average organic carbon content in the host rocks is

� � � �
siderophile elements nickel and cobalt are mostly

�
I ��

�
\\

1�� �
deficient or normal and the chalcophile elements u iang Fm.
L zhij
Heishan Fm.
copper, silver, tin, lead, bismuth and gallium are uoxue Fm.
L-------------
mostly enriched. -

Yinmin Fm.
The chalcophile elements were enriched within
the Yinmin purple bed, transitional bed, Luoxue
dolomite and three beds of the Shishan Member to
make these strata favourable source beds. The trace
element distributions in the strata and ore deposits
at different horizons are similar, which suggests an
inheritance of metals from the strata to the ore
deposits. The association and contents of most trace II
elements in the Lala copper mine of the Hekeu
Formation are similar to those in the Luoxue and
Yinmin Formations.
The total rare earth element content (La to Lu + Y)
in the Yinmin-Luzhijiang Formations of the Fig. 2. Two-stage model of mineralization for the
Kunyang Group, 209·23 ppm, the ratio of LREE: Dongchuan- Yimen strata-bound copper deposits.
Mineralization occurred in syndiagenetic (I) and epigenetic
HREE which is 18·53, and the ratio Eu: Eu* =
(II) stages in cupriferous sediments of the Kunyang Group.
0·70, are compatible with derivation from an evolved Arrows indicate direction of brine movement; ore bodies
crustal source. are black.
Table 1. Composite Precambrian stratigraphy and ore-bearing sedimentary formation in Kangdian Axis

Formation Thickness Lithological character Ore-bearing sedimentary Developing stage Type of ore deposits Cupriferous
(m) formation of geosyncline horizon

Chengjiang Ferruginous molasse formation Rejuvenated Sedimentary iron

(or Dengying) uplifting

(Jinning movement]
Proterozoic Kunyang Group
Upper >3419 Sandstone and slate intercalated with Upper ferruginous terrigenous Subsidence and Sedimentary,
limestone and andesite, with formation rejuvenated metasedimentary
conglomerate at the base uplifting iron

tJ
[Manyingou movement(?)] ()
Luzhijiang 32-3035 Upper siliceous banded dolomite, and Fengshan veined Major
�
(Middle) limestone with stromatolites copper
g..
;;::
�
;:s
Lower carbonaceous, argillaceous, Shishan stratiform Major
I
tuffaceous dolomite and tuff copper
�
Upper blue-grey thin-bedded �
limestone, black slate �
"'
Heishan 115-1900 Middle greyish-green, yellowish- Cupriferous algal reef �
(Middle) green silty banded slate intercalated s
with thin-bedded dolomite 6-
()
;;::
Lower black slate intercalated with Carbonate formation Subsidence Daqinggou stratiform Minor ;:s
!::>..
dolomite and tuff copper

Luoxue
(Middle)
40-500 Stromatolitic dolomite, argillo-
arenaceous dolomite intercalated
Luoxue stratiform
copper
Major
�
"'
....
with thin-bedded slate !::>..

Yinmin 20-1300 Cyclothem composed of purple slate, Xikuangshan �

Minor ()
(Middle) dolomite and sandstone- slate, stratiform Cu-Fc �.
with conglomerate at the base Sedimentary­
1:;"
metamorphosed­
hydrothermal iron

[Dongchuan movement(?}]
Lower >7525 Sandstone and slate intercalated with Lower ferruginous terrigenous Subsidence Sedimentary,
limestone and tuff formation sedimentary­
metamorphosed­
hydrothermal iron

[Palaeo-Dongchuan movement (?)]

Hekou >1250 Green schist Copper-iron-bearing spilite- Subsidence Dahongshan volcanic­ :3
Vl
keratophyre formation hosted Cu-Fe
 -.]
-

a-

Table 2. Average content of trace clements in Dongchuan- Yimen copper deposits (in ppm)

Strata and ore deposits Number of Ba B Cr Cu Pb Ga Ni Bi Nb Mo Sn

samples

Yinmin purple beds 5 519 56 22·6 399 2-4 6·6 16·5 -

10·2 1·8 6·2
Transitional beds 5 344 67 . 16·3 483 6·9 6·8 13-6 22 3·6 57·9 7·9
Luoxue dolomite 6 414 30·7 6·1 725 7·1 4·9 11·1 6·8 3·1 12-4
Shishan purple beds 4 9775 95·8 43 228 33-6 25-4 43 -
10·2 2-4 6·0
Shishan transitional beds 5 1049 1 19·6 60·3 294 68·9 139 72-7 10 3·8 10·6
Shishan black beds 5 458·6 18·2 23·9 279 339·0 48·0 70·1 10·8 79·2 1·8
Fengshan dolomite 5 32·8 4-4 2·4 so 40·6 3·8 4·5 0·6 9-4 22
Fengshan diapir body 3 446 43·4 48·7 228 12·3 27·8 24-4 16·2 7·7 23·3
Lata copper deposits 2 16·6 >1000 18·6 42·5 850 90
Luoxue- Yinmin diagenetic deposits 5 1976 4·7 >1000 50·5 4·6 11-4 188·9 18·9 30·6
Luoxue- Yinmin remobilized deposits 8 837 9·1 2·3 >1000 43·9 14·9 13·0 56·3 36·6 36·2
Shishan diagenetic deposits 8 103 >1000 195 42·8 91·9 35·1 8·09 39·6 73-0
Shishan weakly remobilized deposits 5 131·2 131 >1000 325·9 25-4 275·8 60 13·6 47·8 49·3
Fengshan intensely remobilized deposits 12 135·9 6-4 >1000 330 37·5 27·3 30 15·1 38·3 32
Element abundance in crust 390 13 110 63 12 18 89 4·3X10-3 19 1·3 1·7
(after Li, 1981) 0
;:.;,
Strata and ore deposits Number of v Ag Co Sr La y Ti Zn Be Co:Ni Sr:Ba �
;:s
samples

Yinmin purple beds 5 64-4 0·94 10·8 35·6 7·2 11·2 1310 0·65 0·07
Transitional beds 5 93·3 4·80 10·1 23·8 101·6 12·2 1518 4 0·3 0·74 0·07
Luoxue dolomite 6 47·2 1-20 27·4 31-4 2·5 3·2 359 15 2-47 0·08
Shishan purple beds 4 92·8 0·98 9·8 194·0 35·9 11·7 4775 44·5 2·6 0·23 0·02
Shishan transitional beds 5 152·6 1·80 21·7 66·1 53·6 12·8 8230 86·4 3·4 0·30 0·06
Shishan black beds 5 311-4 7·34 24·7 197·6 47·83 15·6 4820 0·8 0·35 0-43
Fengshan dolomite 5 33·5 1·86 2·9 54-4 3·6 3·2 190 2·3 0·64 1·66
Fengshan diapir body 3 138 1 44·3 77-3 36·7 29 11·7 3·7 1·82 0·17
Lata copper deposits 2 33·5 4·6 >1000 258 15 90 1·18 0·06
Luoxue- Yinmin diagenetic deposits 5 18-4 81·6 10·7 9·8 2-4 386 0·94 0·01
Luoxue-Yinmin remobilized deposits 8 19-4 52·2 8-40 6·8 4·6 125 20 0·65 0·01
Shishan diagenetic deposits 8 42·9 9·6 44-4 50·0 9·6 1231 237 0-48 0·49
Shishan weakly remobilized deposits 5 25·8 8·7 89-4 1·5 6·75 580 383 0·33 0·01
Fengshan intensely remobilized deposits 12 34-4 16·7 42·3 0·65 8·1 596 986 1·55 0·01
Element abundance in crust 140 0·08 25 480 39 24 6400 94 1·3 0·28 1·23
(after Li, 1981)

Determined by Central Laboratory of Yunnan Bureau of Geology and Mineral Resources using ICP-AES quantitative analysis (1986) .
 Dongchuan- Yimen strata-bound copper deposits 177

Table 3. Contents of organic carbon (%) in Dongchuan- Yimen copper mine

Strata or ore deposits Number of Average Range

samples

Yinmin Formation 12 0·050 0·02-0·10

Transitional bed 15 0·040 0·01-0·07
Luoxue Formation 15 0·040 0·03-0·07
Shishan purple bed 4 0·028 0·02-0·04
Shishan light bed 7 0·036 0·01-0·06
Shishan black bed 5 0·196 0·12-0·23
Purple diapir body 3 0·070 0·05-0·09
Fengshan dolomite 6 0·060 0·02-0·13
Luoxue-Yinmin diagenetic deposits 5 0·210 0·16-0·28
Luoxue-Yinmin remobilized deposits 6 0·230 0·14-0·33
Shishan diagenetic deposits 5 0·660 0·11-2·06
Shishan weakly remobilized deposits 5 0·200 0·04-0·56
Fengshan intensely remobilized deposits 4 0·400 0·30-0·53

Determined by Yunnan Research Institute of Petroleum Geology (1986).

Isotopic composition of sulphur

0·03-0·07% , but that in copper sulphide minerals is
much higher than in the host rocks at 0·2-0·66%
(2·06% maximum value). Besides disseminated
organic carbon, there is earthy bitumen in epigenetic
minerals in the Yimen copper mine, globular bitu­
men in dolomites, methane, carbon dioxide and
organic matter in inclusions in dolomites.
The reflectance (Ro) of bitumen in the Yimen
copper mine is 4·3-6·2% , and it is weakly aniso­
tropic. The uncorrected homogenization tempera­
tures of fluid inclusions in the dolomite are
107-234°C. The organic carbon content of dolomite
(C) is 0·05% and its chloroform-bitumen extract
(A) is 0·0076%, so the transformed ratio (A: C =
0·152) is high. The extractive ratio and the maturity
of soluble organic matter are higher (OEP = 0·93).
The pristane: phytane ratio (Pr: Ph = 0·14) is low.
The source organic matter was mainly marine algal
kerogen. The high content of organic carbon in the
ore deposit suggests that it may have played an
important part in the process of copper mineral­
ization. Possible roles for the organic matter include
the solubilization of metals by organic acids, a cata­
lyst for sulphate reduction, and a reductant for
sulphide deposition (Saxby, 1976).
The determined sulphur isotope compositions of
copper sulphides (bornite, chalcocite, chalcopyrite;
analysed by the Nonferrous Metallic Geological
Institute, Guilin, China, 1985) b34ScoT are in the
range -10 to + 16·7%o for the Dongchuan diagenetic
deposits, from -0·1 to + 15·2%o for the Dongchuan
remobilized deposits, from -4·5 to +14·9%o for
the Shishan diagenetic deposits and from -1·5 to
+ 19·5%o for the Shishan-Fenshan remobilized
deposits. The narrow difference between these
ranges of values suggests that the sulphur had a
simjlar source. The sulphur isotopic composition has
a wide range (from -10 to 19·5%o) and is predomi­
nantly positive. It is suggested that the sulphur was
mainly derived from bacterial sulphate reduction in
marine strata. The data are similar to those from
copper sulphides in the White Pine copper deposit
(in USA) and the Katanga copper deposit (in Zaire)
whose values of b34S range from -10 to + 18%o and
from -15·3 to + 19·2%o respectively, and many other
strata-bound sulphide deposits in marine rocks
(Sangster, 1976).
Isotopic composition of hydrogen and oxygen

The isotopes of hydrogen and oxygen can be used to

Isotope geochemistry
Stable isotope data for sulphur, hydrogen, oxygen
and carbon for the copper mine have been
determined.
discriminate the source of water in ore-forming fluids
(Tu, 1988), but at the present time the technique has
its limitations and the data may be susceptible to
different interpretations. Additionally, there is no
definite location of connate water in the bD-6180
cross-plot. On the basis of recent research (Tu,
178 C. Ran

1988), the composition of connate water is located

approximately in the area between the meteoric ¥ Sea water
water line and the region of metamorphic water and , --- --- - - - -- - :
magmatic water composition in the ()D-6180 3
0
::;: -40 : �_ _ Metamorphic
diagram (Fig. 3). Vl • 1 1 1 water
0 1 I I I
The isotopic compositions of hydrogen and oxygen 1 le e I
�
0 I
, --, - - - - - - ---
in minerals from the Dongchuan-Yimen copper 0
mine are recorded in Table 4. Determined values of '-0 -80 ,__'::;-..__Juvenile water
6180 for vein minerals are calculated into 6180H,o
(SMOW) values which range from 0·51 to 12·85%o.
The value of 6DH,o (SMOW) for solutions in fluid -120
inclusions ranges from -34·5 to -83·9%o. These
values plot in the areas of metamorphic water,
-20 -10 0 10 20
magmatic water and connate water in the ()D-6180
diagram (Fig. 3). There is no evidence for meta­ 6180 (%o) SMOW
morphism or magmatism in the region. Considering
Fig. 3. oD-6180 cross-plot for fluid inclusions in five
the value of soi-: Cl- (see below), it can be
carbonate samples from the Dongchuan- Yimen copper
reasoned that the water in the ore-forming fluids was mine (see Table 4).
possibly connate water. Some of these values do not
plot in the area of connate water in the diagram
because of isotopic exchange between the fluids and deposits is -0·74%o, for the Luoxue-Yinmin
wall rocks during fluid migration. remobilized deposits it is -0·84%o, for the Shishan
weakly remobilized deposit it is -1·64%o, and for
the Fengshan intensively remobilized deposit it is
Isotopic composition of carbonate carbon
0·16%o. These ranges are narrow, from -2·79 to
The average 613C (PDB) value in dolomite veins of + 1·30%o (Table 4), and consistent with derivation
the Shishan, Yimen and Luoxue-Yinmin diagenetic of the carbon from marine carbonate. However the

Table 4. Isotopic compositions of carbon, hydrogen and oxygen in Dongchuan-Yimen copper mine (averages in
parentheses)

Mineral Type Sample Analysed 013Co%o o13C%o 0180o%o 0180H,o%o ODH,o%o

deposits number mineral (PDB) (PDB) (SMOW) (SMOW) (SMOW)

Shishan Diagenetic 28 Dolomite - 2·79 17·61 5·31

Luoxue- Diagenetic D30 Dolomite 0·18 18·83 6·53 - 59·7*
Yinmin D14 Dolomite 0-40 - 2·71 18·73 6·43 -83·9
(- 0·74) (18·39) (6·09) (- 71·8)

Luoxue- Remobilized D116 Quartz - 16·41

Yinmin D41 Dolomite - 0·84 15·88 7·42
D40 Dolomite 6·18 -34·5*
(6·80) (-51·55)

Shishan Weakly S30 Dolomite - 2·39 13·98 1·09

remobilized S16 Dolomite -1·08 15·58 0·51
1 Dolomite -1·44 16·85 0·97 - 46·7*
(-1·64) (0·86)

Fengshan Intensively 18-2 Dolomite - 1·57 19·64 8·99

remobilized 19 Dolomite - 1·06 11·91 3·45
F40 Dolomite 1·30 20·07 12·32
F22 Dolomite 1·14 19·56 8·91
F38 Dolomite 0·85 18·34 7·17
F Calcite 0·32 - 0·87 19·62 12·85 -61·3
(0·16) (18·19) (8·95)

* Determined by Institute of Geochemistry, Academia Sinica. All others determined by Isotope Section of Beijing
University.
Table 5. Composition of fluid inclusions in Dongchuan- Yimen copper mine. (Determined by Institute of Geochemistry, Academia Sinica.)

Analysed results I::J

0
(ppm x 10 )
3 ;:
OQ
"'
;:-
* Mi + + + 2+ >::
Mineral Type Number of Analysed K+ Na
+ *Ca2+ F- o- soi- Na : K Na+:Ca + so42-: o- pH
2+ "'
deposits samples minerals Mg ;:
I
Shishan Diagenetic S26 Dolomite 27·9 14-4 3·5 0·4 5·7 50·0 20·2 0·52 3-69 0-40 :::;;
S22 Dolomite 43·8 30·0 12·8 4·1 7·7 67-8 54·8 0·69 1·78 0·71 8·11
�
"'
;:
Weakly S1 Dolomite quartz 4·9 22·4 2·2 1·9 2·9 76·0 6·1 4·50 5·43 0·08 "'

remobilized S5 Dolomite 3·0 3-3 0-4 0·3 0·2 6·0 1-4 1·11 5·05 0·24 �
5 Dolomite 8·7 33·7 182·0 10·5 2·3 82·8 302·0 3·87 0·18 3·60 s
6-
0
Fengshan Intensively 15-2 Dolomite 30·8 125·8 57·0 56·0 10·8 180·8 14·7 4·07 1-11 0·08 >::
remobilized F22 Dolomite 15·1 33·8 6-4 32·6 40·0 86·3 45·5 2·23 0·87 0·53 7·83 ;:
"'-
F3 Quartz 33·9 62·3 393·9 79·1 101·8 454·5 1·83 0·13 2·50 "'
-

�
F4 Dolomite 15·5 15-4 287·5 38·8 0·7 36·6 416·7 0·99 0·05 10·50
15-1 Dolomite 8·6 28·7 149·0 12·7 6·1 71-8 340·0 3·34 0·18 4·70 "'
..,
Luoxue- Diagenetic D30 Dolomite quartz 16·1 18·5 2·6 2·3 6·6 77-2 182·6 1·15 3·74 1·67 "'-
Yinmin D14 Dolomite 18·9 11-4 149·5 22·1 0·9 58·8 132·4 0·60 0·07 2·25 8·06 �
0
"'
Remobilized D40 Quartz dolomite 35·1 19·8 8·7 4·9 1·5 93·3 8·6 0·56 l-45 0·09
�·
D96 Dolomite 20·8 31·7 806·3 85·7 1-1 142·9 1071-4 1·53 0·04 7·50

2+ 2+
* Part of Ca and Mg in inclusion in dolomite probably derived from host minerals.

-.)
-

'D
180 C. Ran
o 13C, value of -16-41%o for the solution in fluid
inclusions suggests that organic matter contributed
to the composition of the solution.
Fluid inclusion geochemistry
The fluid inclusions in minerals of the copper mine
have been grouped into six classes: (I) pure liquid
inclusions; (lA) liquid inclusions (with gas); (II)
gaseous inclusions; (III) liquid carbon dioxide­
bearing inclusions; (IV) crystal-bearing (NaCl, KCl)
inclusions; and (V) organic matter-bearing in­
clusions. Classes (I) and (IA) are widespread and
abundant. Class (II) inclusions are also common
in remobilized deposits, but other classes are less
abundant. In the remobilized deposits, the size
of inclusions is bigger (4-10 !A-m), they are more
abundant, more variable in type, and yield higher
homogenization temperatures than the diagenetic
deposits. The results of salinity and temperature
determination of the inclusions (Table 5) are that
the homogenization temperature is generally in the
range 105-140°C for the Yimen diagenetic de­
posits, 150-200°C for the Dongchuan deposit and
150-280°C for remobilized deposits. The salinity
range is 12·5-23·2 wt% for both deposits, and clearly
the ore-forming fluids were hot brines. The chemical
composition of the brine (Table 5) shows that the
contents of N a+ (or K+), Cl - or sol-in this region
are high compared with modern heavy metal-bearing
solutions in some seas (Jiang, 1983). The values of
S042-: Cl - (mostly >0·14) show that the water type
is neither pure chloride brine nor choride brine
( sensu Jiang, 1983), but a sodium-sulphate­
chloride water whose total mineralization and value
of SO/-: Cl- are higher. In the genetic classification
for hot brines of Jiang (1983) this brine has affinities
with shallow connate water. A growth fault (fault I
in Fig. 1) at the margin of the depositional basin
may have allowed brine flow and a source of heat.
Research on inclusions in various vein minerals
shows that there were two stages of hot brine cor­
responding to the two types of deposits (diagenetic
and vein). The temperature of the hot brine during
the diagenetic stage was relatively low and the ratios
of Na+: K+ (average 0·74) and of SO/-: Cl­
(average 1·26) were also relatively low, but the
temperature and ratios of Na+ : K+ (2-4) and of
sol-: Cl- (3·0) were relatively high during the
remobilization stage.
CONCLUSIONS
Reforming metals were deposited within the marine
sediments of the Yinmin and Luoxue Formations and
the Shishan Member of the Luzhijiang Formation.
Metals were concentrated from the cupriferous sedi­
ments by hot brine flowing through deep faults, with
the influence of organic matter, to form copper
sulphides as stratiform ore deposits. Sulphide pre­
cipitation was engendered by bacterial sulphate
reduction. Intensive faulting introduced hotter brine
to the strata and remobilized the metals into new
vein ore bodies.
ACKNOWLED GEMENTS
I thank the National Natural Science Foundation of
China for their support for our project, and Z.
Zhijun, G. Jianguo, H. Meifang, L. Weihua, W.
Linjang and 0. Xiangwei for participating in work
for this project.
REFERENCES
JiANG, Q.J. (1983) The role of hot vadose brine mineral­
ization and the genetic indicators of the ore deposits.
Min. Deposits, Beijing, China 2, 57-59.
L1, T. (1981) Table of Abundance of Chemical Elements.
Geology & Prospecting Publishing House, Beijing,
China.
RAN, C. Y. (1983) On genetic model of Dongchuan type
strata-bound copper deposit. Scientia Sinica (B) 26,
983-995.
SANGSTER, D.F. (1976) Sulphur and lead isotopes in strata­
bound deposits. In: Handbook of Strata-bound and
Stratiform Ore Deposits, Vol. 2 (Ed. by K.H. Wolf),
pp. 219-236. Elsevier, Amsterdam.
SAXBY, J.D. (1976) The significance of organic matter in
ore genesis. In: Handbook ofStrata-bound andStratiform
Ore Deposits, Vol. 2 (Ed. by K.H. Wolf), pp. 111-128.
Elsevier, Amsterdam.
Tu, G. Z. (1988) Geochemistry ofStrala-bound Ore Deposil
in China, Vol. 3, pp. 18-20. Science Press, Beijing,
China.
 Metal Enrichments Associated with
Organic Matter

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
Spec. Pubis int. Ass. Sediment. (1990) 11, 183-192

Metal enrichments in organic materials as a guide to

ore mineralization

J. P A RNELL
Department of Geology, Queen's University, Belfast BT7 INN, UK

ABSTRACT

The determination of metal enrichments in organic materials can contribute to the geochemical
exploration for metalliferous ore deposits. An enrichment in metals can develop at several stages in the
geological evolution of organic matter, from living tissue through kerogen and liquid hydrocarbons to
solid hydrocarbon products. Scenarios for enrichment include: (1) uptake by organic matter from
groundwaters flowing through ore deposits; (2) organic matter caught up in metal-rich hydrothermal
systems; and (3) organic matter with a signature of low-level synsedimentary metal concentrations which
were subsequently remobilized into ore deposits. Some solid bitumens are so enriched in metal that they
constitute the actual ore body. Uranium is especially found enriched within organic materials, including
bitumens which precipitate around uranium minerals due to radiation-induced polymerization, but
many other metals also form enrichments.

INTRODUCTION

The occurrence of organic materials in ore deposits
and other concentrations of metals is extremely
widespread. In many cases the organic material
played a geochemical role in the concentration of
metals but was not itself enriched in metals. However
some organic materials are enriched with metals.
Metal concentration can be envisaged in several
types of organic material, which represent different
stages in the geological evolution of organic matter.
Living organisms utilize and may take up a large
number of elements including metals (see below).
The decay of dead organisms yields organic acids
and other compounds which may complex with metal
ions. The degradation of sulphur-rich organic matter
by anaerobic bacteria, and bacterial sulphate re­
duction both yield hydrogen sulphide which can help
to precipitate metals as sulphides within organic-rich
sediment. Mixed sequences of organic-rich and
organic-poor sediment contain redox boundaries
which facilitate metal precipitation. Finally epi­
genetic organic materials (migrating petroleum, and
bitumens and pyrobitumens of diverse origin) can
cause the reduction or complexing of metals. At
each of these stages it is possible for the organic
material to become metal-enriched. This paper
discusses how metal enrichments within organic
materials may be a significant guide to metalliferous
ore exploration.
METAL ENRICHMENT IN ORGANIC
MATERIALS
A large number of elements are concentrated by
biological activity. M;�my metals are taken up by
micro-organisms for use in enzymes or for other
metabolic functions, and some organisms can con­
centrate them by several orders of magnitude (see
Robbins, 1983 and references therein for review of in­
teractions between biomass and nutrients). Much data
show that terrestrial plant matter in particular ac­
cumulates metals. For example peat bogs concen­
trate uranium and other metals through adsorption
and the binding action of humus (Boyle, 1982).
Cannon et at. (1968) showed that plants on a tailings
dump were concentrating substantial quantities of
base metals. Determinations of metals in young
coniferous trees suggest that they can be used as a

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun 183

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
184 J. Parnell
sampling medium in geochemical prospecting (King
et al.,1984).
Once organisms have died, the degraded tissues
may still absorb some metals, and it is found that the
metal concentrations in organic-rich sediments in an
anoxic environment are much higher than those in
the overlying water column. Further enrichment of
metals can occur during the diagenesis of the organic­
rich sediment. Metals are already being remobilized
during early diagenesis and transported or deposited
according to the redox conditions. The relative
importance of different metals may change, because
some organometallic complexes are quite stable
during diagenesis, while others break down as the
temperature rises. Vanadium and nickel complexes
are particularly stable and these metals will substitute
for others which are progressively lost (Lewan &
Maynard, 1982). Vanadium and nickel are also im­
portant components of petroleum and bitumens, in
which they are concentrated within certain organic
fractions, particularly the heavy fractions rich in
asphaltenes and sulphur. In addition to vanadium
and nickel, elements regularly concentrated within
petroleum and bitumens include copper, cobalt,
chromium, molybdenum, lead, manganese and iron
(Erickson et al., 1954; Bell, 1960).
The availability of significant quantities of organic
materials and metals together is particularly likely in
certain types of lake basin. In tectonically active
lacustrine basins, such as in rift systems, there may
be rapid erosion of the crystalline basement which
POOR
RICH
LAKE
\\I 1/ POOR RICH
Q ,
�9
If,
RICH
""
may be quite rich in metals and even contain mineral
deposits which can be recycled into the lake system.
Metals may also be introduced by vulcanism and
hot spring activity, and the extensive circulation of
groundwaters through fractured bedrock in a fault­
bounded system will enhance leaching of metals
from the basement. The metals, and other species
like phosphate, will include nutrients to support the
biomass in the lake, and within a deep stratified lake
the dead organic matter and the metals and phos­
phate will become locked up in the anoxic bottom
sediments. Without the organic matter there is no
anoxic environment where the metals and phosphate
can be concentrated. But the mere existence of an
organic-rich sediment and its anoxic environment is
not a guarantee of concentrating metals, because the
influx of metals varies considerably in space and
time (Fig. 1).
While inflowing rivers are draining off a crystalline
basement there is a good chance that those waters
are metal-rich. But as the watershed is gradually
worn down and the reworking of sediment becomes
more important, the flux of new metals into the
basin declines, and the higher beds in the succession
may be relatively metal-poor. However, uplift of the
basin margin may re-expose the basement and herald
a new influx of metal-rich waters. It is also possible
that metals are available but do not reach the sapro­
pelic facies at the lake centre because they are
filtered out by some other facies beforehand. That
other facies may also be organic-rich, in the form of
Fig. I. Schematic scenario for input
of metals into a lake basin. Input
may be metal-rich by erosion of
granitic and volcanic terrains, or
metal-poor due to filtering effect of
lake-margin vegetation and
reworking of sediment to
progressively greater maturities.
 Metal enrichments in organic materials 185

lake-matgin vegetation. Some lacustrine oil shales of metal anomalies which reflect mineralization in
are known to pass laterally into coal at the basin the watershed (Fig. 2).
margins (see below), and in those systems one might In the Mid-Tertiary Lough Neagh Basin of
expect that metals will be concentrated in the coals Northern Ireland, the inflowing drainage was
rather than in the oil shales. predominantly across early Tertiary basalts, and
The factor of over riding importance to metal Precambrian schists which are mineralized by gold­
enrichment is the availability of metals from the bearing quartz veins. Lacustrine lignitic sediments in
rocks in the watershed. The rocks which form the the basin are enriched in vanadium, nickel and iron
basement to the lake system may be particularly which are derived from the basalts (Parnell et al.,
concentrated in certain metals which will be reflected 1989), and in gold which has been recycled from the
as enrichments in the lake sediments. Volcanic rocks Precambrian (Sunday Telegraph, 1987).
in rift systems may particularly give up copper, In central Scotland a thick sequence of Carbon­
nickel and iron, while granites may yield uranium, iferous lacustrine oil shales includes some of the
molybdenum, tungsten and lead. Examples of richest oil source rocks in Europe (Parnell, 1988a).
ancient lake sequences in which metal enrichments They have carbon contents up to 30% but do not
reflect the nature of the underlying basement are contain significant quantities of metals (Pb <40 ppm,
discussed below. Lacustrine basins contain extensive Zn < 160 ppm, Cu <50 ppm). They occur in
redox boundaries that are favourable to the precipi­
tation of metals as they often include rhythmic
alternations between fine-grained lacustrine beds
which may be organic-rich, and oxidized fluvial or
aeolian red beds.
Metal enrichments in organic materials can be
significant to metal exploration in four ways:
1 The organic material could be enriched in metal
that has been taken up from groundwaters flowing
off a metal ore deposit, i.e. the organic matter is
younger than the ore deposit. The enrichments of
metals in present day plants are examples of this.
2 The organic material may contain metal enrich­
ments which are a signature of more limited levels of
enrichment in the host sediments. If the enrichments
in the sediments were later remobilized and concen­
trated into an ore deposit, then the organic material
used as a sampling medium is older than the ore
deposit.
3 The organic material could be so enriched in the
metal that it constitutes the actual ore. Further
metal concentrations could occur in the vicinity, or
the metal may be restricted to the organic material.
4 The organic material could be an epigenetic prod­
uct (bitumen, pyrobitumen) generated at the same
time as the ore deposit, particularly in a hydro­
thermal environment. Traces of the ore metal may
occur as a signature within the organic material.
Examples of these scenarios are given below.
Fig. 2. Three palaeolake basins in northern Britain in
which metal signatures in source terrains are reflected as
enrichments in organic-rich lake sediments: gold, iron,
Post-ore organic material nickel and vanadium enrichments in lignite of Tertiary (i)
Lough Neagh Basin; copper enrichments in stromatolites
Organic materials in ancient lake basins in the of Carboniferous (d) oil shale group: uranium and lead
northern United Kingdom provide several examples enrichments in fish fossils of Devonian (c) Orcadian Basin.
186 J. Parnell

a basin which had already existed through much of
the Devonian, and the drainage was largely through
older sandstones which were not mineralized. There
is also a lateral transition from some oil shale seams
to coal at the lake margin. No data exist for these
coals, which are not exposed at present. However
some coals higher in the sequence do contain limited
concentrations of base metal sulphides which
suggests that metals may have been filtered out by
vegetation. There was also limited drainage off some
Devonian basaltic lavas and newly extruded Car­
boniferous basaltic lavas which are copper-rich, and
copper mineralization is accordingly developed in
lacustine stromatolites in the oil shale sequence
(Parnell, 1983).
In the north of Scotland a lake system in the
Devonian Orcadian Basin received drainage directly
off Caledonian granites, some of which are miner­
alized by uranium and lead. The chemistry of the
Devonian sediments closely reflects that of the base­
ment (Plant et al., 1986). Uranium and lead are
enriched within the lake sediments, particularly in
the vicinity of a small granite outcrop in Orkney
(Fig. 3). Fish fossils in the sediments are enriched in
uranium (Davidson & Atkin, 1953; Bowie & Atkin,
1956; Diggle & Saxon, 1965). Autoradiographic
studies showed that more radioactivity is associated
with hydrocarbons infilling cavities in the fish bone
than with the carbonate-fluorapatite bone itself.
New electron microprobe �Wdies show that the
hydrocarbon in the bone contains numerous discrete
crystals of uraninite (Fig. 4). A regional survey
(Fig. 3) using the thick warty bone fragments of
coccosteid fish yielded bulk concentrations up to
4668 ppm uranium and the highest values were
recorded in the vicinity of the granite outcrop noted
above. The sediments containing the fossils are also
enriched in uranium (Michie & Cooper, 1979) but to
a much lesser degree, in a smaller region (particularly
around the granite outcrop), and only at certain
horizons. Thus not only is the uranium anomaly in
the basin more easily detected by analysing the

u 206 Pb I

�;f
204Pb

� ��
'G
{'
I
I
1723 649

�{1
18·2

\.. ' ....,

'

'· ..
'
..
•

'
:
"
,·,
0 40
1.._..,'/1

/
Km
A B

Fig. 3. (A) Anomalous concentrations of uranium (ppm) in coccosteid fish bones, and (B) zonation of anomalous lead
206 04
isotope composition around granite outcrop G, in Devonian Orcadian Basin. Normal PbP Pb composition for basin is
18·2. For location see Fig. 2.
 Metal enrichments in organic materials
Fig. 4. Backscattered electron micrograph of fish bone,
consisting of apatite (grey) with spheres of bitumen (black)
containing uraninite crystals (bright). Field width =
250 �lin.
fossils (and was first detected thus) but in some parts
of the basin the fossils are the only evidence for the
anomaly. Lead isotope data for galenas (Parnell &
Swainbank, 1985) provide independent evidence for
a focus of mineralization around the granite (Fig. 3),
but the anomaly in isotopic composition does not
occur over as wide an area as the uranium anomaly
in the fossils. It is not possible to date the timing of
the uranium enrichment of the bones, but contem­
poraneous fish debris is known to act as a sink for
metals (Tlig, 1988) and the Devonian occurrences
are likely to be syndiagenetic. A similar example of
uranium uptake by fish debris is reported from
Australia by Ramsden et al. ( 1982).
A widespread product of the interaction of metals
with organic materials is the formation of metal­
rich, organic-rich nodules at the cores of reduction
spots in red beds. The organic matter at the cores of
some spots is detrital (fragments of plant matter) but
those nodules which are mineralized tend to have
spherical cores which clearly developed postcom­
paction by accretion of migrating hydrocarbons.
The nodules contain metals characteristic of red
bed mineralization (uranium, copper, vanadium,
selenium) and typically have a mineralogy of
coffinite, roscoelite (vanadium mica), vanadium
oxides/hydroxides, vanadium-rich clays, copper
nickel arsenides and selenides, and organic carbon.
One model for their formation is through the juxta­
position of metal-bearing groundwaters in red bed
sediments with hydrocarbons migrating along cross-
187
cutting fractures (Parnell & Eakin, 1987). The
nodules are useful in assessing regional metal
anomalies. In any continental basin there is probably
enough uranium, vanadium and copper available to
be remobilized into trace quantities of ore minerals
within these centimetre-scale structures, but where
metals reach very high levels they may be more
significant. For example in several cases where the
uranium content of the nodules is greater than 0·5%
it is possible to identify more extensive uranium
mineralization, either in the basement rocks of the
basin watershed or in the organic-rich facies of lake
sediments.
1 Organic-rich nodules in Devonian red beds in
Easter Ross, Scotland, are mineralized with about
1% uranium, mainly as a component of xenotime
(Parnell, 1985). The uranium enrichment reflects a
regional uranium anomaly in the crystalline base­
ment rocks below the Devonian sediments (Watson
& Plant, 1979).
2 Uraniferous hydrocarbon nodules in Permian red
beds in Oklahoma are thought to be the product of
hydrocarbons migrating up fault planes from a deep
reservoir interacting with uranium-rich ground­
waters (Curiale et a!., 1983). Granites in the basin
watershed are uranium-rich, and uranium ore miner­
alization occurs within the coarse sediment between
the granites and the finer-grained red beds (Fig. 5).
3 Organic-rich nodules from the Permian Lodeve
Basin, France, occur in red beds, in a sequence
which also contains lacustrine black mudrocks. The
organic-rich nodules are significantly mineralized
by uranium (Fig. 6) in the form of coffinite, ac­
companied by roscoelite, clausthalite (lead selenide)
and copper arsenides. The black mudrocks are
mineralized with a major economic uranium deposit.
Some uranium is dispersed within the mudrocks,
but much is concentrated within solid bitumens in
brecciated fracture systems (Landais eta!., 1987), so
that in this case the nodules are pre-ore.
Perhaps the largest regional metal anomaly in
hydrocarbons is the high level of vanadium found
in oils and bitumens throughout much of South
America (Kapo, 1978). The anomaly is so marked
that Gold (1984, 1985) has suggested that it reflects a
vanadium anomaly in the mantle which was trans­
ferred to the upper crust through a flux of abiogenic
hydrocarbons. An alternative, more conventional
explanation is suggested here. In the case of
Venezuela, the anomaly may in part reflect ore
deposits in the local basement. Kapo ( 1978) has
suggested that waters flowing over deposits of
188 J. Parnell

��-="tj} Red Beds

S.W. OKLAHOMA
Permian (Curiale et al 1983)
U Conglomerate
Q Ordovician � Uranium in groundwaters

U Cambrian granite
� Petroleum along faults

• Uraniferous hydrocarbons

��--����-=--��=
+ Fig. 5. Origin of uraniferous
hydrocarbon nodules in southwest
+ Oklahoma, through intersection of
+ + petroleum migrating along faults
with red bed groundwaters draining
+ + + off uranium-rich granites. (Based on
Curiale et al., 1983.)

abundant and/or the metal must be a very scarce

Fig. 6. Backscattered electron micrograph of organic-rich
core of reduction spot from Permian Lodeve Basin,
France, showing concentration of coffinite, roscoelite and
copper-bearing phases (all bright) around detrital quartz
grains. Field width = 250 �un.
vanadium, nickel and copper transported the metals
and reprecipitated them in organic-rich sediments
including coals (Fig. 7). The vanadium enrich­
ments were conveyed to subsequently generated
hydrocarbons.
Organic material as an ore
For a metal-rich hydrocarbon to have value as an
ore in its own right, the hydrocarbon must be very
one.
The vanadiferous hydrocarbons in South America
are locally both sufficiently abundant and enriched
to have been considered as potential vanadium ores
(Abraham, 1945). Several mines in central Peru
contain bitumen which was ashed to a vanadium­
rich concentrate (Baragwanath, 1921). The most
important deposit, at Minas Ragra, is the richest
vanadium ore body ever recorded. The Minas Ragra
bitumen is a highly sulphur-rich variety ('quisqueite')
in which the vanadium occurs segregated out as
inclusions and veinlets of the vanadium sulphide
patronite. Detailed examination of the bitumen
shows that it consists of several phases of varying
sulphur content which may represent successive
periods of hydrocarbon mobilization (Fig. 8). A
thick vein of patronite adjacent to the bitumen may
have segregated out during the thermal maturation
of the bitumen by an igneous intrusion (McKinstry,
1957). Pilot projects for the extraction of vanadium
and nickel from solid bitumens have also been set up
elsewhere, including the USSR (Shabad, 1984).
Uranium-rich hydrocarbon deposits are very
widespread, and in a few cases are large enough to
constitute viable ore deposits. Deposits in the USSR
and France in which the uranium is largely confined
to bitumen are described by Zubov & Kotel'nikov
( 1968) and Landais & Connan ( 1980) respectively.
Kerogen, in the form of cyanobacterial mats, also
hosts a major fraction of the uranium in Precambrian
deposits in Canada and the Witwatersrand
 Metal enrichments in organic materials
Columbia
Fig. 7. Distribution of vanadium­
nickel-rich petroleum and 0 Ore deposit
vanadium-copper-rich coal in
basinal areas, relative to • Coal rich in V, Cu
vanadium-nickel-copper ore
• Petroleum rich in V, Ni
deposits in basin watersheds,
Venezuela. (After Kapo, 1978.)
Fig. 8. Backscattered electron micrograph of sulphur-rich
pyrobitumen from Minas Ragra, Peru, showing multiphase
nature. Earliest bitumen (dark grey) cut by bitumen vein
(light grey) cut and displaced by later bitumen vein
(bright); phases distinguished by different sulphur
contents. Small black masses are vanadium-enriched but
appear darker because of lower sulphur content. Field
width = 280 >UTI.
(Willingham et al., 1985). In many more deposits,
only a limited proportion of the uranium may be
held within organic materials, but in these cases the
organic materials are a good sampling medium for
189
0 Km 300
Trinidad
f)
VENEZUELA
N
r
prospecting the deposits. For example in the Moonta
copper deposit, South Australia, radioactivity was
first detected from organic material, and only sub­
sequently was torbernite mineralization recorded
(Mawson, 1944). The copper lode, in Precambrian
schists and quartz-porphyry, has yielded radioactive
organic materials where it is intersected by cross­
courses (Davidson & Bowie, 1951; Mumme, 1965).
The organic material (which appears to be a type of
bitumen) contains abundant inclusions of a mineral
referrable to xenotime (with 22% uranium substi­
tution for yttrium and coupled substitution of silicon
for phosphorus) and a variety of copper sulphides
(Fig. 9).
Several examples of uranium-enriched bitumen
occur in uranium prospects in the Scottish Devonian
lake basin discussed above (Michie & Cooper, 1979).
As the uranium anomaly in the basin was first
detected as syndiagenetic enrichments in fish, this is
also an example of an organic sampling medium
which predates formation of the ore.
Uranium-rich bitumens may be formed by two
distinct processes. Pre-existing uranium-bearing
minerals can cause the precipitation of solid bitumen
around the minerals by the polymerization/conden­
sation of migrating fluid hydrocarbons, a con­
sequence of radiation. Alternatively uranium may
be precipitated from metal-bearing fluids on contact
190 J. Parnell

case all the uranium is likely to be within the bitumen,

but much bitumen may not contain uranium.

Ore coeval with organic material

An example of the fourth scenario for the formation

Fig. 9. Backscattered electron micrograph of
carbonaceous matter from Moonta copper mines, South
Australia, showing inclusions (bright) of uranium-rich
xenotime (diffuse boundaries) and chalcopyrite­
covelline (sharp boundaries). Field width = 300 J.tm.
of uranium-rich bitumens is in a set of vein-hosted
deposits around the Irish Sea (Fig. 10) . The uranium
in these deposits is restricted to solid bitumens. The
bitumens contain inclusions of uraninite, nickel­
cobalt arsenides and at one locality bismuth­
antimony sulphides ( Parnell, 1988b ) . In the same
region, nickel, cobalt, arsenic, bismuth and antimony
also form ore deposits (Fig. 10) , although at some
bitumen localities the only trace of these metals is
within the bitumen. The chemistry of the bitumens
is therefore useful as a pointer towards the nature of
ore deposits in the region.

with fluid or solid hydrocarbons, by reduction and DISCUSSION

adsorption. In the former situation all solid bitumen
is likely to be uranium-rich but some uranium may In the assessment of how metal enrichments in
be unassociated with hydrocarbons. In the latter organic materials can be used as a guide to metal

Ni
A
tf lf-,-
N -,-,--
o
' --::
iC B
:-:-
iS
::-:b W
--:- --, U
:-c
1

A INiAsI : BITUMEN OCCURRENCE WITH METALLIFEROUS INCLUSIONS

Fig. 10. Occurrence of metals as

D
inclusions in bitumens around the
AsSb : ORE DEPOSIT : LOWER PALAEOZOIC OUTCROP Irish Sea, relative to ore deposits of
those metals in the same region.
 Metal enrichments in organic materials 191

anomalies, it is important to consider how the metals Table 1. Behaviour of metal relative to organic material
come to be associated with the organic matter. Four during progressive evolution of organic matter

mechanisms may be distinguished for metal enrich­

Organic material Metal
ment in organic materials (Parnell, 1988c).
1 The metals in hydrocarbons may be inherited Living organic matter Metals used as enzymes
from the hydrocarbon source rock as organometallic Other metabolic functions

complexes. Source rocks contain variable quantities Decay of organic matter, Adsorption of metals
of organophilic metals, including vanadium and conversion to kerogen Release of organic acids
nickel, which may have been inherited in turn from with complexed metals
Sulphate reduction to metal
the living tissues.
sulphides
2 Uptake of metals by hydrocarbon fluids, from the
Hydrocarbon products Reduction and complexing
rocks through which the fluids migrate.
of metals
3 Enrichment at sites of mixing between metal­
Alteration of hydrocarbons Progressive enrichment of
bearing fluids and hydrocarbon-bearing fluids.
metals
4 Enrichment of uranium and/or thorium in bitu­
Mineral exsolution
mens precipitated through the effects of radiation
Graphitization Loss of heteroatoms
(see above). The enhanced precipitation of bitumens Expulsion of metals from
around radioactive sources results in this type of graphite structure
enrichment being widespread.
These mechanisms have varying import for the
possible roles of organic materials as signatures of
regional metal anomalies. The uptake of metals and the processes involved, it will be necessary to
from groundwaters flowing off a metalliferous make a detailed assessment of the metal flux at
deposit, and enrichment of organic materials coeval different stages in the evolution of organic matter
with an ore deposit, could involve all except the (Table 1). Generally, there is a progressive enrich­
inheritance mechanism. Pre-ore organic material ment in metals through the maturation of organic
with a signature of enrichments in the host sediment matter, generation of petroleum and alteration to
could be either syngenetic or epigenetic. Syngenetic complex solid hydrocarbons, and then a loss of
organic material could have inherited the metal in metals as they cannot be accommodated by the
the case of organophilic elements whereas epigenetic ordered structure developed during graphitization.
organic material could be involved in any mechan­ This simple trend belies the many complex processes
ism. The unusual occurrences of organic materials which have yet to be systematically investigated.
which are ores are produced by the radiation mech­
anism in the case of uranium-thorium ore, and
probably by the inheritance mechanism in the case ACKNOWLEDGEMENTS
of vanadium ore.
On a cautionary note, it cannot be assumed that I am grateful to A. Thickpenny and J. Arthurs for
organic matter will contain a signature of any ore critical reading of the manuscript. The Peruvian
deposit in the vicinity. Some metals are much more bitumen was kindly supplied by the British Museum
readily taken up by organic matter than others (e.g. (Natural History) (sample regd. no. 1908, 413), and
tin and tungsten very rarely form enrichments). The J. McCrae and E. Mulqueeny provided valuable
circumstances of fluid migration may be such that technical assistance.
the organic matter does not have the opportunity to
take up the metal. It is also important to appreciate
that in some ore deposits wltich contain significant REFERENCES
quantities of organic materials, those materials may
not exhibit enrichments. For example the bitumen ABRAHAM, H. ( 1945) Asphalts and Allied Substances, 5th
commonly encountered in Mississippi Valley type edn. Van Nostrand, New York.
BARAGWANATH, J.G. (1921) The vanadiferous asphaltites
lead-zinc deposits generally does not contain lead
of central Peru. Eng. Mining. JI. 1 1 1, 778-781.
or zinc enrichments. BELL, K.G. (1960) Uranium and other trace elements in
In order to further understand the degrees to petroleum and rock asphalts. US Geol. Surv. Prof. Paper
which organic materials become enriched in metals, 365B.
192 1. Parnell
BOWIE, S.H.U. & ATKIN, D. (1956) An unusually radio­
active fossil fish from Thurso, Scotland. Nature 177,
487-488.
BOYLE, R.W. (1982) Geochemical Prospecting for Thorium
and Uranium Deposits. Elsevier, Amsterdam.
CANNON, H.L., SHACKLEITE, H.T. & BASTRON, H. (1968)
Metal absorption by Equisetum (Horsetail). US Ceo!.
Surv. Bull. (A) 1278, 1-21.
CURIALE, J.A., BLOCH, S., RAFALSKA-BLOCH, J. &
HARRISON, W.E. (1983) Petroleum-related origin for
uraniferous organic-rich nodules of southwestern
Oklahoma. Bull. Am. Ass. Petrol. Ceo/. 67, 588-608.
DAVIDSON, C.F. & ATKIN, D. (1953) On the occurrence of
uranium in phosphate rock. C. r. 19th Congr. Ceo!. Int.
11, 13-31.
DAVIDSON, C.F. & BowiE, S.H.U. (1951) On thucholite
and related hydrocarbon-uraninite complexes. Bull.
Ceo/. Surv. GB 3, 1-19.
DIGGLE, W.R. & SAXON, J. (1965) An unusually radioactive
fossil fish from Thurso, Scotland. Nature 208, 400-401.
ERICKSON, R.L., MYERS, A.T. & HORR, C.A. (1954) As­
sociation of uranium and other metals with crude oil,
asphalt and petroliferous rock. Bull. Am. Ass. Petrol.
Ceo/. 38, 2200-2218.
GoLD, T. (1984) Contributions to the theory of an abiogenic
origin of methane and other terrestrial hydrocarbons.
Proc. 27th Int. Ceo/. Congr. 13, 413-442.
GoLD, T. (1985) The origin of natural gas and petroleum,
and the prognosis for future supplies. Ann. Rev. Energy
10, 53-77.
KAPO, G. (1978) Vanadium: key to Venezuelan fossil
hydrocarbons. In: Bitumens, Asphalts and Tar Sands
(Ed. by G.V. Chilingarian and T.F. Yen), pp. 155-190.
Elsevier, Amsterdam.
KING, H.D., CURTIN, G.C. & SHACKLEITE, H.T. (1984)
Metal uptake by young conifer trees. US Ceo/. Surv.
Bull. 1617, 1-23.
LANDAIS, P. & CoNNAN, J. (1980) Relation uranium­
matiere organique dans deux bassins Permiens Francais:
Lodeve (Herault) et Cerilly-Bourbon-L'Archambault
(Allier). Bull. Cent. Rech. Explor-Prod. Elf-Aquitaine
4, 709-757.
LANDAIS, P., CONNAN, J., DEREPI'E, J.M., GEORGE, E.,
MEUNIER, J.D., MONTHIOUX, M., PAGEL, M., PIRONON,
J. & PoTY B. (1987) Alterations of organic matter: a clue
for uranium ore genesis. Uranium 3, 307-342.
LEWAN, M.D. & MAYNARD, J.B. (1982) Factors controlling
enrichment of vanadium and nickel in the bitumen of
organic sedimentary rocks. Geochim. cosmochim. Acta
46, 2547-2560.
McKINSTRY, H. (1957) El Vanadio en el Peru (review).
Econ. Ceo/. 52, 324-325.
MAWSON, D. (1944) The nature and occurrence of ura­
niferous mineral deposits in South Australia. Trans.
Roy. Soc. S. Aust. 68, 334-357.
MICHIE, U. MeL. & CooPER, D.C. (1979) Uranium in the
Old Red Sandstone of Orkney. Rep. Inst. Ceo/. Sci. 78/
16.
MuMME, l.A. (1965) An hypothesis on the origin of
thucholite mineralization at the Wallaroo-Moonta
mining field, South Australia. Trans. Roy. Soc. S. Aust.
89, 255-256.
PARNELL, J. (1983) Stromatolite-hosted mineralization in
the Oil Shale Group, Scotland. Trans. Inst. Min. Metall.
(B) 92, 98-99.
PARNELL, J. (1985) Uranium/rare earth-enriched hydro­
carbons in Devonian sandstones, northern Scotland. N.
lb. Miner. Mh. (H) 3, 132-144.
PARNELL, J. (1988a) Lacustrine petroleum source rocks in
the Dinantian Oil Shale Group, Scotland: a review. In:
Lacustrine Petroleum Source Rocks (Ed. by A.J. Fleet,
K. Kelts & M.R. Talbot), pp. 235-246. Spec. Pub!.
Ceo!. Soc. London 40.
PARNELL, J. (1988b) Mineralogy of uraniferous hydro­
carbons in Carboniferous-hosted mineral deposits, Great
Britain. Uranium 4, 197-218.
PARNELL, J. (1988c) Metal enrichments in solid bitumens: a
review. Min. Deposita 23, 191-199.
PARNELL, J. & EAKIN, P. (1987) The replacement of sand­
stones by uraniferous hydrocarbons: significance for
petroleum migration. Min. Mag. 51, 505-515.
PARNELL, J., SHUKLA, B. & MEIGHAN l.G. (1989) The
lignite and associated sediments of the Tertiary Lough
Neagh Basin. Irish J. Earth Sci. 10, 67-88.
PARNELL, J. & SWAINBANK, l.G. (1985) Galena mineral­
ization in the Orcadian Basin, Scotland: geological and
isotopic evidence for sources of lead. Min. Deposita 20,
50-56.
PLANT, J.A., FORREST, M.D., HODGSON J.F., SMITH, R.T.S.
& STEVENSON, A.G. (1986) Regional geochemistry in the
detection and modelling of mineral deposits. In: Applied
Geochemistry in the 1980s (Ed. by I. Thornton & R.J.
Howarth), pp. 103-139. Graham & Trotman, London.
RAMSDEN, A.R., DICKSON, B.L. & MEAKlNS, R.L. (1982)
Origin and significance of the Toolebuc gamma-ray
anomaly in parts of the Eromanga Basin. J. Ceo!. Soc.
Aust. 29, 285-296.
RoBBINS, E.l. (1983) Accumulation of fossil fuels and
metallic minerals in active and ancient rift lakes.
Tectonophysics 94, 633-658.
SHABAD, T. (1984) Growing interest in Soviet resources of
bitumen, heavy oil and tar sands. Sov. Geog. 25,
702-704.
SuNDAY TELEGRAPH (1987) Financial News, 24 May, p. 26.
TuG, S. (1988) Fish debris as chemical scavengers of
zirconium and lanthanum in oceanic environments - Zr
and Hf fractionation in marine phosphates. Chem. Ceo!.
69, 59-71.
WATSON, J.V. & PLANT, J. (1979) Regional geochemistry
of uranium as a guide to deposit formation. Phil. Trans.
Roy. Soc. Land. (A) 291, 321-338.
WILLINGHAM, T.O., NAGY, L.A., KRJNSLEY, D.H. &
MosSMAN, D.J. (1985) Uranium-bearing stratiform
organic matter in paleoplacers of the lower Huronian
Supergroup, Elliot Lake-Blind River region, Canada.
Can. J. Earth Sci. 22, 1930-1944.
Zusov, A.I. & KOTEL'NIKOV, G.N. (1968) Vein asphaltites
in a uranium deposit. Sov. At. Energy 24, 637-641.
Spec. Pubis int. Ass. Sediment. (1990) 11, 193-202

Relationships between organic matter and metalliferous deposits

in Lower Palaeozoic carbonate formations in China

R . Jl A , D . Ll U and J. FU
Institute of Geochemistry, Academia Sinica, PO Box 1131, Wushan, Guangzhou, China

ABSTRACT

Organic matter in carbonate rocks from Cambrian to Devonian age in China is distributed inhomoge­
neously, and asphalts occur in two belts in northern and southern China. Some metal deposits are
associated with the two asphalt belts. Based on the characteristics of soluble organic matter, reflectance
and the structure of the asphalts associated with metal deposits, it is inferred that most of the vanadium,
nickel, molybdenum and uranium deposits were formed in stable pressure and temperature conditions,
while arsenic and mercury deposits were formed in open system conditions near to natural gas pools. A
comparison of the content of metallic elements in asphalts, black shale and carbonate shows that most
metallic elements in asphalts could be derived mainly from black shales, but some lead, tin, silver, zinc
and manganese were possibly contributed from hydrothermal solutions. The metallic elements in
minerals associated with organic matter are mainly chalcophile and variable-valency elements. Accord­
ing to simulated experiments the combination between organic matter and metals occurs during two
particular stages, when Ro is less than 1·2% and greater than 2%.

INTRODUCTION

Carbonate formations are widely distributed through
Precambrian to Devonian sequences in China.
Excepting some gas fields in Sichuan and Shanxi
Provinces, productive fields are not found in these
rocks. However, a lot of solid asphalt representing
the products of migration, accumulation and degra­
dation of oil is exposed at the surface in the carbon­
ates (Liu et al., 1985; Liu & Fu, 1989). There are
two asphalt belts in Lower Palaeozoic strata in
China. One belt is usually associated with oil seep­
ages, and is called the oil-bearing asphalt belt,
located from east to west in northern China, includ­
ing the southern Talimo Basin, the Ordos Tableland,
south of Yanshan Mountain to Tanshan City. The
second belt, called the carbonaceous asphalt belt, is
located around the Jiangnan Swell in southern China
(Fig. 1). In some cases there is much solid asphalt in
metalliferous ore deposits, including mercury, zinc,
lead, copper, gold and uranium deposits.
There has been much recent research on the re-
lationship between organic matter and metalliferous
deposits, including the relationship between oil and
ore deposits in sedimentary rocks (Connan, 1977),
hydrothermal maturation of organic matter in gold
deposits (Ilchik & Brimhall, 1986), relationships
between oil-gas fields and ore deposits (Tu, 1988),
the significance of organic matter in strata-bound ore
deposits (Rashid, 197 1; Lu & Yuan, 1986), charac­
teristics of organic matter in mercury- gold deposits
(Fu & Liu, 1983; Chen et at., 1987), vanadium­
nickel minerals in carbonaceous asphalt (Liu &
Lin, 1984; Zhang et al., 1984) and the relationship
between uranium precipitation and organic matter
(Wang, 1983; Hu et at., 1988).
The occurrence of organic matter distributed in
metalliferous deposits in China has been reported in
many papers (e.g. Fu & Liu, 1983; Liu & Lin, 1984).
This paper reports the results of field work and
experimental simulations in the laboratory.

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun 193

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
194 R. Jia,
GuiyangA &;.�
Fig. 1. Major occurrences of asphalts in China.
CHARACTERISTICS OF ORGANIC
MATTER IN METALLIFEROUS
DEPOSITS
Abundance and maturation of organic matter
The contents of organic matter in Precambrian to
Devonian rocks in some provinces of China are
shown in Table 1. The values of TOC (%), A (ppm),
and HC (ppm) represent the quantity of total organic
carbon, total soluble organic matter and saturated
hydrocarbons, respectively.
The abundance of organic matter in the tin­
polymetallic deposit in Dachan, Guangxi Province is
listed in Table 2. In this deposit it is found that
carbonate is light-coloured and silicified carbonate is
dark-coloured. The results show that the amount of
organic matter in the silicified carbonate is 1- 3
times greater than that in the carbonate strata, which
possibly indicates that the organic matter may have
migrated and become enriched in the silicified rock
due to the action of hydrothermal solutions.
D. Liu and J. Fu
Xi'an
0
Changsha�
0
;.
0
The relationship between the abundance and
maturation of organic matter in different deposits is
shown in Fig. 2. The TOC content and maturation
(reflectance, Ro) of organic matter in each deposit
show a wide range. The contents of organic matter
are highest in nickel, vanadium, uranium and
molybdenum deposits, but lower in mercury and
arsenic deposits. However, research in the field and
analyses in the laboratory indicate that the mercury
and arsenic deposits are associated with both natural
gas and solid asphalt, while the nickel, vanadium,
uranium and molybdenum deposits are only associ­
ated with solid asphalt. In accordance with the
reflectance measurements with Ro over 2%, there
are few oil occurrences (Fu et al., 1983) and most of
the metalliferous deposits are only associated with
asphalt and natural gas.
Soluble organic matter
The composition and alkane characteristics of sol­
uble organic matter in Cambrian- Devonian car-
 Organic matter and metalliferous deposits 195

Table l. Abundance of organic matter in Middle- Upper Proterozoic and Lower Palaeozoic carbonate rocks in China

Strata Northern China Sichuan Yunnan Hunan Zhejiang Jianghan

Ordovician c (%) 0·10 0·06 0·05 0·10

0·03-0·55 [0·13 (76)]*
A (ppm) 50 29 <5
41-650 [210 (32)]
HC (ppm) 24
22-579 [108 (26)]

Cambrian C (%) 0·07 0·17 0·33 0·09

0·02-0·30 [0·10 (53)]
A (ppm) 77 10 <5 61
15-1056 [171 (25)]
HC (ppm) 25
19-756 [ 92 (25)]

Proterozoic C (%) 0·08-0·10 0·04-0·55 0·18 0·14

0·02-0·48 [0·12]
A (ppm) <5 54
20-690 [95] 34·3
HC (ppm)
8-410 [52]

* Average value [ ]; number of samples ( ).

Table 2. Average amount of TOC (%) in different strata of Sn-polymetallic ore deposit*

Unit Devonian 3-2d Devonian 3-2c Devonian 3-2b Devonian 3-2a Devonian 3-1

Petrography Lenticular Lenticular Lenticular Carbonate Silicified Carbonate Silicified Silicified Silica
carbonate silicified carbonate carbonate carbonate carbonate rock
carbonate
TOC (%) 0·11 1·5 0·028 0·078 0·15 0·076 0·43 1·31 0-43
Number (10) (7) (95) (4) (11) (7) (5) (7) (8)

* Data from Lu (1986).

R"

(%)1
12

10
u

Sn IMn.Ni .vi
IL________c
_ " __ -�
l r_p,���

Fig. 2. Cross-plot of Ro (%) and

TOC (%) for organic matter in
Chinese ore deposits. 10 15 20 Corg (% J

bonate rocks in southern China are listed in Table 3,
which shows that the saturated fraction is more
abundant than the aromatic fraction. The amount of
non-hydrocarbons increases with maturation. The
organic matter in Lower Palaeozoic deposits is
probably the product of oil evolution.
The pristane : phytane (Pr: Ph) and the
C21- : C22+ alkane ratios are indicators of maturity
and environment; the lower the ratios, the more
reducing the environment arid the more mature the
organic matter (Liu & Jia, 1990). The data for
saturated hydrocarbons in some deposits (Table 4)
196 R. Jia, D. Liu and J. Fu

Table 3. Composition (%) of soluble organic matter in carbonate formation of Cambrian-Devonian systems, China

Area Petrology Layer Saturated CH Aromatic CH Non-CH + Asphalt

E. Guizhou Carbonate D2-3 27·41 4·15 68·84

E. Guizhou Limestone S2 30·16 15·42 54-45
E. Guizhou Limestone 01 75·35 4·87 19·79
E. Guizhou Limestone El 39·30 7·08 53-62
Northern
China Carbonate 01 48·34 12·76 44·66
Northern
China Carbonate E 31-36 12·02 56·12

E, Cambrian.

Table 4. Character of saturated hydrocarbons in some deposits, southern China

Ore & Area Layer Range of n-alkane Main peak CPI nC21-:nC22+ Pr:Ph

Hg, Guizhou (SE) E nC14-nC30 C16 1·053 6·957 1·15

Hg, Guizhou (NE) E nC14-nC30 C17 1·263 2·931 1·30
Pb-Zn, Hunan E nC14-nC31 C17 1·136 3·582 0·59
Pb-Zn, Hunan E nC14-nC36 C17 1·084 2-414 0·89
V-Ni, Anhui Sl nC15-nC31 C23 1·131 0·441 0·33

E, Cambrian.

show that the most highly reducing and most
mature sequence was the source of organic matter in
the vanadium-nickel- uranium deposits, and the
least mature was the source of organic matter in the
mercury deposits.
Insoluble organic matter
During the evolution of the parent organic matter,
some hydrocarbons migrated as liquids, a part of
which was degraded to leave a residue called solid
asphalt.
The 0 C and H: C ratios of the asphalts associ­
:
ated with metallic deposits allow them to be plotted
on a Van Krevelen diagram (Fig. 3). The hydrogen
content of the asphalt samples is very low, and the
oxygen content is highly variable, especially in the
samples from the tin-polymetallic deposit. These
asphalts are rich in carbon and have no effective
potential for oil or gas. They are derived from

H/C /
/

1.5
(/
\
\
I
I
1.0 I Fig. 3. Aromatic H : C and 0 : C
I ratios of asphalts plotted on the
I -- -- Van Krevelen diagram. (From
I ...---- -- --- - Hu et a!., 1988 and Tu, 1988. )

/•3
I / (1) Uranium deposit in

0.5 5il /
Proterozoic-Cambrian,
Guangxi; (2) tin-polymetallic
I
1•1 .3. fs-----:1·---/�;--5�;-- (___ _
deposit, in Devonian, Guangxi;
(3) lead-zinc deposit in

------ ----- --------- Cambrian-Carboniferous,

Jiangsu; ( 4) lead-tin deposit in

0.1 0.2 0.3 0.4

Cambrian, Shanxi; (5) lead-tin
0/C deposit in Devonian, Hunan.
 Organic matter and metalliferous deposits 197

liptinite-rich hydrogen precursors (in the marine
pre-Devonian). These asphalts were highly altered
by hydrothermal solutions (Lu, 1986; Yang, 1988).
X-ray diffraction (XRD) of different coal rank
vitrinites shows that the Z8 angle of OOZ diffraction is
changed from 17° to Z6°. The Z8 angle at 17-zoo
represents aliphatic straight-chain and aliphatic ring
structures, and the Z8 angle at Z4-Z6° represents
aromatic structure. Besides the OOZ diffraction, there
is a peak at 43° representing 100 diffraction in highly
mature vitrinite.
X-ray diffraction also offers information about
asphalt structure, especially the degree of aromati­
city. We regard the d002 parameter as an important
measurement of asphalt maturity and oil-gas po­
tential (Fu et a/., 1983). The d002 and d1oo para­
meters represent the vertical separation of aromatic
nuclei along the OOZ and 100 directions. The Lc and
La parameters represent the size of aromatic nuclei
along the OOZ and 100 directions. X-ray diffraction
analysis of different asphalts shows that the relation­
ships between asphalt/oil-gas and metallic deposits
are: ( 1) in general, oil is associated with asphalt with
an OOZ diffraction at about 17- zoo, and 100 diffrac­
tion is not found; (Z) the OOZ diffraction is at 17-Z6°
(two peaks are combined) and 100 diffraction is
visible in some asphalts associated with mercury
deposits; (3) the OOZ diffraction at Z6° and 100
diffraction at 43° are very clear in asphalt associated
with lead, zinc and tin deposits.
The cross-plots of d002 with Lc and d 100 with La
are shown in Fig. 4, reflecting the degree of crystal­
linity of asphalts sampled from different deposits
(Qin et al., 1987). The degree of crystallinity depends
on: (1) the carbonization of asphalts- the higher the
carbon content, the higher the asphalt crystallization;

dooz
3.40

3.42

3.44

3.46

Fig. 4. Cross-plots of d002 and

Lc, and dlOO and La, for some
Chinese asphalts. Samples 0 10,
016 and Gu2 from tin­
0.08
polymetallic deposit, Guangxi;
H2114, Wa-5 and Dz-5 from
mercury deposit, Guizhou; H22o
from lead-tin deposit, Hunan;
and H221 from asphalt vein;
Guizhou.
198 R. Jia, D. Liu and J. Fu

and (2) the temperature and pressure, which at higher
levels produce more crystalline asphalt. A compari­
son of asphalts from different deposits suggests that
mercury deposits formed in relatively low-pressure
systems containing natural gas (rich in hydrogen),
but the lead, zinc and tin deposits formed in the
relatively closed systems far from gas pools, because
the degree of asphalt crystallization is greater in the
latter deposits.
METALLIC ELEMENTS AND
MINERALS IN ASPHALT
Abundance of metallic elements in asphalt
The abundance of metallic elements in asphalt
is compared with the average abundance in carbon­
ates (Geological Department of Nanjing University,
1987) and black shales (Fan et a!., 1973) in Fig. 5. It
was found that: ( 1) the following elements are not
present in the asphalts-Ta, Hf, Sc, Ge, In, Ga, W,
Nb, Zr, Co, Be, Li, U, Th, La, Ce, Y, Yb, Au, K
and Na; (2) the abundance of Ag, Pb, Zn, V and Ni
in asphalts is 100 to 10 000 times greater than the
average abundance in carbonates; and (3) the con­
tents of metallic elements are generally lower than
the average contents in black shales, except Sb, Sn,
Ag, Pb, Zn and Mn. Possibly some Sb, Sn, Ag, etc.
was contributed from hydrothermal solutions.
Minerals in asphalts
Some minerals found in asphalts in southern China
are listed in Table 5. The metallic elements in the
minerals are mainly chalcophile elements and most
of them are variable-valency elements. There are
temporal and regional variations in the enrichment
of metallic elements in asphalts. For example va­
nadium and nickel minerals occur mainly in asphalts
in Cambrian, Silurian and Devonian rocks around
the Jiangnan Swell, but lead and zinc minerals occur
particularly in asphalts along the juncture of Yunnan,
Guizhou and Guangxi Provinces and south of Qinglin
Mountain.
SIGNIFICANCE OF ORGANIC
MATTER IN METAL ORES
Direct combination of organic matter with metals
Living organisms contain many enzymes which con­
tain metallic ions, i. ncluding Na, K, Fe, Cu, Zn, Mn,

1:�
0 0
2 0
0
0
(a) M1 ppm (Asphalt) 0
0 0
M2ppm Black shale) 0 0
0
0 0
-2
0

-4

•
4 •

• •
•
2
•
•
(b) MJPPm CAsphaltJ •
0 •
MaPPm (Carbonate) •
•
-2
•

-4

Sr Ba Pb Zn Sb v Mo Sn Ti Mn Ni Cu Ag

Fig. 5. Metal abundances in asphalts. (a) Compared with average for black shale (Fan
eta/., 1973). (b) Compared with
average for carbonate rock (Geological Department, Nanjing University). Ml, M2, M3 represent amount of metallic
elements in asphalt, black shale and carbonate, respectively.
 Organic matter and metalliferous deposits 199

Table 5. Some minerals recorded in asphalt

Name Formula Location Stratigraphy Reported

Pyrite FeS Hunan E and S Fan T.

Marcasite FeS Yang X.
Jordisite MoSz Chen N.
Bravoite (Ni, Co, Fe)S2 (1973-1985)
Millerite NiS
Polydymite Ni3S4
Gersdorffite NiAsS
Sulvanite Cu3VS4
Sphalerite ZnS
Galena PbS
Violarite (Fe, Ni)3S4
Tetrahedrite 5CuS·2(Cu, Fe)S·2As2S3

Uraninite UOz Guangxi . Z-E Chen R. (1983)

Simulated in lab. Hu K. (1987)

Montroseite Guangxi D Liu D.

Karelianite Lin M. (1983)

Mo, Ca, Mg and Se ions, which are important in
metabolic processes (Chen & Li, 1983).
The content of some metallic elements in living.
organisms is generally higher (up to 10 000 times)
than that of the surrounding medium. For example,
the contents of metallic elements in plants growing
in the sea compared with those of the seawater are:
>10 times Ag, B, Mo, Rb
>100 times W, K, Li, Ca
>1000 times Al, Au, Ba, Cd, Co, Cs, Cu, Hg
>10 000 times As, Cr, Fe, Mn, P, Pb, Ti, Zn
(data from Yang, 1989).
In addition, organic acids produced by the de­
composition of living organisms allow the formation
of organometallic complexing, such that the abun­
dances of lead, zinc, copper and nickel in humic
2 of metallic elements and consequent precipitation to
acids are 104, 103, 103 and 10 times more than the
average abundance in shales respectively (Rashid,
1971; Lu & Yuan, 1986).
[UOzS04JZ- +CH4 ____,. U02 +H2S +COl- +H20
Na4[UOz(C03h] + H2S ____,. U02 + S + 2Na2C03
+ C02 + H20
2HgS + CH4 ____,. 2Hg + C + 2H2S
As a result, some metal ore is associated with organic
matter.
Simulated experiments of uranium precipitation
by organic matter support the possibility of the
above reactions (Hu et al., 1988). The experimental
results show that there are two stages of uranium
uptake in the evolution of organic matter, at
Ro <1·2% and >2% (Fig. 6). The mechanisms of
the two stages of uranium enrichment are different.
In the first stage (Ro <1·2%), the enrichment is
mainly by absorption and complexing. When Ro
>2%, the enrichment is mainly through reduction
ore. Some of the vanadium and nickel ore in the
asphalt vein surrounding the Jiangnan Swell may be
formed by the latter process.

Reduction of metal ions by organic matter

The content of organic carbon in the uranium ore­ SUMMARY

bearing rocks in Zazipin, Guangxi Province, ranges
from 4·27 to 19·14%, but the partition of uranium in
the organic matter is only 0·1-1% (Hu et al., 1988).
Native mercury has been found in mercury ore
deposits which are rich in organic matter (Chen et
al., 1987). The role of organic matter may have been
to reduce metal ions to minerals. Examples may
include
1 Organic matter in carbonate rocks from Cambrian
to Devonian age is distributed inhomogeneously.
Although the average TOC is less than 0·1% in most
regions, oil-bearing asphalts and carbonaceous as­
phalts outcrop in two belts in northern and southern
China, respectively.
2 Some metal deposits are associated with the two
200 R. Jia, D. Liu and J. Fu

Table 6. Partition of uranium in host rock and organic matter

Sample Lithology U content U content Org. matter Partition of

in host rock in kerogen content U in org. matter
(ppm) (ppm) (%) (%)

8818-41 Slate 7·2 6·5 3·92 3·5

18 Slate 10·4 5·5 4·80 2·5
5-52 Slate 36-4 7·0 10·72 2·1
D20 Ore 1560·0 83·0 19·14 1·0
D2 Ore 26300·0 39·0 4·27 0·01

When Ro >2%, metal precipitation is dominated by

., 50
:i the reduction of metallic ions to ore minerals by
� organic matter.
c
"
0
40
§
"0
Q) ACKNOWLEDGEMENTS
..0
.... 30
0
"'
..0 This study was funded by National Scientific In­
-<
vestment Bureau grant No. 86040129. We thank
20
0.5 1.0 1.5 2.0 2.5 3.0 3.5RO% X. Chen and Q. Chen for reading the paper and
offering good suggestions. X. Yan kindly supplied
Fig. 6. Relationship between amount of absorbed uranium
data for minerals in black shale.
(�tg) and Ro (%) of organic matter, from experimental
precipitation of uranium by organic matter.

REFERENCES

asphalt belts. Most V, Ni, Mo and U deposits are
associated with solid asphalt, while most As and Hg
deposits are related to both solid asphalt and natural
gas. Based on the asphalt structure, the former
deposits are concluded to have formed in stable
conditions of pressure and temperature, while the
latter deposits formed in open system conditions
near to natural gas pools.
3 Ta, Hf, Sc, Ge, In, Ga, W, Nb, Zr, Co, Be, Li, U,
Th, La, Ce, Y, Yb, Au, K and Na have not been
found in asphalts. The abundance of Ag, Pb, Zn, V
CHEN, H. & LI, W. (1983) Molecular Enzymology,
pp.130-177. People's Sanitation Publishing House.
CHEN, Q., JI A, R. & Liu, D. (1987) Some characteristic
features of organic matter and metals in Danzhai
mercury-gold deposit. In: Annual Research Reports of
the Organic Geochemistry Laboratory, 1986, Institute of
Geochemistry, Academia Sinica, pp. 145-158. Guizhou
People's Publishing House.
CoNNAN, J. (1977) Relationship between oil and ore in the
Saint-Privat barite deposit, Lodeve Basin. In: Forum on
Oil and Ore in Sediments, pp. 167-187. Imperial College
London.
FAN, T., YANG, X. & C!iEN , N. (1973) Petrological and

and Ni in asphalts is 100-10 000 times greater than
the average abundance in carbonates; the content
of metallic elements in the asphalts is generally less
than the average in black shales, except Sb, Sn,
Ag, Zn and Mn. Possibly some Sb, Sn, Ag, etc. was
contributed from hydrothermal solutions.
4 The metallic elements in minerals associated with
organic matter are mainly chalcophile elements.
5 The combination between organic matter and
geochemical characteristics of a nickel-molybdenum
multi element-bearing Lower-Cambrian black shale
from a certain district in south China. Geochemica 3,
143-160.
Fu, J., JIA, R. & LIU, D. (1983) Organic geochemical
criterion of evaluation for oil-gas prospect in carbonate
strata. In: Symposium on Petroleum Science, Chinese
Academy of Sciences, pp. 131-138. Science Publishing
House, Beijing.
Fu, J. & LIU, D. (1983) Evolution of organic matter and
origin of sedimentary deposits (II) hydrocarbons orig­

metals occurs in two stages. At the stage when Ro inating from coal and strata-bound deposits. Acta
Sedimentol. Sinica, 1, 13-28.
<1·2%, processes are dominated by complexing and
GEOLOGICAL DEPARTMENT OF NANliNG UNIVERSITY (1987)
absorption of metallic elements by enzymes in living Geochemistry, pp. 80-92. Science Publishing House,
organisms and by organic acids from dead organisms. Beijing.
 Organic matter and metalliferous deposits
ILCHIK, R.P. & BR I M HALL , G.H. (1986) Hydrothermal
maturation of indigenous organic matter at the Alligator
Ridge gold deposit, Nevada. Econ. Ceo!. 81, 298-306.
Hu, K., ZHANG, Z., ZHING, B. & JIA , R. (1988) The role
of organic matter in the formation of the Chanziping
uranium deposit. In: Annual Research Reports of the
Organic Geochemistry Laboratory, Chinese Academy
of Sciences, pp. 161-177. Science Publishing House,
Beijing.
L1u, B. & ]lA, R. (1990) Characteristics of normal and iso­
alkanes in Middle-Upper Proterozoic source rocks and
thermal alteration experiments of kerogen. Geochemica
3 (in press).
L1u, B., LIANG, D., FANG, J., JIA, R. & Fu, J. (1985)
Organic matter maturity and oil-gas prospect in
Middle- Upper Proterozoic and Lower Paleozoic
carbonate rocks in northern China. Geochemica 2,
150-162.
L1u, D. & Fu, J.(1989) Asphalts and stratabound deposits
in carbonate rocks. In: Organic Geochemistry of Car­
bonates Applied to Evaluating Origin of Oil-Gas Fields
and Stratabound Deposits (Ed. by J. Fu), pp. 172-193.
Science Publishing House, Beijing.
L1u, D. & LIN, M. (1984) Discovery of some vanadium and
nickel minerals from anthraxolite and discussion of their
origin. Scientia Sinica (B), XXVll (11), 1197-1202.
Lu, G. (1986) Research on sedimentology and sedimentary
geochemistry of late Devonian system in Danchang basin,
201
Guangxi Province. Thesis, the Institute of Geochemistry,
Academia Sinica, Guiyan.
Lu, J. & YU AN , Z. (1986) Experimental studies of
organic-Zn complexes and their stability. Geochemica
1, 66-77.
Q1N, G., ZHAN, X. & LAO , Y. (1987) Research on X-ray
diffraction of kerogen. Acta Sedimentol. Sinica 5, 1,
26-36.
RASHID, N.A. (1971) Role of humic acids of marine origin
and their different molecular weight fractions in com­
plexing di- and tri-valent metals. Soil Sci. , 3, 298-306.
Tu, G. (1988) The relationship between Hg, As, ore
deposits and natural gas fields. In: Stratabound Deposits
in China, Vol. 3 (Ed. by G. Tu), pp. 27-36. Science
Publishing House, Beijing.
WANG, J. (1983) Natural organic substance and oil-gas
prospect: its implication in uranium mineralization.
Geochemica 3, 294-302.
YANG, W. (1989) The action of organic matter on forming
ore deposits in stratabound deposits. In: Stratabound
Deposits in China, Vol. 3 (Ed. by G. Tu), pp. 255-310.
Science Publishing House, Beijing.
ZHANG, A., PAN, Z. & E NG , C. (1984) The geochemistry
of vanadium in Yang Jiabao stone coal of Upper Cam­
brian. In: Selected papers of Sedimentological and
Organic Geochemical Meeting, Beijing, pp. 263-274.
Science Publishing House, Beijing.
Spec. Pubis int. Ass. Sediment. (1990) 1 1, 203-216

Comparative geochemistry of metals and rare earth elements

from the Cambrian alum shale and kolm of Sweden

J . L E V E N T H AL
US Geolog ical Survey, Federal Center MS 973, Denver CO 80225, USA

ABSTRACT

The Cambrian Alum Shale Formation of Sw eden is a metal-rich black shale. The metal distribution ,
however, varies with stratigraphy as well as organic carbon content and shows increases for certain
metals in areas of tectonism. In the non-metamorp hosed areas, the elements uranium, molybdenum,
vanadium and lead are enriched by factors of 2-4 relative to other black shales. The organic-rich (50%
organic carbon) kolm of the Upper Cambrian shale is more enriched in uranium (0·5 % ), radiogenic-lead
(200 ppm), yttrium (800 ppm) and heavy rare earth elements (HREE, e.g. ytterbium 45 ppm), but
depleted in other elements (molybdenum, vanadium, nickel) . Normalizing to aluminium accounts for
the major and rock-forming elements in the kolm that are the same as the surrounding shale, but not for
uranium, lead, yttrium and HREE in kolm.
In many shales, increased metal or trace element contents can be accounted for by parallel increases
in organic matter, pyrite or p hosphate as hosts or sites. However, increases in content of trace elements
are often not correlated with the content of hosts (sites) for the metal and trace element contents in
non-metamorphosed alum shale or kolm. Therefore a combination of unusual source rocks (rich in
uranium and other elements) coupled with selective element transport and efficient concentration by
organic matter in an unusual depositional environment is suggested as a method of element enrichment.
In the metamorphosed areas, the carbon content of the Cambrian shales is similar to the non­
metamorp hosed areas but vanadium (0·2% ), nickel (500 ppm), zinc (500 ppm), cadmium (10 ppm) and
barium (1500 ppm) are greatly increased. Epigenetic addition of metals from external source(s), rather
than internal redistribution, is suggested to account for increased amo unts of metals (vanadium, nickel,
zinc, cadmium and barium) in the metamorphosed/tectonically affected areas.

INTRODUCTION

The Alum Shale Formation of Scandinavia is an
organic-rich marine sequence of middle Cambrian
to early Ordovician age (Andersson et al., 1985, and
references therein). The Alum Shale Formation in
Sweden (Figs 1 and 2) is generally between 15 and
35 m thick (in central Sweden). Locally it can be
separated into Upper, Middle and Lower Members
based on interlayered carbonate concretions
(stinkstones) or other lithological characteristics and
well-preserved marine fauna. The shales are rep­
resented by black laminated, dark-brown organically
banded and grey mudstones and referred to as alum
shales because of their potassium, aluminium and
sulphate content. The sedimentation rate is esti­
mated to have been between 1 and 5 mm/1000 years
(Thickpenny, 1984, and references therein). The
geochemistry of the Swedish alum shale is presented
in the summary papers by Armands (1972), Edling
(1974), Hessland & Armands (1978), and Andersson
et at. (1983, 1985).
The work reported here began in 1979 with a
suite of core samples from Ranstad, courtesy of
D. Gee (Swedish Geological Survey) and A.
Andersson (Swedish Alum Shale Co) and a few
hand specimens from J. Erdman (US Geological
Survey); these were supplemented by additional
core samples from Narke and Jamtland supplied by
D. Gee. The initial interest was in extending the
earlier inorganic geochemical work and new empha­
sis on the study of the organic matter association and

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun 203

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
204 1.
SOUTHEASTERN BALTOSCANDIA
I '
SWEDEN
f.::.·.J
• Cambrian, on-shore
l':c\\\/'1
t
N
CJ
I 0
control on uranium and other anomalous elements
(Leventhal, 1981, 1983, 1986). Since then a number
of other workers have reported results on various
aspects of geology and geochemistry (Andersson
eta/ . 1983, 1985; Thickpenny, 1987), sedimentology
(Thickpenny, 1984; Dworatzek, 1987), carbon iso­
topes (Buchardt et a/., 1986), and organic geo­
chemistry and radiation effects (Leventhal et al.,
1986; Dahl et a/. , 1988a, b; Lewan & Buchardt,
1989). However none of these recent reports deals
with the kolm which is the most enriched in uranium
and organic matter.
The uranium- and organic carbon-rich kolm
nodules were studied in detail by Davidson (1961)
and Cobb & Kulp (1961) and have been mentioned
in many reports, but have only been further studied
by Parnell (1984), who identified uranium- and
Leventhal
' 0
z
I-<(
_J
' z
'G:
LEGEND
Post-Cambrian
Fig. 1. Map showing Cambrian
Alum Shale Formation in south­
Cambrian, off-shore
eastern Baltoscandia. (From
Andersson et al., 1985.) Note
Precambrian
localities of interest (names out­
lined): Himtland in the north;
Narke in the centre; Sydbillingen/
100 200 300 km
Ranstad samples are from
Vastergotland (B-F ) .
cerium-rich minerals in the kolm. The kolm is part
of the Pel tura scarabaeoides zone of the Upper
Cambrian Olenid Series and is thickest in the Mt
Billingen area (Armands 1972; Dahlman & Gee,
1977). Andersson etal. (1985) describe the kolm in
more detail: it is restricted to the P. scarabaeoides
zone and occurs as lenses and ( <10 em thick) bands
in two levels (i.e. Billingen) or three levels (i.e.
Vastra Falbygden). A brief report of the organic
geochemistry of the kolm and its comparison to
other uranium-enriched organic matter were pre­
sented in Leventhal et al. (1986). The summary
papers by Armands (1972), Hessland & Armands
(1978), Andersson et al. (1983) and Andersson
etal . (1985) on the geochemistry of the alum shale
mention the kolm but give no new data. This may be
due to its thin and discontinuous nature such that it
 Black s hale geoc hem istry 205

ALUM SHALE (RANSTAD)

U-1
...J
-<
:r:
(/)
Q..
0
f-

Peltura
scarabaeoides

c 6
::::
..c
·�
E: 7
::::
c
"'
::;
-- 8 Ezz:Z%Z:Z:z:.::z:;2?Zj}
Bottom shale

9
Great stinkstone

11

Fig. 2. Schematic section of the

Alum Shale Formation at Ranstad.
12�------,_--�
(From Andersson et al., 1985.) Note Middle Cambrian
two kolin layers in the uranium-rich
zone between 5.5 and 7.5 m below c::Jshale � Stinkstone- Kolm
the Ordovician.

is not considered to be of major economic import­
ance despite early attempts to mine it for radium.
However, it appears that although the kolm is
extremely unusual in its geochemistry it may actually
help to understand the geochemistry of the alum
shale formation as a whole. In most reports, the
kolm has been treated as a more organic-rich part of
the alum shale formation, although it also has been
suggested that it may be a migrated bitumen, based
on microscopic examination of polished blocks
(J. Dahl, pers. comm.). However, the mineral con­
tent of the kolm is around 40%, much higher than in
a bitumen, and the major element abundances are
proportional to the surrounding shale. In addition,
although the kolm is present in the Mt Billingen
(Ranstad) area where there has been intrusion of a
diabase sill nearby, kolm also occurs at Narke, where
there is no evidence of igneous activity and the
organic matter in the shales is less mature.
In this paper, a summary of results of the geo­
chemical characterization of kolm are presented
(Leventhal, 1988). The origin and geochemistry of
the kolm have not been reported or discussed in
many studies. This may be because it is 1zotmerely an
206 J. Leventhal
extension of the alum shale in many of its geo­
chemical properties: the uranium content is much
higher than expected based on extrapolation of
uranium and organic carbon contents of the sur­
rounding shale. Neither is the uranium correlated
with phosphate or other potential hosts or sulphur
content. In most shales the sulphur content is related
to the organic content; this is not true for the kolm.
In fact, the sulphur content of the kolm is actually
lower than the sulphur content of shale because the
iron content of the kolm is lower and in both shale
and kolm the iron appears to be completely sul­
phidized (i.e. iron is all as FeS2; Leventhal, 1983).
Thus, many of the correlations of metals with organic
carbon or sulphur that are found for many black
shales (for example, Leventhal & Hosterman, 1982;
Leventhal et al. , 1981) and the alum shale have not
been found for the kolm. Thus the kolm has been, at
least, a component that did not fit in with the shale
geochemistry and, at most, something of an enigma.
Also in this paper, the geochemistry of the
uranium-rich upper unit from Ranstad and Narke in
southern Sweden is contrasted with the vanadium­
rich Cambrian alum shale from Jamtland, in the
Caledonian front, where the organic matter is
thermally mature (Gee, 1980). Both of these shales
are contrasted with the kolm.
REGIONAL GEOLOGY AND SAMPLES
Sydbillingen area
In this area the shale is 22-24 m thick and is at or
only a few tens of metres below the present land
surface. The beds are flat-lying and undisturbed
(Andersson et al. , 1983, 1985). Shale samples in this
study were from Sydbillingen core 16/74 near
Ranstad from four depths, two in the uranium-rich
unit (of the P. scarabaeoides zone) and two below
this in the Middle Member (A. pisiformiszone). The
kolm samples were hand specimens collected in the
Ranstad open pit mine. In this area there is a
diabase sill that lies approximately 100 m above the
Cambrian strata which has caused some local heating
(Cobb & Kulp, 1961; Dahl et al. , 1988a, b). This is
supported by Rock-eva! results (see Leventhal etal. ,
1986, for explanation and references) that show that
T ax is 427 -440°C and HI (hydrogen index) values
m
are between 100 and 200 mg/g org. carbon (Leventhal
& Daws, new data).
Narke area
This area is somewhat different from Ranstad
because the Middle Member is absent; the alum
shale is approximately 12-19 m thick and is buried
about 30 m below the present surface (Andersson
et al . , 1983, 1985). Shale samples were from six in­
tervals of core from the Kvarntorp 11/53 borehole
and the kolm was a hand specimen. At Narke the
organic matter is thermally immature (Rock-eva!
T x 422°C, HI is between 400 and 500 mg/g org. C)
ma
(Leventhal & Daws, new data).
Jamtland area
In this region of the Caledonian front the alum shale
is deformed and has been subjected to low grade
metamorphism (Andersson eta/. , 1985; Snail, 1988).
Regional overthrusting has resulted in tectonic rep­
etition of the alum shale beds (total thicknesses up
to around 150 m) Andersson et al. , 1985, fig. 19).
Samples were from the southern Storsjon-Myrviken
drilling project and were from cores Myrviken 78001
and 78004. No kolm has been recognized from this
tectonically disturbed area. Rock-eva! results con­
firm the overmaturity of the organic matter ( Tmax is
greater than 460°C and the HI is only 5-20 mg/g
org. C) (Leventhal & Daws, new data). The maturity
of the organic matter for the entire alum shale
implies that there has also been a Caledonian ther­
mal effect due to loading of thrust sheets and prob­
ably also from heated fluids that may have been
heated and expe!Jed during the thrusting.
ANALYTICAL METHODS
Most major, minor and trace elements were
measured after mixed acid digestion of samples by
inductively coupled plasma-atomic emission spec­
troscopy (Lichte et al. , 1987). However Si02 was
measured by X-ray fluorescence (Taggart et al. ,
1987), and uranium was measured by delayed
neutron activation analysis (McKown & Millard,
1987).
Rare earth elements were measured by three
methods: ICP analysis, instrumental neutron acti­
vation analysis (Baedecker & McKown, 1987) and
radiochemical neutron activation analysis
(Wandless, 1987). Organic geochemical methods
are described in Leventhal et al. (1986).
Table 1. Detailed analytical results for kolm samples

Sample Org C s Fe AI u Mo v Ni Zn Cd Pb Cu As Mn Ba
(% ) (% ) (% ) (% ) (ppm) ( ppm) (ppm) (ppm) (ppm) (ppm) (ppm) ( ppm) ( ppm) ( ppm) ( ppm )

Ranstad H 49·9 1 1·7 9 2·1 5940 89 290 98 50 <2 250 54 50 200 360
Ranstad I 53-4 3·2 2·4 H 4960 130 410 92 375 5 220 69 180 280 515
Narke 52·9 7·7 5·8 1·5 4 1 00 51 100 48 7 <2 240 48 160 150 120

Si02 K Ca Mg Ti Na p Co Li Sc Sr Nb Cr
(% ) (% ) (% ) (% ) (% ) (% ) (% ) (ppm) ( ppm ) (ppm) (ppm) ( ppm) ( ppm)
O:l
s-
Ranstad H 12·2 1·3 0·36 0·21 0·1 5 0·08 0·04 9 40 30 42 5 24 '"'
Ranstad I 20·1 2·1 0·22 0·3 0·21 0·12 0·06 11 50 29 56 <4 31 ?;-
"'
Narke - 0·62 0·23 0·25 0·09 0·05 0·05 8 37 24 22 5 19 ;:;-
I;)
�
OQ
"'
C)
'"'
Table 2. Representative results for alum shale and kolm ;:;-
"'
;:s
Sample Org C s Fe A1 u Mo v Ni Zn Cd Pb Cu As Mn Ba p SiOz �;;·
(% ) (% ) (% ) (% ) ( ppm) ( ppm) (ppm) (ppm) ( ppm) ( ppm) (ppm) ( ppm) ( ppm) ( ppm) (ppm) ( ppm ) (% ) �
Kolm 50 7·7 5·8 2 4500 90 290 95 200 3 230 60 150 240 400 500 15
Sydbillingen 12 8 7 6-4 410 260 695 245 90 <2 48 150 1 30 390 490 800 46
Narke 16 6 6 5·3 220 200 460 160 90 <2 35 130 70 200 350 700
Jii mtland 13 4·3 3·9 6·6 240 340 2000 510 410 11 40 1 30 1 00 430 1 200 1100 52
SD0-1 10·2 5·5 6·6 6·6 53 160 160 1 10 60 <2 36 62 70 340 410 600 50
Avg Shale 1·6 0·24 4·7 8 4 3 130 68 95 <2 20 45 13 850 580 700 59

N
s
208 J. Lev enth al

Table 3. Rare earth elements in kolm, shale and standards

( ppm) La Ce Nd Sm Eu Gd Tb Dy Yb Lu y Method

Kolm H Ranstad 14 35 41 25 6·3 44 8-4 67 45 6·5 RNAA

O pen p it mine 16 40 40 47 860 ICP
Kolm l Ranstad 24 61 45 6 37 690 !CP
Open pit mine
Kolm Narke 7 22 42 7 67 1 200 !CP
Shale core 16/74 45 85 37 <2 4 53 reP
Sydbillingen 6·0 m 41 74 33 8·1 1 ·5 6·2 7·3 3-4 0-45 RNAA
Myrviken 78004 42 82 41 <2 4 43 ICP
Shale 7799083 37 57 32 7· 1 1·1 5·7 5·9 3·2 0·52 INAA
Ja mtland
North Am. shale 32 73 33 5·7 1·2 5·2 0·9 5·8 3· 1 0-48 27 H68
SD0-1 36 64 35 7·5 1 ·2 6·9 1-1 6·9 3·4 0·53 40 ICP

Methods: RNAA, radiochemical neutron activation analysis; ICP, ind uction cou pled p lasma; INAA, instrumental
neutron activation analysis; H68, Haskin et al. 1968.

NEW DATA 1000

100
Table 1 gives the detailed chemical analyses for
three kolm samples. Table 2 gives representative so
values for selected elements for the kolm samples
for the uranium-rich portion of the alum shale from
southern Sweden (Sydbillingen and Narke, 10 sam­ 20
ples), for alum shale from the Jamtland Caledonides
(Storsjon, 9 samples), for USGS SD0-1 black shale
standard (data from Leventhal et al. 1978 and un­ 10
Ill

published), and for 'average shale' (Turekian & ....

Ill
""
Wedepohl, 1961). Rare earth element (REE) data .... 5
:z:
for the kolm samples and for specific samples of A.
en
shale from Ranstad (Narke is similar), for Jamtland, ::E
"" "
and for North American shale composite (NAS:
en >
Haskin eta!., 1968) are given in Table 3. Alum shale
""
representative values ·are derived from unpublished 1.0
USGS data and are quite similar to the results listed
in Andersson et al. (1985). The complete set of 0.5
geochemical data will be presented elsewhere
(Leventhal et al., in preparation).

D ISCUSSION OF RESULTS s AI Mo Pb v Cu P
0.1��--�--�_,,_L-,--L-r�-,,-�
org C Fe U As Zn Ni Ba Mn
Figure 3 shows selected element contents as ratios to
average shale. At the left side are the major con­ Fig. 3. Ratios of selected major and trace constituents of
kohn, shale from Sydbillingen/Ranstad (Ran) and shale
stituents of shales (except silicon) and organic carbon
from Jamtland (Jamt); data from Table 2. The ratios of
and sulphur. It is clear from this diagram that the each value to average shale of Turekian & Wede pohl
kolm is enriched in organic carbon and depleted ( 1961) are taken. Sec text for discussion.
 Black shale geoch emistry 209

in aluminium relative to the other sample groups.
Examination of the detailed data (Leventhal, un­
publ. data) shows that aluminium and also other
major elements (silicon, potassium, magnesium,
titanium, sodium, calcium) are diluted by the organic
carbon. The trace elements are shown on the right
side of Fig. 3; the elements are ordered in decreasing
enrichment for the kolm (relative to average shale).
Relative to average shale, the samples of kolm and
alum shale are enriched in most of these metals (Fig.
4) except manganese, phosphorus and barium. In
particular, the alum shale and kolm samples are all
greatly enriched in uranium and molybdenum and to
lesser degrees in the other plotted elements relative
to average shale. However, there are differences in
the degrees of enrichment in the shale and kolm that
need to be considered.
The kolm is most enriched in uranium and lead.
A simple calculation shows that approximately
1000
100
50
• Kolm
. Ran
• Jamt
20
10
Ill
5 gives the abundances for selected elements in basaltic
..1
IILUI
:Eel
ccz
Ill
1.0
300 ppm lead will result from decay of the uranium
in kolm in 500 Ma. However, in their detailed
isotope work on uranium and lead, Cobb & Kulp
(1961) report that kolm has probably lost daughters
in the uranium decay series (radium, radon and/or
lead) by diffusion and/or leaching. It is important to
note that the kolm is enriched only in uranium (and
lead by uranium decay) and organic carbon relative
to the adjacent alum shale and not in other elements,
such as molybdenum, vanadium, copper, etc., that
are often enriched in organic-rich units. The shale
samples from Sydbillingen are enriched in uranium,
molybdenum, arsenic, lead, vanadium, nickel and
copper (in that order) relative to average shale. In
contrast, alum shale samples from Jiimtland, on the
Caledonian front, are enriched in vanadium, nickel,
zinc, barium and phosphorus (in that order), but
not uranium, relative to the samples from southern
Sweden (Sydbillingen and Niirke).
The element enrichments of the kolm and
Jiimtland samples will be discussed. It is assumed
that the element contents in the Sydbillingen
samples (southern Sweden) represent normal syn­
genetic non-metamorphosed shale. The Jiimtland
samples are especially enriched in vanadium, nickel,
zinc and barium relative to the Sydbillingen
samples. The tectonic events on the Caledonian
front were probably accompanied by heated fluids
during thrusting. This suite of enriched elements
could be derived by the interaction of hot water and
rocks in the Caledonian cover and basement, the
latter including subordinate basic rocks. Table 4
and granitic rocks. Although manganese is not en­
riched in the Jiimtland samples relative to average
Table 4. Geochemical abundances (ppm) of selected
samples from Turekian & Wede pohl ( 1961)

Element Basalt Granite

0.5
v 250 65
Mn 1600 100
Ni 130 10
Cu 87 20
La Nd Eu Tb Yb y u Zn 105 50
As 2 1·7
Ce Sm Gd Dy Lu Mo orgC y 21 37
Mo 1·5 1 ·2
Fig. 4. Ratios of rare earth elements and yttrium in kohn , Ba 330 630
Sydbillingen/Ranstad (Ran) and Himtland (Jamt) samples Ce 48 86
(data from Table 2) to 'North American shale' (NAS, Yb 2·1 3·7
values from Haskin et al., 1968) . Also shown are ratios of Pb 6 17
molybdenum, uranium and yttrium to average shale (from u 1 3
Fig. 3) . See text for discussion .
210 1. Lev enth al
shales this could be because of the solubility of
manganese under reducing conditions. The enrich­
ment in vanadium, which is greater than the other
elements, could also have come from the circulation
of the heated waters interacting with the overlying
vanadium-rich Ordovician Dictyonema-bearing
shales that have been reported locally in these
Himtland shales (Gee, pers. comm. , 1989).
Alternative explanations could involve differing
source areas for vanadium and uranium or facies
controls in enrichment and deposition. Along
these lines, Gee (1981) and Sundblad & Gee (1984)
suggest that the high vanadium contents of the black
shales in the higher Caledonian thrust sheets are
syngenetic and related to the Dictyonema-bearing
shales, based on stratigraphic relationships.
Rare earth element abundances and distribution
Another set of interesting geochemical comparisons
are shown in Table 3 for the REE. The kolm shows
an enrichment in the REE that increases with the
increasing atomic number. This is shown in Fig. 4,
where the REE are ordered by increasing atomic
number and their concentrations in the samples
plotted relative to NAS values (Table 3). Also in­
cluded are yttrium, molybdenum and uranium that
are enriched by even greater factors than the heaviest
REE; but note that organic carbon is not nearly as
enriched as uranium. The lightest REE actually
appear to be depleted, but if the organic content of
the kolm is taken into account (as a diluent) then the
light (L) REE are very near normal NAS values.
Rare earth elements have been used as geo­
chemical tracers for both low temperature (usually
marine chemistry) and high temperature (magma
and mineral formation) processes (Taylor &
McLennan, 1985). Rare earth element enrichments
and abundance patterns for the kolm are unusual:
they require discussion in terms of possible element
sources and transport and concentration mech­
anisms. Thus, it is necessary to consider REE
abundances from possible source rocks (from high
temperature processes) and transport and concen­
tration (low temperature processes) to explain the
abundance and distribution of REE in the kolm.
Certain sedimentary minerals are enriched in heavy
(H) REE, for example apatite pellets and glauconite
from offshore Peru (Piper et al. 1988; also see
McArthur & Walsh, 1984, for review and discus­
sion). One study of the clay mineral fraction of
samples related to a Jurassic sandstone-hosted
uranium ore in New Mexico, USA, reported REE
enrichment (but not HREE enriched) near epi­
genetic uranium ores and suggested transport of
REE by organic complexing and/or adsorption on
colloidal species (Della Valle & Brookins, 1983).
Some igneous minerals are also enriched in HREE:
sphene, zircon, xenotime and clinopyroxene (Sawka
& Chappell, 1988). These minerals are not present
as hosts for REE in the kolm, and only sphene or
clinopyroxene could have sourced the REE during
weathering with subsequent preferential enrichment
in the kolm.
Another possible source of REE is the erosion of
uranium deposits or weathering of source rocks that
subsequently contribute to uranium deposits. This
possibility can be considered for the Swedish
uranium deposits in the Precambrian basement. The
uranium-enriched granites of Sweden give ages of
1000-850 Ma (Wilson & Fallick, 1982): they often
contain mineral assemblages that are enriched in
REE, such as zircon and sphene (Smellie, 1982).
In a study of the Lilljuthatten uranium deposit
(420 Ma) the source rock was postulated to be the
1650 Ma Olden Granite (Stuckless & Troeng, 1984).
Although the Olden Granite is in northern Sweden
it could have also been a source rock during the
Cambrian. The REE of this granite show a flat to
increasing REE abundance for REE heavier than
europium, with Yb : Sm > 1.
The sites of the REE also need to be considered
because the REE abundances in the kolm are dif­
ficult to explain. If the REE were sited in clay
minerals, as they often are, their contents should be
decreased, as are the aluminium and other clay­
forming elements, because of the relatively smaller
amount of clay (due to dilution by the increased
amount of organic matter) in the kolm. Although
this is true for the light REE (such as lanthanum and
cerium), the REE samarium through lutetium are
enriched. The REE are probably not present in
phosphate because phosphorus is depleted in the
kolm (Fig. 3) relative to both average shale and to
the alum shales. Part of this is due to dilution by
organic matter, although many organic-rich samples
are enriched in phosphorus. Detrital heavy minerals
are also not a possible site for the REE because
elements characteristic of heavy minerals (zircorium,
neodymium, hafrium and thorium) are not en­
hanced (in fact, they are low: Zr 150, Nb 5, Hf <5,
Th 4 ppm). Thus, if the REE and yttrium are not
located in the clay, phosphate or heavy minerals,
 Black shale geochemistry
they must be associated with another site, perhaps
the organic matter.
In an electron microprobe study, Parnell (1984)
was able to identify that some of the cerium and
uranium occurred in the phosphate minerals xeno­
time and monazite. However, this does not account
for the occurrence of other REE and yttrium. A
consideration of the material balance of the phos­
phorus and REE (Table 1) shows that whereas the
REE could theoretically be accommodated in phos­
phate minerals (only cerium was identified by
Parnell, 1984), the yttrium is too abundant to be
sited wholly in phosphate. Further microprobe work
may determine if there are mineral hosts for the
other abundant REE (neodymium and ytterbium)
and especially yttrium.
Unusual REE abundances and distributions have
been found to be associated with uranium deposits
(McLennan & Taylor, 1979, 1980; Fryer & Taylor,
1987; Leventhal et al., 1987). These unusual REE
patterns and enrichments are also commonly associ­
ated with granitic host rocks (Taylor & Fryer, 1984),
where HREE were enri�hed in the fluid phase during
transport by carbonate complexing (McLennan &
Taylor, 1979) at hydrothermal temperatures. How­
ever these uranium deposits are mainly epigenetic
unconformity vein-type deposits hosted in Pro­
terozoic rocks that were associated with heated
fluids. This is in sharp contrast to the alum shale and
kolm of syngenetic-sedimentary origin that have
never been heated above 60-80°C at Narke and
only slightly higher at Sydbillingen based on Rock­
eva! and burial history.
Another way to consider the REE problem is to
.
examine seawater as a likely source. De Baar etal.
(1985) reported that present day seawater is pro­
gressively enriched in HREE with depth (data to
3250 m) by preferential scavenging of the LREE by
settling particles. A somewhat different explanation
was given by Klinkhammer et al. (1983) who also
reported HREE enrichment at depth in the Pacific
Ocean, but attributed it to regeneration of REE at
hydrothermal vents where iron and manganese
oxides preferentiaUy scavenge the LREE. In the
Cariaco Trench seawater, a sharp discontinuity in
the REE abundance is seen at the oxic-anoxic
boundary where two effects are noted (De Baar
et al., 1988): the cerium and europium show
anomalies that are related to their possible +4 and
+2 oxidation states, respectively. Of more relevance
to the present problem is the reduction of iron
oxides that had scavenged the REE, with subsequent
211
formation of iron sulphides and release of adsorbed
REE, in this case mainly LREE.
Hoyle eta/. (1984) reported on the behaviour of
REE during the mixing of river and seawater where
the REE in the organic-rich Luce River are chiefly
associated with iron -organic matter colloids rather
than being in solution. In experiments using different
salinities to simulate mixing they found that approxi­
mately 70-80% of the REE were removed from the
water during the salinity increase from 0 to 10%o;
most of this change occurred in the 0-5%o region.
Hoyle et al. (1984) explained this as being due to
flocculation of the organic matter colloids. They also
found that the HREE formed stronger complexes
with the organic colloids than the LREE and thus
were preferentially removed (e.g. 95% Yb vs 60%
La) in the estuary. By way of contrast; they observed
essentially no removal of REE from an organic-poor
river in conditions simulating the estuary from sal­
inities 0 to 25%o.
The problem with the above interpretation is that
the nearshore precipitation of REE is indirect, being
due to their complexation to organic matter (or
iron-organic matter) colloids. In Cambrian times
there were no land plants and therefore no soil
organic matter to form organic matter colloids in
river water. Thus the well-documented regime of
the present day river-estuary removal of REE by
organic flocculation in the estuary did not occur
during the time of deposition of the alum shale.
In another study, Sholkovitz & Elderfield (1988)
studied REE in Chesapeake Bay and the related
Susquehanna River and estuary. They found that
the dissolved REE were strongly enriched in HREE
compared to the particulate (colloidal) fraction. The
basin becomes anoxic at depth and the HREE are
depleted in the oxygen-poor deep waters. They also
found that the sediments were enriched in LREE
over HREE (relative to average shale), whereas
the sediment pore waters were enriched in HREE
over LREE (but lower corrcentrations by a factor of
106 than in sediments). They believe that the
Chesapeake Bay system is more complex than the
stable redox conditions in the Cariaco Trench and
involves an indirect coupling to the redox cycle of
manganese.
Another factor to consider is the REE complex­
ation by carbonate and oxalate anions at low
temperature (Cantrell & Byrne, 1987). Their exper­
imental work shows that the HREE are more ef­
fectively complexed (Yb 75%) than the LREE (La
20%) by the carbonate anion (e.g. Yb(C03)z -) that
212 J.
would predominate in seawater. Thus, the LREE
could be removed early (estuary and nearshore),
leaving the HREE to be enriched in the deeper
basin offshore (Goldstein & Jacobsen, 1988). It has
been suggested (B. Dahlman, in Cobb & Kulp,
1961) that the kolm was deposited in the central axis
of the basin; this can partly explain the HREE
enrichment. However, Thickpenny (1984, 1987) and
Andersson et a!. (1985) favour deposition of the
alum shales in an exceedingly stable epicontinental
sea below wave base but offer no explanation for the
kolm.
GENERAL SUMMARY
The Scandinavian alum shale is an unusual metal­
rich black shale with several additional anomalies:
the stratigraphically controlled geochemically
unique kolm and the tectonically disturbed
vanadium-rich shale on the Caledonian front. The
alum shale in southern Sweden in the Sydbillingen
and Narke regions is flat-lying and undisturbed by
significant burial or deformation. It is enriched in
organic matter of marine origin that was deposited
offshore at a depth of at least 100 m to allow
stratification of the water column and formation of a
lower stable euxinic layer. The euxinic bottom waters
caused efficient trapping, by reduction, of metals
and the preservation of organic matter and associated
metals. A low sedimentation rate also enhanced
metal contents because of a lack of clastic dilution.
As a result, iron was completely sulphidized and all
reducable metals were fixed in the sediment as
sulphides or associated with organic matter. The
suite of enriched metals (uranium, molybdenum,
vanadium, arsenic, nickel, copper, lead) could have
come from either a basic source (richer in vanadium,
nickel and copper) or a granitic source (richer in
uranium) or, more likely, a combination of these
such as basalt for most metals and erosion of a
uranium deposit for the uranium. The lead is mostly
radiogenic and the elevated arsenic and molybdenum
contents could have come from either basalts or
granites, where these elements are equally abundant.
The alum shales on the Caledonian front have
undergone low grade metamorphism and during this
process heated waters probably leached associated
metasediments and/or underlying basement rocks
and added vanadium, nickel, zinc, copper and
barium (but not uranium) during the Caledonian
Orogeny, about 100 my after the shale was de­
posited. The vanadium in the Cambrian shales could
Leventh al
have been added during water circulation by mobil­
ization of vanadium from the overlying Dictyonema
shale. Other enriched metals (nickel, zinc and cop­
per) are a suite that is most likely derived from
a basic (basaltic or gabbroic) source. This in­
terpretation is reasonable, based on the tectonic
history and basement rocks of the area.
The kolm enrichment in uranium, molybdenum,
yttrium and HREE is less easy to explain. It requires
some combination of the following: a unique source,
selective transport and/or specific concentration
mechanisms. The uranium and REE are not derived
directly from heavy minerals because the elements
zironium, hafrium, and thorium, which are usually
associated with heavy minerals, are not enriched in
the kolm. The stratigraphic control and richness in
organic carbon of the kolm suggest a unique de­
positional setting, with low dilution by clastic mat­
erial, a rich source for uranium and HREE and
extremely low sedimentation rates. The high organic
content of the kolm may be due to the lack of clastic
dilution, higher organic productivity or a greater
thickness of the euxinic water column or some com­
bination of these. From sulphur and iron data, the
iron is completely sulphidized (Leventhal, 1983),
indicating that the environment of deposition must
have been euxinic so that high preservation of
organic matter was effected. However, the euxinic
condition probably held for the adjacent shale as
well, based on the sulphur intercept on the SIC plot
(Leventhal, 1979, 1987; Thickpenny, 1987). Thus
there is no problem in the preservation of organic
matter and sulphides even at very low sedimentation
rates. Because preservation was not unique to the
kolm, low clastic dilution and/or high productivity
of organic matter must have caused the kolm 's
organic richness.
Selective enrichment of HREE by carbonate com­
plexing noted by McLennan & Taylor (1980) at
increased temperatures is also possible at low tem­
perature in seawater (Cantrell & Byrne, 1987). Thus,
removal of LREE by selective adsorption on iron
and manganese oxides in the estuary or near shore
coupled with carbonate complexation of HREE may
account for the enrichment in the kolm.
The suggestion of 'organic complexing' by Della
Valle & Brookins (1983) has not been tested. The
epigenetic uranium deposits studied by Della Valle
& Brookins are however enriched in organic matter
(Leventhal, 1986). An argument against this
suggestion is the observation that many organic-rich
shales, including the alum shale, do notshow HREE
 Black shale geochemistry
enrichments. It is possible that severe (or pref­
erential) weathering of a rock that is rich in this suite
of elements (or heavy minerals), such as a granite,
could have contributed them. A host rock similar to
the Olden Granite is such a rock. Another possibility
is the contribution of uranium and HREE from
destruction (weathering and erosion) of an existing
uranium deposit. This is illustrated by the geo­
chemistry of the Pine Creek Geosyncline uranium
deposits that are enriched in HREE and also in
yttrium (McLennan & Taylor, 1980) but is only
partly analogous to the deposits related to the
Swedish Olden Granite (Stuckless & Troeng, 1984)
which show less depletion in HREE. Destruction
(by uplift or faulting) and weathering of a local,
existing vein-type uranium deposit at the time of
sedimentation of the kolm could account for the
uranium enrichment. This fortuitous timing of de­
struction of an unusual uranium- and HREE-bearing
ore at the time of kolm formation may not seem a
very probable event, but the alum shale is very
unusual and an even more unusual event may be
necessary to account for the unusual elements in the
kolm. Selective concentration of HREE in the kolm
as a result of removal of LREE by adsorption in the
nearshore and/or selective complexation/transport
of HREE further into the basin where the kolm was
formed could account for the REE pattern. The
high organic carbon content of the kolm requires
that the basin be starved, that the kolm be formed
at water depths of at least 100 m to maintain water
column stratification below wave base and/or pos­
sibly that production of organic matter was greater.
ACKNOWLEDGEMENTS
I especially thank D.G. Gee (formerly with Swedish
Geological Survey, now at Institute of Geology,
University of Lund, Sweden) who provided the
carefuLly chosen representative samples and also
provided important geological information, dis­
cussions of the results and helpful review of the
paper. I thank J. Erdman, USGS, for providing
several samples and my USGS colleagues F. Lichte,
D. McKown, E. Daws and M. Stanton for detailed
analytical chemical results. I thank B. Hofmann, J.
Hatch, A. Thickpenny and B. Buchardt for very
complete reviews of the manuscript.
REFERENCES
ANDERSSON , A . , DAHLMA N , B. & G EE , D. ( 1983) Kerogen
213
and uranium resources in the Cambrian Alum Shales of
the Billingen-Falbygden and Narke areas. Sweden.
Geol. Foren. Stockholm Forh. 104, 197-209.
A N DERSSON, A . , DAHLMAN , B ., GEE, D . & S NALL, S .
( 1 985) The Scandinavian Alum Shales. Svcr. Gcol.
Unders. Ser. (Ca) N R56, Uppsala, 50pp .
ARMANDS, G. ( 1972) Geochemical studies of uranium,
molybdenum and vanadium in a Swedish Alum Shale.
Stockholm University Contrib. Geol. 27, 1-148 (in
Swedish) .
BAEDECKER, P . & M c KowN , D . ( 1 987) Instrumental neu­
tron activation analysis of geological sam p les. USGS
Bull. 1770, H1-14.
BucHARDT, B . , CLAUSEN, 1. & THOMSEN , E. (1986)
Carbon isotope composition of lower Paleozoic kerogen.
Organic Geochem. 10, 127- 1 34.
CANTRELL, K . & BYRNE, R . ( 1987) Rare earth element
complexation by carbonate and oxalate ions. Geo­
chim. cosmochim. Acta 51, 597-605 .
CoBB, 1. & K ULP , 1. ( 1961) Isoto pic geochemistry of
uranium and lead in the Swedish kolm and its associated
shale. Geochim. cosmochim. Acta 24, 226-249.
CROCK, 1. & LICHTE, F . ( 1982) Determination of
rare earth elements in geological materials by ICP­
AES. Anal. Chem. 54, 1 329- 1333.
DAHL, 1. HALLBERG, R . & K APLAN , l. ( 1988a) The
effects of radioactive decay of uranium on elemental
and isotopic ratios of alum shale kerogen. Appl.
Geochem. 3, 583-589.
DAHL, 1. HALLBERG, R. & KAPLAN , l. ( 1 988b) Effects
of irradiation from uranium decay on extractable
organic matter in the alum shales of Sweden. Organic
Geochem. 12, 559-571 .
DAHLMAN , B . & GEE, D . ( 1977) Oversikt over
Billingen-Falbygdens geologi. In: Betakande av
Billingen-tredningen, Billingen 4, exampel Suaens
offentliega utredninger 1977, Vol. 47, pp . 2 19-255.
Industri departmentet, Stockholm (in Swedish).
DAVIDSON, C. ( 1961) The kolm de posits of Sweden.
Mining Mag. 105, 201-207.
D E BAAR, H . , B A CON , M. & B REWER, P. ( 1985) Rare
earth elements in the Pacific and Atlantic Ocean.
Geochim. cosmochim. Acta 49, 1943- 1959.
D E BAAR, H . , GERMAN, C . , ELDERFIELD, H. & VAN
GAA N S , P . ( 1988) Rare earth element distributions
in anoxic waters of the Cariaco Trench. Geochim.
cosmochim Acta 52, 1203-12 19.
DELLA VALLE, R.S. & B ROO KINS , D . G. (1983) Geo­
chemical studies of the Grants mineral belt, New
Mexico. In: The Signii f cance of Trace Elemems in
Solving Petrogenic Problems, pp . 793-818.
Theo phrastus, Athens.
DwORATZEK, M. ( 1987) Sedimentology and Petrology
of Carbonate Intercalations in the Upper Cambrian
Olenid Shale Facies of Southern Sweden. Sver. Geol.
Unders. Ser. (C) N R 819, U ppsala, 73pp .
EDLING , B. ( 1 974) Distribution of Uranium in the
Upper Cambrian Alum Shale fi"om Ranstad,
Billingen, Vastergotland. Pubis Paleontol. Inst.,
Univ . Uppsala. S pec. Vol. 2, 1 1 8pp . (in Swedish) .
FRYER, B . J . & T AYLOR, R . P . ( 1987) Rare-earth element
distribution in uranini tes: im plications for ore gen­
esis. Chem. Geol. 63, 10 1-108.
2 14 J. Leven tha l
GEE. D . G . ( 1980) Basement-cover relationshi ps in
the central Scandinavian Caledonides. Ceo/. Foren.
Stockholm Forhandl. 102 , 455-474.
GEE, D . G. ( 1981) The D ictyonema-bearing phyllites
at Nordaunevoll, eastern Trondelag, Norway . Norsk
Geologisk Tidsskrift, 6 1 , 91-95.
GoLDSTEIN S . & JACOBSEN S. ( 1988) Rare earth
elements in river water. Earth Planet. Sci. Lett. 89 ,
35-47.
HASKI N , L . . HASKI N , M . . FREY, F. & WILDEMAN, T .
( 1968) Relative and absolute abundances terrestrial
of the rare earth elements . In: Origin and Distri­
bution of the Elements (Ed. by L. Ahrens) pp . 889-
9 12. Pergamon Press, Oxford .
HESSLA N D , I . & ARMANDS, G. ( 1978) Alunskiffer Under­
lagsmaterial geologi. Utredning Fran Stcuens Industri,
(SIND 1978 : 3) Stockholm, pp . 1- 146, 1-94 and 1-38
(in Swedish).
HOYLE, J., ELDERFIELD, H., GLEDHILL, A. & McLENNAN, S . M . & TAYLOR, S . R . (1980) Rare earth
GREAVES, ( 1984) The behaviour of rare earth el­
ements during mixing of river and sea waters. Geochim.
cosmochim. Acta 48 , 143- 149.
KLINKHAMMER, G . , ELDERFIELD, H. & H U DSON , A. ( 1983)
Rare earth elements in seawater near hydrothermal
vents. Nature 305, 185- 188.
LEVENTHAL, 1. ( 1979) The relationshi p between carbon and
sulfur in recent and ancient marine and euxinic sedi­
ments . EOS Trans. Am. Geophys. Union 60, 282.
LEVENTHAL, 1. ( 1981) Origin, distribution and controls of
syngenetic metals in black shales and resource imp li­
cations. Ceo!. Soc. Am. Abstracts 13, 497.
LEVENTHAL, J. ( 1983) Organic carbon, sulfur and iron
relationshi ps in ancient shales as indicators of de position.
EOS Trans. A m. Geophys. Union 64, 739.
LEVENTHAL, 1. ·(1 986) Roles of organic matter in ore
deposits. In: Organics and Ore Deposits (Ed. by W .
Dean), pp . 7-20. Denver Region Ex ploration Ge­
ologists Symposium, Wheat Ridge, Colorado.
LEVENTHAL, J. ( 1 987) Carbon and sulfur relationshi ps in
Devonian Shales from the Appalachian basin as an
indicator of environment of de position. Am. I. Sci. 287,
33-49.
LEVENTHAL, 1. ( 1 988) Comparative geochemistry of metals
and trace elements from Cambrian Alum Shale of
Sweden. In: International Symposium on Sedimentology
Related to Mineral Deposits, pp . 1 22-123 . Beijing.
LEVENTHAL, J . , CROCK, J . & MALCOLM , M. ( 1981) Geo­
chemistry of trace elements and uranium in D evonian
Shales of the Appalachian Basin. US Ceo!. Survey Open
File Report, 81-778, 76 pp .
LEVENTHAL, J . , CROCK, J . , MOUNTJOY, W. & T HOM AS , J .
( 1978) Results o f analysis o f USGS black shale standard
SD0- 1 : US Ceo!. Survey Open File Report, 78-447,
l l pp .
LEVENTHAL, J . , DAws, T. & FRYE, J . (1 986) Organic
geochemical analysis of organic matter associated with
uranium . Appl. Geochem. 1 , 24 1 - 247 .
LEVENTHAL, J . , GRAU C H , R . , THRELKELD, C . , LICHTE, F . &
HARPER, C. ( 1 987) Unusual organic matter associated
with uranium from Cluff Lake, Canada. Econ. Ceo!. 82,
1 169- 1176.
LEVENTHAL, J. & HoSTERMAN, J. ( 1 982) Chemical and
mineralogical analysis of Devonian black shale samples
from Kentucky, Ohio, Virginia and Tennessee. Chem.
Ceo/. 37, 239-264.
LEWAN , M. & B ucHARDT, B. ( 1 989) Irradiation of organic
matter by uranium decay in the alum shale, Sweden.
Geochim. cosmochim. Acta. 53, 1 307- 1322.
LICHTE, F . , GoLIGHTLY , D. & LAMOTHE, P. ( 1 987) Induc­
tively coupled plasma-atomic emission sp ectrosco py .
In: Methods for Geochemical Analysis (Ed . b y P .
Baedecker) . US Geol. S urvey Bull . 1770, B 1-B10.
McARTHUR, J . & WALSH, J . ( 1984) Rare-earth geo­
chemistry of phosp horites. Chem. Ceo!., 47, 19 1-220.
McKow N , D . & MILLARD, H. ( 1987) Determination of
uranium by delayed neutron counting. In : Methods for
Geochemical Analysis (Ed. by P . Baedecker). US Geo l .
Survey B ul l . 1770, 1 1- 12 .
McLEN N AN , S . & TAYLOR, S . ( 1979) Rare earth element
mobility associated with uranium mineralization. Nature
282, 247-250.
elements in sedimentary rocks, granites and uranium
deposits of the Pine Creek geosyncline. In: Proceedings
of International Uranium Symposium on the Pine Creek
Geosyncline (Ed . by J . Ferguson & A. Goleby ) ,
pp . 175-190. International Atomic Energy Agency ,
Vienna.
PARNELL, J. ( 1984) The distribution of uranium in kolm:
evidence from backscattered elecron imagery . Ceo!.
Foren. Stockholm Forhandl. 106, 231-234.
PIPER, D . , BAEDECKER, P . , CROCK, J . , B U R N ETT, W .
& LOEBNER, B . ( 1 988) Rare earth elements i n the
p hos p hatic-enriched sediment of the Peru shelf. Marine
Ceo!. 80 , 269-285.
SAWKA, W . & CHAPPELL, B . ( 1 988) Fractionation of U, T h
and R E E i n a vertically zoned granodiorite , Sierra
Nevada batholit h , California , USA. Geochim. cosmo­
chim. Acta 52, 1 13 1 - 1 143.
SHOLKOVITZ, E . & ELDERFIELD, H. ( 1 988) Cycling of dis­
solved rare earth elements in Chesapeake Bay . Global
Biogeochem. Cycles 2, 157-176.
SMELLIE, J. ( 1 982) Radioactive mineral p hases from Pre­
cambrian Granites within the Olden window, Jamtland,
N. Sweden. OCED Nuclear Energy Agency . Proc.
Symp. Uranium Exploration Methods, Paris, 1982,
pp . 415-428.
SNALL, S. ( 1988) Mineralogy and maturity of t he alum
shales of south-central Himt land. Sweden. S ver. Ceo/.
Unders. (C) 818, Upp sala, 46 pp .
STUCKLESS, J . & TROEN G , B . ( 1984) Uranium mineralization
in response to regional metamorphism at Lilljuthatten,
Sweden. Econ. Ceo!. 79, 509-528.
SuN DBLAD, K. & GEE, D . ( 1 984) Occurrence of a
uraniferous-vanadiferous grap hiteic p hyllite in the
Koli Nappes of the Stekenjokk area, central Swedish
Caledonides. Ceo!. Foren. Stockholm Forhandl. 106,
269-274.
TAGGART, J . , LINDSAY, J . , ScoTT, B . , VIVIT, D . , BARTEL, A.
& STEWART, K . ( 1987) Analysis of geologic materials by
wavelength dis persive X-ray fluorescence spectrometry.
In: Methods for Geochemical A nalysis (Ed. by P .
Baedecker) . U S Geol. S urvey Bull. 1770, E 1 -:- E19.
TAYLOR, R. & FRYER, B . ( 1984) Rare earth element litho­
geochemistry of granitoid mineral de posits. Can. Inst.
Min. Met. Bull. 76, 74-84.
 Black shale geochem istry
TAYLOR, S. & M cL ENNAN , S. ( 1 985) The Continental Crust:
its Composition and Evolution. Blackwell Scientific,
Oxford, 312pp .
THtCKPENNY, A. (1984) The sedimentology of the Swedish
Alum Shales. I n : Fine Grained Sediments: Deep Water
Processes and Environments (Ed. by D . Stow & D .
Pi per) , Spec. Pub! . , pp . 5 1 1 -526. Geol. Soc. 1 5 . Black­
well Scientific Publications, Oxford .
THtCKPE N N Y , A. ( 1987) Palaeo-oceanography and depo­
sitional environment of the Scandinavian alum shales:
sedimentological and geochemical evidence. I n : Marine
Clastic Sedimentology (Ed. by J . K . Leggett & G .
215
Zuffa pp ) , pp . 156- 17 1 . Graham & Trotman, London.
TuREKlAN , K. & WEDEPOHL, K. ( 1961) Distribution of
elements in the earth's crust. Ceo/. Soc. Am. Bull. 72,
175- 192.
WAND LESS, G. ( 1987) Radiochemical neutron activation
analysis of geological materials. US Ceo/. Surv. Bull.
1770, J l - 8.
WtLSON , M . & FALLlCK, A . ( 1 982) The relationshi p between
uranium-enriched granites and hydrothermal mineraliz­
ation in northern Sweden. OCED Nuclear Energy
Agency, Proc. Symp. Uranium Exploration Methods,
Paris, 1982, pp . 293-306.
Spec. Pubis int. Ass. Sediment. (1990) 11, 217-224

Uranium enrichment in the Permian organic-rich Walchia shale,

Intra-Sudetic Depression, southwestern Poland

S. WOLKOWICZ

Geological Survey of Poland, Rakowiecka 4, 00-975 Warsaw, Poland

ABSTRACT

The Lower Permian section of the Intra-Sudetic depression includes black shales of lacustrine origin. Of
these shales, the Walchia shale ( Ratno Dolne Member) has the widest distribution. The rocks are
further subdivided into several complexes according to lithology. They represent sedimentary environ­
ments varying from oxidized and unoxidized parts of the pelagic zone to the littoral and coastal plain.
Horizons with uranium mineralization occur within beds of organic-rich pelagic sediment. Facies
analysis and studies of organic matter suggest that the mineralization was syndiagenetic and occurred in
rocks below wave base. The presence of migrated bitumens on fracture surfaces and a correlation
between uranium and organic carbon contents suggest the possibility of reconcentration of uranium
within migrated bitumens.

INTRODUCTION

The Intra-Sudetic Depression is a substantial region lain by poorly sorted conglomeratic sandstones
of the Sudety Mountains (northeast part of the of the Radkow Formation, dated as Saxonian
Bohemian Massif; Fig. 1). The development of the (Dziedzic, 1961).
Depression began in the Early Carboniferous and Anomalous uranium concentrations, some of
had a multiphase history including infill with Car­ economic value, are known from several lithostrati­
boniferous, Permian, Triassic and Cretaceous rocks graphic units of the Permian in the Intra-Sudetic
(Fig. 1). The sediments of early Carboniferous to Depression (Fig. 2). This paper describes those
early Triassic are of the molasse type. The Carbon­ found in the Walchia shale.
iferous sequence is mainly represented by continen­
tal sediments with mudstone units including coal
seams. Lower Permian rocks, also continental in SEDIMENTOLOGY OF THE
character, may be subdivided into four mega­ WALCHIA SHALE
cyclothems (Fig. 2). Each of these cyclothems begins
with fluvial conglomerates and sandstones, usually Rocks of the Walchia shale form several complexes
oxidized, and ends with mainly unoxidized lacustrine varying in lithology. The base of the Walchia shale is
mudstones. Fairly thick complexes of volcanic here defined by the first appearance of dark-coloured
rocks are known from the contact of the third and silty-sandy or, locally, clay rocks in the section.
fourth megacyclothems in the Slupiec Formation The subtuffite complex, 45 m thick, is built of mud­
(Kozlowski, 1963). The volcanogenic rocks include stones and sandstones with horizontal and cross­
trachybasalts, latites, rhyolites, andesites and bedding, dispersed pyrite and (in the upper part)
rhyolite tuffs (Nowakowski, 1968; Gorecka, 1982; carbonized plant remains (Fig. 3). The basal part
Kubicz et al., 1986). Tectonic movements at the end also includes two carbonate beds each 2 m thick.
of the Autunian resulted in a break in sedimentation The beds are of similar magnitude over distances of
and partial restructuring of the depression. Rocks of about 12 km. The middle part of the complex is
the Walchia shale (Ratno Dolne Member) are over- characterized by intercalations of brown-red ripple-

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun 2 17

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
2 18 S. Wolkowicz

Fig. 1. Location of the studied area

and geological map of the
southeastern part of the Intra­
Sudetic Depression. (After Nemec
et a!., 1982. ) (1-9) Sedimentary and
volcanic rocks: (1) Upper
Cretaceous; (2-4) Lower Permian:
(2) Radkow Formation, (3) Slupiec
Formation, (4) Krajanow
Formation; (5-7) Upper
�. "'·
...... ....

Carboniferous: (5) Ludwikowice

./ Formation, (6) Zacler Formation,
r·f":,..,...
.,J'-
0 5 km
�----'
(7) Walbrzych Formation; (8)
Lower Carboniferous, Szczawno
Formation; (9) Lower Permian
C]1 r=::a2 �3 �4 OJ] �6 5 .
volcanics (undifferentiated).
(10-13) Surrounding units: (10)
Gory Bardzkie, (11) Klodzko
OliliiiJ �8 �9
7 10 �11 �12 metamorphics, (12) gabbros and
diabases of Klodzko area; ( 13)
EEEl]13 l.r-�'114
.
.
15 Sowie Gory Block; (14) state
boundary, (15) boreholes.

Relative intensity
of uranium
Stratigraphy Lithostro.ti gro.phy Lithology mineralization
low high

0 0 0 0 0
c .

.�
. ' 0 0 0 0 0
0 0 0 0 0 0 0
c
0 Radkciw Formation 0 0 ' 0
0
0
0
0
0
0
X 0 0 0
d 0 0 0 . . 0 .

VJ . 0 0 . . .

Ratno Dolne �::�

-- ��
Member
-
-----

-
--

- -- -
- -- - c
�
- ---=

�
z
S.i:"upiec ( Walchia Shale)

K /
<t Volcanic
�

:L Complex
0:: Formation
w
o_ Zagorzyn
Member
c
0::
d . 0 . " .
w ·- . 0 • 0 .

3 c ......:... ;....__• ---=---=--

0
:::J
+-
u. Anthraces ia Shale
---:- - �--:--:-
_J :::J
------
�
. .
� '"'-' ,-..._,
<t
Krajanow
Member . .

�wierki 0 0 ' . 0 0
. . 0 0 0 0 0
L.Anthracosia Shale -
�
----

-- - ---
----
Formation --- - -
� � �,..__,

Fig. 2. Permian stratigraphy of

Ludwikowice . .
southeastern Intra-Sudetic
Upper
Member . 0 . 0 . . .
Depression, indicating levels of
Carboniferous 0 0 0 0 0 0 0
anomalous uranium concentration.
 VII VIII IX

�
�
i5.
E
0
u

50

VII VIII

u <9 pu

100

�
"
i5.
E
"
u

150

I I
I I
I I
I
1 v11

�. 1?/�
111112 vu 2
.-- 3
,..,..,...,.... 4
"��� �
� 61 5

§. 1111?,
"
i5.
E
��J
0a
� �
C><r 8
0
u

Fig. 3. Borehole log Wambierzyce IG-12 (W-12), and

section of complex III in the Wambierzyce lG-15 (W-15)
borehole: (l) the studied lithologic complex; (II) thickness
(depth) in metres; (III) lithologic column: (1) mudstone,
(2) silty mudstone, (3) muddy siltstone, (4) siltstone, (5)
sandy siltstone, (6) silty sandstone, (7) sandstone, (8)
conglomerate; (IV) colour of rock: (1) grey and black, (2)
variegated, (3) brown and red; (V) erosional boundaries;
(VI) sedimentary structures: (1) horizontal bedding, (2)
cross-bedding, (3) ripple marks, ( 4) flaser bedding, (5)
� wavy bedding, (6) erosional channels, (7) mud cracks and
i5. mud flakes, (8) rain prints; (VII) bioturbation: ( l) single,
E
8 (2) few, (3) numerous, (4) very numerous, (5) interior
mould of branches, (6) coprolites, (7) floral remains, (8)
fish remains; (VIII) interpretation of sedimentary
palaeoenvironments: pu, pelagic anoxic, po, pelagic oxic,
L, littoral, cp, coastal plain, af, alluvial fan; (IX) uranium­
rich horizons.
220 S. Wo/kowicz

laminated sandy rocks and moulds of branches. environment and partly in the coastal plain zone.
Rocks of the subtuffite complex originated in the The calcareous grey-black clay-silty series with
predominantly oxidized pelagic zone of the lacustrine horizontal lamination was deposited in both the
basin. The exception is the brown-red sandy oxidized and unoxidized pelagic zone. Towards the
intercalations, which were deposited in the littoral southeast, i.e. in the direction in which the basin was
zone of the basin. becoming shallower (borehole W - 15), sedimentation
The subtuffite complex is overlain by a horizon of was in the littoral zone or even in an alluvial fan
rhyolitic tuffs 25-40 m thick. Deposition of the tuffs environment.
resulted in shallowing of the sedimentary basin and Black clay-silty rocks reappear in the section
levelling of the basin floor, and was followed by above complex III. This series, assigned to complex
sedimentation of brown-red silty-sandy rocks IV, is characterized by limited sandy mudstone inter­
throughout the area. The rocks assigned to the calations (Fig. 3). Its basal part displays inter­
supratuffite complex are about 30 m thick and gen­ calations of alternating laminae of mudstone and
erally display cross-bedding (Fig. 3) and thorough carbonate. Individual laminae are 1-10 mm thick
bioturbation. Mud cracks, mud flakes and rain prints and show marked epigenetic deformation. The whole
are known from the middle part and erosional complex IV is 80-100 m thick and very similar to
boundaries are fairly common. The rocks displaying the complex II described above. It was deposited in
mud cracks, mud flakes and rain prints originated in both the oxidized and unoxidized parts of the pelagic
a coastal plain zone, and the remaining rocks were zone of the basin.
deposited in the littoral zone of the lacustrine basin.
Rocks of complex I are overlain by a 40-60 m
series of laminated or structureless black mudstones URANIUM- POLYMETALLIC
with intercalations of bituminous limestones. The MINERALIZATION
latter, assigned to complex II (Fig. 3), are fairly rich
in pyrite and organic matter, include asphaltite lenses The Walchia shale includes numerous horizons
and smell bituminous. Bituminous limestones from enriched in uranium and other metals, especially
the upper part of the complex, known as the lead, zinc, copper and vanadium. The anomalous
Ruprechtice horizon in the Czech part of the de­ horizons may be assigned to four groups. The first
pression (Tasler eta/., 1979), are characterized by group is related to the subtuffite complex and com­
a fine lamination of algal origin. The rocks were prises three horizons (Fig. 3). The uranium mineral­
formed in the anoxic-pelagic zone of the basin. ization is found in mudstones, and sometimes in
·

Erosional boundaries become progressively more carbonates with pyrite, dispersed organic matter and
frequent in the upper part of complex II. These asphaltite lenses. The weighted mean contents of
boundaries, and intercalations of calcareous sandy uranium for layers 0·90-1· 50 m thick range from 60
limestone, mark the transition to complex III, of to 100 ppm. The mineralization is richest in the
very variable lithology. Complex III consists of uppermost horizon of this group. The contents of
alternating beds of red sandy-silty rocks, and grey­ other metals are also high at this level (zinc up to
black clay-silty or rarely sandy beds which are 2700 ppm, lead up to 400 ppm, molybdenum up to
usually calcareous and contain pyrite and organic 1 10 ppm).
matter in amounts up to 10%. In the southeastern The second group of anomalies is related to com­
part of the studied area (borehole W-15; Fig. 3) all plex II and comprises two to four horizons (Fig. 3).
the rocks of complex III are brown-red in colour, The mineralization is connected here with clay
because some rocks which were originally grey­ shales. The horizons are 0·20-1·50 m thick and
black were oxidized (Wolkowicz, 1988). In that area their weighted mean contents of uranium are from
the complex is composed of several sandstone­ 40 to 80 ppm.
mudstone cycles with subordinate intercalations of The third group of anomalies corresponds to
mudstones and conglomerates and the total thickness complex III (Fig. 3), in which the mineralization is
is estimated at about 120 m. The changes in lithology associated with laminated calcareous shales with
reflect rapid changes in environment during sedi­ laminae and streaks of organic matter, asphaltite
mentation. The brown-red silty-sandy series lenses and dispersed pyrite and galena. The horizons
is characterized by bioturbation and numerous vary from 0·75 to 1·20 m in thickness and the mean
erosional boundaries. It was deposited in the littoral contents of uranium in the most strongly mineralized
 Uranium-rich shale
horizon are from 120 to 200 ppm. The uranium
mineralization is accompanied by increased contents
of zinc, lead, molybdenum, vanadium and arsenic.
The fourth group of anomalies is weakly devel­
oped, and related to complex IV.
GEOCHEMISTRY OF ORGANIC
MATTER IN THE WALCHIA SHALE
In the present study attention was focused on the
organic matter in the Walchia shale, because of the
possible role of organic matter in the concentration
of metals in black shales (see Szalay, 1964; Breger,
1974; Nakashima et al., 1984).
The Walchia shale was deposited in a sedimentary
basin about 50 km wide, and the zone of mixing
due to surface waves extended down to depths of
8-20 m, depending on wind force (Sly, 1978). Sedi­
ments deposited at greater depths are richer in
organic matter than those formed in the zone of
mlXlllg.
The content of organic matter varies from 0·2 to
over 10% in the unoxidized Walchia shale rocks
characterized by uranium mineralization. The cor­
relation coefficient for the contents of organic carbon
and uranium (72 samples) is high, at +0·60 (data in
Fig. 4). The uranium mineralization was found to be
limited almost exclusively to the finest grained rocks:
mudstones, silty mudstones and carbonates of the
shaly type in the classification of Lundegard &
U [ppm]
600
500
400
300
Fig. 4. Correlation between
uranium (U) and organic matter
(Corg) .
221
Samuels ( 1980). Coarser grain sizes, resulting from
higher energy sedimentary environments, appear
unfavourable for the concentration of uranium m
this case.
Studies on organic matter were also aimed at
a more precise reconstruction of the depositional
environment of the uranium-bearing rocks (Table
1). There is a high variability in the content of
bitumens (from 1·2 to 13·5%) in the total organic
carbon, and the highest content of bitumens is found
in rocks of complex II (Table 1). Analyses of iso­
prenoids show a low pristane: phytane ratio (Pr: Ph
= 0·78 to 2· 1), which indicates a strongly reducing
sedimentary environment (Didyk eta/., 1978; Tissot
& Welte, 1978). Low CPI (carbon preference index)
values indicate relatively mature organic matter and
may also indicate a predominantly aquatic origin
(Hunt, 1979). The n-alkane distribution for the
majority of samples peaks at Cl8 (Fig. 5). The
exception is a sample from a uranium-bearing layer
(with uranium content of 272 ppm), characterized
by two n-alkane maxima at C18 and C25 and also
the lowest CPI value (0·61) and a low ratio of
saturated to aromatic hydrocarbons (Table 1).
However, some differences in the geochemical
characteristics of this sample may be due to the
effects of radiation from uranium on the organic
matter, as observed widely elsewhere (e.g. Landais
& Connan, 1980).
The content of hydrocarbons in bitumens is also
important for estimating the potential for remobil-
6 8 10 12 Corgo/o
222 S. Wolkowicz

Table 1. Characteristics of organic matter in the Walchia shale

Depth Lithological U content Total Bitumen BE/TOC Pristane: CPI Hydrocarbon

(m) complex (ppm) organic extract (BE) (%) Phytane content
carbon (TO C) (%) in bitumen
(%) (%)

32·5 IV 9·0 0·6 0·008 1·3 18

56·5 IV 23·7 0·6 0·014 2·3 1·2 1·2 52
114·0 III 3·2 0·6 0·007 1·2 34
124·5 III 272-0 3·9 0·064 1·6 0·6 35
139·2 III 12-0 1·8 0·078 4·3 43
192·7 II 4·2 2·7 0·365 13·5 1·9 0·85 55
194·2 II 12·0 1·6 0·047 2·9 0·8 0·99 50
199·0 II 4·2 0-4 0·054 13·5 2·1 0·96 69
217·0 II 5·5 0·4 0·033 8·2 1·8 0·92 55
297·0 subtuff. 7·0 0·2 0·016 8·0 0·82 43

% Intra-Sudetic Depression are related to a deep lacus­

40
u�4.2 [ppm] trine sedimentary environment. This environment
saw the accumulation of planktonic organic matter
30
of mainly aquatic origin. Concentrations of uranium
20 in the Walchia shale are closely related to the con­
tent of organic matter, and are inferred to be syndia­
10 genetic. High contents of hydrocarbons within
bitumens and the presence of migrated bitumens on
fracture surfaces suggest the possibility of recon­
% centration of uranium within the migrated bitumens.
[ppm]
40
u� 270

30

20 REFERENCES

10 BREGER, LA. (1974) The role of organic matter in the

accumulation of uranium: the organic geochemistry of
the coal-uranium association. Proc. Symp. IAEA
Athens, pp. 99-124.
DIDYK, B.M., SIMONEIT, B.R.T., BRASSELL, S.C. &

Fig. 5. Distribution of n-alkanes in samples with uranium EGLINTON, G. (1978) Organic geochemical indicators of

content of 4.2 and 270 ppm. paleoenvironmental conditions of sedimentation. Nature

ization of the uranium. The hydrocarbon contents in
the bitumen extracts are high, usually in the range
34-69% (Table 1). This, together with a strong
correlation of uranium and organic carbon and the
presence of migrated bitumen on the surfaces of
272, 216-222.
DziEDZIC, K. (1961) Lower Permian of the Intra-Sudetic
Basin. Studia Geol. Pol. 6, 1-121.
GORECKA, A. (1982) Some remarks on Permian volcanic
rocks in the vicinities of Tlumaczow (eastern part of the
Central Sudetic Depression). Kwart. Geol. 26, 599-607.
HUNT, J.M. (1979) Petroleum Geochemistry and Geology.
WH Freeman, San Francisco, 617pp.
KozLOWSKI, S. (1963) The geology of Permian volcanites

fractures suggest the possibility of migration of
uranium. Such phenomena have been reported from
Lodeve (Massif Central, France) by Landais &
Connan ( 1980), and from Scotland by Parnell ( 1985).
CONCLUSIONS
Mineralized Lower Permian black shales from the
in the Central part of the Inner Sudetic Basin (Lower
Silesia). Pr. Geol. Kom. Nauk Geol. PAN 14, 1-84.
KuBICZ, A., MoLENDA, R. & ZuPNIK, K. (1986) Notes on
Permian pyroclastics from Nowa Ruda Region. Kwart.
AGH Geologia 12,77-108.
LANDAIS, P. & CONNAN, J. (1980) Relation uranium­
matiere organique dans deux bassins permiens· francais:
Lodeve (Herault) et Cerilly-Bourbon-l'Archambault
(Allier). Bull. SNEA 4, 709-757.
LUNDEGARD, P.D. & SAMUELS, N.D. (1980) Field classifi-
 Uranium-rich shale
cation of fine-grained sedimentary rocks. J. Sedim.
Petrol. 50, 781-786.
NAKASHIMA, S., DISNAR, J.R., PERRUCHOT, A. & TRICHET,
1. (1984) Experimental study of mechanism of fixation
and reduction of uranium by sedimentary organic matter
under diagenetic or hydrothermal conditions. Geochim.
cosmochim. Acta 48, 2321-2330.
NEMEC, W., POREBSKI, S.J . & TEISSEYRE, A.K. (1982)
Explanatory notes to the lithotectonic Molasse Profile of
the Intra-Sudetic Basin, Polish Part (Sudety Mts,
Carboniferous- Permian). In: Tectonic Regime of
Molasse Epochs. Report on Activities of Working Group
3.3 (Ed. by H. Lutzner & G. Schwab), pp. 267-278.
Potsdam.
NowAKOWSKI, A. (1968) Permian volcanites of the Suche
Mts in the Intrasudetic Basin. Ceo!. Sudetica 4,
289-400.
223
PARNELL, J. (1985) Uranium/rare earth-enriched hydro­
carbons in Devonian sandstones, northern Scotland. N.
lb. Miner. Mh. H. 3, 132-144.
SLY, P.G. (1978) Sedimentary processes in lakes. In: Lakes,
Chemistry, Geology, Physics (Ed. by A. Lerman),
pp. 65-90. Springer, New York.
SzALAY, A. (1964) Cation exchange properties of humic
acids and their importance in the geochemical enrich­
ment of UO/ + and other cations. Geochim. cosmochim.
Acta 28, 1605-1614.
TISSOT, B. & WE LTE, D.H. (1978) Petroleum Formation
and Occurrence. Springer, New York.
WOLKOWICZ, S. (1988) On the sedimentation of the Lower
Permian Walchia Shales from Ratno Dolne (Intra­
Sudetic Depression). Przegl. Geol. 36, 214-218.
 Index

References to figures appear in italic type

References to tables appear in bold type.

Abu Hamata 165, 166, 167, 169 metals in 185-6 Humber Arm Allochthon
Abu Thora Formation 161, 162 cobalt 99 geochemistry 122-5
akaganeite 63-4 colemanite 151 metal distribution 123-5,
Algoma type iron formations 33,37 copper 128-9, 130-2, 133-4, 137 128-9, 130-2, 133-4
alum shale, metals in see metals and copper deposits see Dongchuan- sulphur-carbon ratios 125-8
rare earth elements, Sweden Yimen copper deposits sulphur isotopes 134-5, 136,
aluminium mineralization 168 copper mineralization, Sinai 159, 137
alunite 166,168 161,168-70 geology 119-120, 121, 122
America, South 187-8 Cow Head Group 121,122,123, sedimentology 122
antimony 99 126-9,131-2, 133-7 hydrocarbons, metals in 187-91
asbolane-buserite 103-4,105,106
asbolanes 69,103
asphalt beds, China 193-9 Datangpo Formation 39-40 Irish Sea, uranium mineralization
atacamite 169 fossils from 110-12 190
Atlantis-Il Deep 58, 63,71 geological setting 39-40, 41, 42- l rishtown Formation 122, 126,128,
iron oxyhydroxides 59-62, 63-5 3 130, 134-5
manganese oxyhydroxides 60, 61, manganese deposits 39, 42-3, iron and manganese deposits, China
62-3,65-8 44-9 109
Australia see Groote Eylandt Dongchuan-Yimen copper deposits geology 109-10
manganese norm stratigraphy 175 microbial fossils 110-12
azurite 169 geochemistry microbiota and minerals 113-16
fluid inclusion 179, 180 iron and manganese facies see

isotope 177-8, 180 manganese and iron facies in

barite 124-5,134, 135,136,137 organic 175,177 hydrolithic sediments
barium precipitation 123-5 trace element 173, 176 iron carbonate layers, Borneo
Bela Stena magnesite deposit 151 analytical data 141
Bezymiannaya Seamount see formation 142-4
manganese-iron crusts, Eagle Island Formation 122,123, outcrops 139, 140, 141
Bezymiannaya Seamount 640 126,129-30 iron-manganese oxyhydroxides
birnessite 103, 104,106 Egypt see Urn Bogma region, Sinai 60-2
bitumen, metals in 188-91, 221-2 iron mineralization 114,143-4,168
borates 151 iron oxyhydroxides 57-8
Borneo see iron carbonate layers, Fengshan copper deposits 178, 179 in Atlantis-II Deep 58-9,63-5,
Borneo ferrihydrite 58,59, 60, 65 71
brochantite 169 fossils, metal enrichments in 186-7 in Thetis Deep 68-71
: buserite 62, 105 iron vernadite 103, 105,106
ironstone 151, 152-3, 154-5
goethite 58,59, 64, 69, 70 isotope geochemistry
Cahuasas Formation 19, 20 Groote Eylandt manganese norm Datangpo manganese
Cape Verde Plate 96, 99 3-4,14 deposits 45-6
carbonate deposition 26-7 methodology 4, 5-7, 8-9, 10-13 Dongchuan deposits 177-8,180
China see Datangpo Formation; Guacamaya Formation 18, 19 Mineoka Umber 84-5
Dongchuan-Yimen copper Newfoundland 134-5,136,137
deposits; iron and manganese Tetzintla mine 23
deposits, China; Lijiang basin; Hare Bay Allochthon 120
organic matter and Hatcho Formation 75
metalliferous deposits, China Heguri Formation 75 Japan see Mineoka Umber
Chipoco facies 21,22,23,24, 25 hematite 58,59, 65, 69, 70 Jarandol Basin 149, 151, 152-3
chrysocolla 163,166,169-70 Hequing manganese deposit 55
Clarion-Clipperton Fracture 105 howlite 151
coal Huayacocotla Formation 18,19-20 Kalimantan Province 139-44
Borneo 140, 141 Huizachal Formation 19 Kamogawa Formation 75-6, 87

Sediment-Hosted Mineral Deposits Edited by John Parnell, Ye Lianjun 225

and Chen Changming © 1990 The International Association of Sedimcntologists
ISBN: 978-0-632-02881-8
226 Index

Kangdian axis 174, 175 Thetis Deep 69,70-1 Northern Head Group 122,123-9,
kaolinite 168 manganite 63, 67-8 130, 133,134-7
Karadzhal deposits 33 metal enrichments in organic
materials 183-5
organic material as an ore 188- oil shales 148,185-6
lacustrine basins, metals in 184-5 90,191 organic materials, metal enrichment
lacustrine oil shales 185 ore coeval with material 190 see metal enrichments in
Lahn-Dill type iron ore 154 post-ore organic material 185-8 organic materials
Lake Superior type iron formations metalliferous deposits and organic organic matter
32,33, 37 matter see organic matter and in alum shale 203-6,209-13
lead 128-9, 130-2, 133-4,137 metalliferous deposits, China in copper minerals 163,174,177
lepidocrocite 58,59,60, 65, 69,70 metals and rare earth elements, in manganese deposits 45-7, 48
Liangiiehe Formation 40, 42 Sweden 203-6 in Red Sea sediments 65
Lijiang Basin 53 analysis 206, 207, 208 in Walchia shale 221-2
basin analysis 51-3 discussion of results 208-9 organic matter and metalliferous
basin evolution 53 rare earth enrichments 210-12 deposits, China 193,
manganese geochemistry 52-3 regional geology 206 199-200
manganese mineralization 53-6 Mexico, East see Molango District characteristics 194-8
Lough Neagh Basin 185 microbial fossils 110-16 metals and minerals in asphalt 198
Lower Dolostone Member 161, 162 microbiota from iron and manganese significance 198-9
lueneburgite 151 deposits oxisol formation, Borneo 142-3
Luoxue-Yimen copper deposits 178, microbial fossils 110-16
179 microbiota-mineral relationships
112-16 Permian Lodeve Basin 187,188
sequence of deposits 109-10 phosphorus 168
magnesite 151 Mid-Atlantic Ridge 103 Pimienta Formation 21
magnesium 209 Middle Arm Point Formation 122, podsols, Borneo 143-4
magnesium asbolane 104,106 123,124-5,126, 130, 135 Poland see uranium enrichment,
magnetite 39,69, 70 Minas Ragra 188,189 Poland
malachite 162, 163,164, 166, 169 Mineoka-Kobotoke-Setogawa potassium 168
manganese 123, 124 tectonic belt 73, 74 Proterozoic Datangpo Formation see
manganese and iron facies in Mineoka Umber 73-4,76,87 Datangpo Formation
hydrolithic sediments analysis 77-9,80-1,82,83-5 pseudomalachite 163,170
globular distribution 32-3,34-6, geological setting 74-6 pyrite 136
37-8,105 occurrence and samples 76-7 pyrolusite 82, 83, 86
related facies 31-2 origin 85-6
see also iron and manganese site of deposition 86-7
deposits in China mineral deposits, Yugoslavia 147 radioactive organic materials 189
manganese deposits, Datangpo facies 147-8, 149, 150, 151 rare earth elements 84,86,174,
Formation 39, 42-3,44-9 ironstone 151,152-3, 154-5 210-13
manganese feroxyhyte 103 Minette-type iron ore 154,155 Red Sea sediments 57-8 see also
manganese goei�ite 66-7,70 Minle Formation 110, 111 Atlantis-II Deep; Thetis Deep
manganese-iron crusts, fossils from 112 rhodochrosite 22,23,42,43,46, 47
Bezymiannaya Molango district rhodonite 33
Seamount 640 89,101-2, manganese mineralization 17-18, Rocett (Bezymiannaya) Seamount see
106-7 23-4,27 manganese-iron crusts on the
analytical methods 89-90 mineralogy 22-5 Bezymiannaya Seamount 640
genesis 99 palaeogeography 24-7 Rungan River deposits 139,140,
geochemistry 90,92-3, 94,95-6, petrography 21-2 141,144
97, 98, 100 stratigraphy 18-21
geological setting and structure Moonta copper deposit 189, 190
90,94 San Andres Member 21,22,24,25
mineral composition 100,103-4 San Francisco manganese-iron
model of formation 104-5 Nantuo Formation 40, 42 deposits 33
structure 91 natural gas, metalliferous deposits in 'Santiago' Formation 20,22,23,24,
manganese mineralization 194 26,27
Lijiang Basin 53-6 Nazas Formation 20 sea level and sedimentation 26-7,
Mexico, East 17-18,23-4,27 Newfoundland see Humber Arm 46,47
Sinai 168 Allochthon Setogawa Umber 75-6, 86-7
South China 39,43-9, 114-16 nickel 94,97,128-9,130-2, Shirataki limestone 85
manganese oxyhydroxides 133-4,137 Shishan-Fengshan copper deposits
Atlantis-!I Deep 60,61, 62-3, normalization techniques 3-4,5-7, 177,178
65-8,71 8-9, 10-13 siderite 139,140, 141, 144
 Index 227

silicon 168 Tielin Formation 110, 111 uranium-rich bitumen 189-90

silver 97, 99 fossils from 112
Sinai see Urn Bogma Region, Sinai Tiesiao Formation 40, 42
Slanci Basin 148, 149 tincalonite 151 Valjevo-Mionica Basin 148, 149
sodium 209 todorokite 60,61, 66-7 vanadium
Songgui Formation 51,53, 54 turquoise 163,166, 170 in alum shale 209-10
stratafer sediments 31-2 in organic matter 184,185,188
sulphate minerals, stability 124-5, Venezuela 187-8, 189
177 ulexite 151 Vranje Basin 148, 149
sulphide ores, Newfoundland 128, Urn Bogma region, Sinai 159
129, 133-4,137 copper mineralization 159, 161,
sulphur-carbon ratios 125-8 168-70 Walchia shale, uranium enrichment
sulphur isotopic analysis 134-5, geochemistry 166 ; 167, 168 see uranium enrichment,
136,137 lithostratigraphy 160,161-2,165 Poland
Sweden see metals and rare earth minerals 162-3, 164, 166
elements, Sweden Upper Dolostone Member 161, 162
uranium Yangtze Craton 39-40
in alum shale 204, 205,206, 208- Yimen copper deposits see

Tajmiste ironstones 152-3, 154 14 Dongchuan-Yimen copper

Taman Formation 21,22,24 in organic matter 185,186-7, deposits
'Taman Mixto' 21 188-90,191, 199 Yugoslavia see mineral deposits
Tepexic Formation 20, 21-2, 26 uranium enrichment, Poland 217, Yugoslavia
Tetzintla mine 18,19, 23,26 218
Thetis Deep organic matter in shale 221-2
iron oxyhydroxides 68-71 sedimentology of shale 217,219 zeolites 148
manganese oxyhydroxides 69, uraniurn-polymetallic zinc 128-9, 130-2, 133-4,137
70-1 mineralization 220-1 Zlatokop-Vranje Basin 150