association of manganese ore and phosphorite-bearing facies.pdf

ISSN 0024-4902, Lithology and Mineral Resources, 2009, Vol. 44, No. 1, pp. 1–18. © Pleiades Publishing, Inc., 2009.Original Russian Text © V.N. Kholodov, R.I. Nedumov, 2009, published in Litologiya i Poleznye Iskopaemye, 2009, No. 1, pp. 3–22.

1

The concept of spatial association (parasteresis) ofminerals in different regions of the Earth originated inthe terminal 18th–initial 19th centuries.

The idea of spatial association of some minerals wasfirst proposed by the Russian Academician V.M. Sever-gin (1798–1816), who studied regularities of their spa-tial distribution in Russia. He demonstrated that theoccurrence frequency of minerals varies notably at theEarth’s surface and formulated the concept of mineralcontiguity, i.e., the ability of minerals to form associa-tions.

The same idea appeared later in works by pupils ofthe famous German scientist A. Werner. One of them,an outstanding mineralogist from Freiberg Breithaupt(1849), who emphasized the significance of the con-cepts of mineral contiguity, proposed the term“paragenesis”

1

and described numerous examples oftheir spatial association. Since that time, the term“paragenesis” is widely used in the mineralogical liter-ature.

The works by V.I. Vernadsky and A.E. Fersman wid-ened substantially its essence. As is known, theseresearchers developed the principles of geochemistry.Naturally, they included chemical elements into thenotion of paragenesis.

Vernadsky (1910, 1923), who developed the theoryof paragenesis, imparted a dual sense to this notion.Paragenesis was interpreted as a geochemical process

1

The term consist of two Greek words: “para” (near) and “gene-sis”).

that determined the formation of certain mineral bod-ies, associations, and generations, on the one hand, andas the mineral bodies, associations, and generations, onthe other hand.

According to Vernadsky, isomorphism is of greatsignificance in the formation of geochemical paragene-ses. He defined 18 typomorphic series, which deter-mined the cooccurrence of chemical elements.

In

Geochemical and Mineralogical Methods ofProspecting for Mineral Resources

published in 1940,Academician A.E. Fersman proposed the followingdefinition of the notion of paragenesis: “paragenesis isa cooccurrence of minerals (or elements) in a certaingeochemical system related to a certain geochemicalprocess” (Fersman, 1953).

It should be emphasized that both Vernadsky andFersman accepted the persistence of cooccurrence (themain feature of paragenesis) as a criterion of similargenesis. Despite the discrimination of smaller catego-ries (associations and generations of elements or min-erals), they considered occurrence frequency and gene-sis as different aspects of the same phenomenon.

In (Pustovalov, 1940), the notion of paragenesisgained a wider interpretation: it included not onlychemical elements and minerals, but also sedimentaryrocks. Postulating that mechanical and chemical differ-entiation of matter represents the main regularity insedimentary rock formation, Pustovalov wrote: “…thenormal sedimentary process is characterized by thesuccession of certain types of sedimentary rocks, whichreplace each other in both lateral and vertical direc-

Association of Manganese Ore and Phosphorite-Bearing Faciesin Sedimentary Sequences: Communication 1. Parastereses and Parageneses of Phosphorus

and Manganese in Mesozoic–Cenozoic and Upper Paleozoic Rocks

V. N. Kholodov and R. I. Nedumov

Geological Institute, Russian Academy of Sciences, Pyzhevskii per. 7, Moscow, 119017 Russiae-mail: [email protected]

Received May 19, 2008

Abstract

—It is shown that cooccurrences (parastereses) of chemical elements, minerals, sedimentary rocks,facies, and formations should be distinguished from their parageneses, which represent geological formationsrelated to a single geological process. It has been established that phosphorus is concentrated in sedimentarymanganese ores and is not accumulated in volcanosedimentary and hydrothermal deposits. Parageneses of Mnand P in sedimentary deposits are characterized. Parastereses of manganese ore and phosphorite-bearing faciesin Oligocene rocks of southwestern Eurasia, Mesozoic and Upper Paleozoic sections of the Urals, and Meso-zoic–Cenozoic sequences of Morocco are considered.

DOI:

10.1134/S0024490209010015

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tions, resulting in the formation of regular associationsdetermined by the character of surficial differentiationin each sedimentation zone. This provides grounds fordefining

the paragenesis of sedimentary rocks.”

Hewrote further: “…the dominant accumulation of genet-ically related sediment types at the Earth’s surface fol-lows a certain succession in line with sedimentary dif-ferentiation; replacement of the dominant sedimenttypes is repeated periodically according to the generalrhythm of the Earth’s geological development; there-fore, we have grounds for defining

the paragenesis ofsedimentary sequences

(Pustovalov, 1940, p. 381).Accepting such a wide definition of paragenesis

proposed by Pustovalov, we should note the followingfact: vagueness and uncertainty of this notion areamplified when we pass from formations of a low orga-nization level (chemical elements) to those of a higherlevel (sedimentary rocks, sequences, formations, andothers).

Pustovalov’s ideas of the paragenesis of sedimen-tary rocks were supported and further developed bysome tectonists (primarily, N.P. Kheraskov andN.S. Shatsky).

In the fundamental work by Kheraskov (1952), thesedimentary formation was defined as paragenesis ofsedimentary rocks. He wrote: “Rocks represent aparagenesis of minerals; formations, a paragenesis ofrocks. Similarly as rocks characterized on the basis oftheir mineral composition and structure (texture), for-mations should be described and classified according totheir composition and structure” (Kheraskov, 1952,p. 37).

In the later work dedicated to phosphorite-bearingformations, Shatsky developed in fact the same ideas:“Geological formations are assemblages or associa-tions of rocks, separate elements (rocks, beds, and sed-iments) of which are paragenetically correlated in bothtemporal (interlayering and succession) and spatialaspects (facies zones and others).” He wrote further:“Formations represent natural assemblages, com-plexes, and parageneses of rocks rather than arbitrarysets of rocks and facies, as supposed by some research-ers” (Shatsky, 1955, p. 8).

It is interesting that according to Shatsky andKheraskov, identification of specified formationsrequires the purely empirical discrimination of similarassociations of rocks or facies that are developed uni-versally in different regions of our planet.

Academician Betekhtin (1949, 1950) proposed aquite different interpretation of the notion of paragene-sis. He was first to show that the permanent cooccur-rence of minerals not necessarily indicates their similarorigin. He noted, for example, that iron and copper sul-fides always occur together with iron oxides and mala-chite in hydrothermal veins. However, a detailed analy-sis of the sequence of mineral formation reveals the fol-lowing fact. Iron and copper sulfides represent an earlygeneration related to the interaction of metals with

hydrogen sulfide; the sulfides were subsequently oxi-dized, and the influence of carbon dioxide results in theformation of malachite. Thus, we are dealing with two

different

(in terms of time and dominant chemical reac-tions) processes. Hence, the association of perma-nently occurring minerals includes two parageneses:paragenesis of sulfides and paragenesis of oxides andcarbonates.

Thus, according to Betekhtin, the empiricallydefined assemblage of minerals, chemical elements, orsedimentary rocks cannot be considered a genetic unityor paragenesis. According to the authors of articledevoted to paragenesis in (

Geologicheskii Slovar

,1973), such cooccurrence should be called parastere-sis.

2

Only the comprehensive study of spatiotemporalrelationships between components of parasteresismakes it possible to outline genetically different associ-ations or parageneses.

It is clear that empirical discrimination of associa-tions of chemical elements, minerals, or sedimentaryrocks (parastereses) represent a first stage of theresearch, while observations of spatiotemporal rela-tionships, discrimination between generations, andgenetic interpretations (parageneses) crown the studyof geochemistry, mineralogy, sedimentology, facies,and formations.

Concluding this brief historical review and passingto the description of manganese ore and phosphate-bearing faces, we should emphasize that this article isonly devoted to general characteristics of the cooccur-rence of manganese ores and phosphates. More compli-cated issues of their paragenesis are discussed here onlypartly and only for cases furnished with a sufficientamount of factual material.

Cooccurrence of Mn and P in sedimentary rocks isa well-known phenomenon. It is considered in manyworks (Betekhtin, 1946; Rozhnov, 1967; Gryaznov andChervonookaya, 1967; Gavrilov, 1972; Varentsov andRakhmanov, 1974; Danilov, 1982; Roy, 1986; and oth-ers). Recently, it became clear that issue of the paraster-esis of Mn and P includes several aspects:

(1) regularities of phosphorus distribution in UpperPaleozoic, Mesozoic, and Cenozoic sedimentary man-ganese deposits;

(2) spatiotemporal relationships between manga-nese ore and phosphate-bearing facies in the UpperPaleozoic and Mesozoic–Cenozoic sequences;

(3) cooccurrence of deposits of old pelletal phos-phorites with sedimentary ferromanganese ores andsedimentary manganese deposits in the Lower Paleo-zoic and Precambrian sequences.

2

The term consists of two Greek words: para (near) and stereo(volumetric, spatial); i.e., it indicates spatial association.


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ASSOCIATION OF MANGANESE ORE AND PHOSPHORITE-BEARING FACIES 3

We shall attempt to discuss these aspects in two arti-cles.

REGULARITIES OF PHOSPHORUS DISTRIBUTION IN THE UPPER PALEOZOIC, MESOZOIC, AND CENOZOIC SEDIMENTARY

MANGANESE DEPOSITS

It is well known that Mesozoic and Cenozoic sedi-mentary manganese ores are always enriched in phos-phorus. As was shown in (Betekhtin, 1930, 1946),phosphorus is a harmful admixture in manganese ore.Therefore, like the Fe content, the P content alwaysdetermines the quality of this mineral resource.

Table 1 based on data of many researchers demon-strates the distribution of P and Fe in ores from differentsedimentary deposits of Russia and some other coun-tries. Provided that the average or clarke P content insedimentary rocks is estimated at 0.093% (Vinogradov,1962) and the average P content in stratisphere is esti-mated at 0.078% (Ronov, 1993), it becomes clear thatthe quantity of phosphates buried in bottom sedimentstogether with Mn is tens or even hundreds of timeshigher than its clarke concentrations.

It should be emphasized that the quantity of Pinvolved in the sedimentary process exceeds substan-tially that in hydrothermal and volcanosedimentarymanganese ores.

Table 2 presents published data characterizing thedistribution of Fe, Mn, and P in hydrothermal and sed-imentary exhalative deposits of different countries. Theanalysis reveals that volcanic-associated manganesedeposits are always enriched in Fe, slightly depleted inMn, and extremely depleted in P (Figs. 1, 2).

Deficit of P in hydrothermal and volcanosedimen-tary ores was first suggested by Rozhnov (1967) andGavrilov (1972) and subsequently confirmed bySokolova (1982). This inference is substantiated by thecomparison of diagrams (Figs. 1, 2) and is consistentwith the following fact: phosphorus participatesactively as apatite in the magmatic process, but it isinvolved rarely in hydrothermal and volcanogenicexhalative processes. This issue is scrutinized in ourprevious works (Kholodov and Butuzova, 1999;Kholodov, 2002, 2003a, 2003b, 2006).

The Guberly, Kos-Istek, and Karagala manganesedeposits associated with Ordovician volcanosedimen-tary formations of the Sakmara allochthon (Urals) rep-resent exceptions among hydrothermal exhalativedeposits: the P content in them amounts to 2–3%(locally, 11–18%). This is, however, explained bysuperimposition of the hydrothermal volcanogenicmanganese mineralization on sedimentary phosphoriteformation widely developed in Ordovician organic-richsiliceous phtanite sequences (Gavrilov, 1972;Khvorova et al., 1978).

Similar situation was likely characteristic of theUpper Paleozoic manganese deposits in the Czech

Republic and some volcanosedimentary deposits inJapan, where significant quantities of phosphorus wereaccumulated (Takabatake, 1956). These areas werecharacterized by the superimposition of sedimentaryphosphorite formation and volcanosedimentary manga-nese deposition.

The geological setting in these deposits resemblesthat in the Caradocian uranium–rare metal–phosphatedeposits of northern Kazakhstan, which are consideredby many researchers (S.D. Levina, L.V. Khoroshilov,and others) as hydrothermally altered sedimentarydeposits. Their origin is attributed to a multistage pro-cess, which commenced with the formation of old nod-ular-stratiform phosphate bodies, and the subsequenthydrothermal redeposition (Kholodov and Butuzova,1999).

Hydrothermal and volcanosedimentary manganesedeposits are characterized by high-quality ores with avery low content of phosphates. It should also be notedthat volcanosedimentary and hydrothermal manganesedeposits frequently contain elevated admixtures of Cu,Pb, Zn, As, Ba, Be, W, and other elements (Rozhnov,1967; Strakhov et al., 1967, 1968; Varentsov and Rakh-manov, 1974; Roy, 1981). Combined with the deficit ofP, this feature imparts a unique geochemical appear-ance to ores of this group and even serves as a geneticsignature of endogenic ores.

Of particular interest is the behavior of phosphorusin sedimentary oxide and carbonate ores. Table 1 dem-onstrates that almost each sedimentary deposit containsoxide ores usually composed of pyrolusite, psilo-melane, cryptomelane, todorokite, and birnessite, aswell as carbonate ores represented by rhodochrositeand manganiferous carbonates.

Analysis of the behavior of P in these two differentmineral types of manganese ores reveals that averagevalues of percentage variations of P contents areapproximately equal (Fig. 3). In other words, elevatedP concentrations are characteristic of both mineralogi-cally different groups and they represent a single cooc-currence (parasteresis) of high contents of phosphatesand manganese ores.

However, observations of occurrence forms of phos-phates in manganese deposits in the South Ural Basin(Gryaznov and Chervonookaya, 1967; Khodak, 1976;Shnyukov and Orlovskii, 1993) suggest that phospho-rus is precipitated and fixed in oxide and carbonate oresby different ways. It should primarily be noted thatphosphorus occurs in both manganese ores varieties asphosphatized bone breccia, accessory apatite, phos-phate admixture in large psilomelane beans and concre-tions, vivianite, and phosphate fringes on clay minerals.

The first group of phosphate inclusions is repre-sented by clasts and small crystals of accessory apatite,as well as fragments of phosphatized mammal and rep-tilian bone remains. They were mechanically depositedin the manganese ore bed and were derived from the

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Table 1.

Distribution of Fe, Mn, and P (%) in sedimentary manganese deposits

Deposit, occurrence Fe Mn P Source

Zelenyi Dol

(Ukraine) – 6–19.9 0.222 Shnyukov and Orlovskii, 1993

Ordzhonikidze

(Ukraine)average 0.86–2.05 45.91–54.99 0.152–0.78 Betekhtin, 1946oxide ores 0.35–7.44 6.96–73.76 0.07–1.04 Gryaznov, 1967carbonate ores 1.41–3.30 7.00–33.86 0.08–0.24 The sameoxide ores 2.63–2.84 19.4–22.58 0.173–0.226 Shnyukov et al., 1993oxide–carbonate ores 2.13–3.10 22.20–34.87 0.137–0.220 The sameaverage 2.50 25.60 0.212

"

Marganets

(Ukraine)average 0.7–3.5 30–55 0.16–0.35 Betekhtin, 1946oxide ores 0.35–7.44 6.9–73.76 0.07–1.01 Gryaznov, 1967carbonate ores 1.41–3.30 7.0–33.86 0.08–0.24 The sameoxide ores 0.57 51.2 0.02 Varentsov and Rakhmanov, 1974oxide–carbonate ores 1.07–1.53 18.3–44.4 0.25–0.31 The samecarbonate ores 1.31 23.70 0.09

"

oxide ores 2.60–2.88 22.76–26.22 0.15–0.17 Shnyukov et al., 1993oxide–carbonate ores 2.25–3.23 20.47–28.87 0.14–0.20 The samecarbonate ores 2.45 21.71 0.38

"

Tokmak

(Ukraine)oxide ores – 35.68 0.32 Gryaznov and Chervonookaya,

1967carbonate ores – 24.65 0.18 The sameoxide ores 4.35–8.90 11.66–45.87 0.18–0.54 Shnyukov et al., 1993oxide–carbonate ores 2.45–6.29 10.29–52.31 0.16–0.27 The samecarbonate ores 2.24–10.13 8.88–32.56 0.09–0.25

"

Chiaturi

(Georgia)oxide ores 0.1–1.2 42–58 0.10–0.22 Betekhtin, 1946carbonate ores 2–4 6–30 0.20–0.30 The sameoxide ores 0.33–1.73 11.57–60.61 0–0.2 Shterenberg et al., 1967carbonate ores 0.26–1.42 3.55–32.22 0–0.58 The sameoxide ores 0.82–1.46 29.3–49.3 0.14–0.16 Tabagari, 1980carbonate ores 0.59–1.62 14.4–25.2 0.03–0.39 The same

Kvirili

(Georgia)oxide ores 1.09–5.2 11.2–39.3 0.10–0.47 Dolidze et al., 1980carbonate ores 3.4–16.8 8.1–24.3 0.14–0.54 The same

Laba

(Russia)average 1.98–4.25 13.45–26.13 tr.–0.19 Betekhtin, 1946oxide ores 1.80–2.25 21.18–28.85 0.014–0.03 Kalinenko et al., 1967carbonate ores 1.04–6.03 12.36–34.63 tr.–0.65 The sameoxide ores 1.80–2.25 21.48–28.85 0.014–0.03 Kalinenko, 1990carbonate ores 1.22–5.15 14.82–33.30 tr.–0.06 The same

Mangyshlak

(Kazakhstan)oxide ores 1.30–6.34 7.23–46.90 tr.–0.91 Tikhomirova and Cherkasova, 1967carbonate ores tr.–3.57 tr.–23.08 tr.–0.79 The same

Polunochnoe

(Russia)oxide ores 4.16–4.88 20.74–32.17 0.11–0.6 Betekhtin, 1946oxide–carbonate ores 3.05–3.60 20.7–21.88 0.19 The samecarbonate ores 4.1–4.70 27.14–27.18 0.15–0.17

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Jurassic–Cretaceous weathering crust underlying theore bed (Fig. 4).

As was shown in (Kholodov, 2006), this weatheringcrust was composed of material eroded from the apa-tite-bearing gabbro–anorthosite massifs in the Ukrai-nian crystalline shield. The crust contained numeroushigh-grade apatite and titanomagnetite placer deposits

(Irsha placer group, Novopoltavsk rare-metal–apatiteplacer group, and others), in addition to clayey elu-vium.

Erosion of these terrigenous accumulations andwashout of numerous phosphate bone remains pro-moted the universal enrichment of ore-bearing beds inthe South Ukraine Basin by phosphate fragments.

Table 1.

(Contd.)

Deposit, occurrence Fe Mn P Source

Marsyat

(Russia) 4–10 25–35 0.2–0.6 The same

Ulutelyak

(Russia)

total content 1.01–1.63 6.20–8.27 0.05–1.05 The same

total content 1.97–2.43 5.58–9.39 0.05–0.06

"

oxide ores 0.42–2.79 19.97–20.95 –

"

carbonate ores 0.99–1.02 3.7–12.56 –

"

Imini

(Morocco) 1.5–2.3 47.51–56.57 0.03–0.06 Bouladon and Jurovski, 1956

Bu Aggun

(Morocco)

oxide ores 0–0.1 46.75–52.40 0.01–0.23 Thai, 1990

oxide–carbonate ores 0 10.07 0.01–0.23 The same

carbonate ores 0.5 31.30 0.01–0.23

"

Saint Bebe

(Morocco)

oxide ores 0.05 46.7–50.84 0.01–0.14

"

carbonate ores 0.05 1.67 0.01–0.14

"

Note: (–) no data.

%10

9

8

7

6

5

4

3

2

1

0

%80

70

60

50

40

30

20

10

0

%1.1

1.0

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0

16.8Iron Manganese Phosphorus

Ord

zhon

ikid

ze

Mar

gane

ts

Tok

mak

Chi

atur

i

Kvi

rili

Dep

ress

ion

Lab

a

Man

gysh

lak

Polu

noch

noe

Mar

syat

Ulu

tely

ak

Imin

i

Ord

zhon

ikid

ze

Mar

gane

ts

Tok

mak

Chi

atur

i

Kvi

rili

Dep

ress

ion

Lab

a

Man

gysh

lak

Polu

noch

noe

Mar

syat

Ulu

tely

ak

Imin

i

Ord

zhon

ikid

ze

Mar

gane

ts

Tok

mak

Chi

atur

i

Kvi

rili

Dep

ress

ion

Lab

a

Man

gysh

lak

Polu

noch

noe

Mar

syat

Ulu

tely

ak

Imin

i

Fig. 1.

Distribution of Fe, Mn, and P in sedimentary manganese ores.

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The second and third groups include typical authi-genic either diagenetic or sedimentary phosphate min-erals formed in the Oligocene basin.

The second group consists of phosphates forminglarge psilomelane concretions (nodules), vivianiteinclusions, and phosphate rims on clay minerals. Theyare most typical of manganese oxide ores related to col-loidal processes of sorption or chemosorption.

It should be remembered that orthophosphate, awidespread form of phosphates in marine and intersti-tial waters, is characterized by the negative charge; irontrioxide, by the positive one. It means that interstitialwaters are more favorable for the formation of vivianitein manganese ore beds.

It is more difficult to explain the formation of otherphosphorous compounds because both manganeseoxide and silica are characterized by negative charges,which hamper their precipitation together with ortho-phosphate.

This issue can likely be explained by the recent dis-covery of an additional form of phosphorus occurrenceas polyphosphates in seas and oceans. The polyphos-phates appeared to be widespread and closely associ-ated with biological processes in marine settings.

According to (Hooper, 1974; Van Veser, 1974; andothers), polyphosphates represent complex compoundsconsisting of phosphate chains, in which phosphatecompounds are interconnected with oxygen bridges

and multiply repeated. They are defined by the generalformula

å

n + 1

P

n

O

3n + 1

, where M is metal, hydrogen ion,and others. The characteristic feature of polyphos-phates is their ability to carry both positive and negativecharges. Like structures of clay minerals, the “head”and “tail” of such complex molecules may be charac-terized by positive and negative charges, respectively.

Such a property is responsible for the ability ofpolyphosphates to precipitate together with clay miner-als. It is conceivable that polyphosphates are present inpsilomelanes (complex colloids).

In any case, the main process in manganese orezones with dominant manganese and Fe hydroxides isthe coprecipitation of complex colloid compounds.

The third group of phosphate accumulations includesphosphate minerals associated with manganese carbonateores. In addition to rhodochrosite (MnCO

3

), siderite(FeCO

3

), and sideroplesite (Mg,Fe(CO

3

), they containwidespread kurskite or francolite. The last mineral isdefined by the formula

Ca

10

[PO

4

]

6

[F

2

(OH)

2

(CO

3

)O]

or

Ca

10-n/2

(PO

4

)

6-m

(CO

3

)

m

F

2

, where m < n. In fact, it repre-sents apatite with

PO

4

in the lattice replaced by carbon-ate. It can likely be stated that all minerals of this groupformed in the same chemical precipitation settings.

It should be mentioned that phosphates in the sedi-mentation zone dissolve readily under slightly acidconditions and precipitate in slightly alkaline settings

%10

9

8

7

6

5

4

3

2

10

%80

70

60

50

40

30

20

100

%1.1

1.0

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.10

Iron Manganese Phosphorus

Kar

adzh

alK

tai

Tak

hta-

Kar

achi

Koz

haev

sk Z

haks

yT

asob

aL

os C

hivo

sC

harc

o R

edon

doB

arra

ncos

Ponu

poE

l Cri

sto

Fran

cisc

an F

orm

atio

n

19.312.4

14.123.3

11.8

Tet

rits

karo

i

Kar

adzh

alK

tai

Tak

hta-

Kar

achi

Koz

haev

sk Z

haks

yT

asob

aL

os C

hivo

sC

harc

o R

edon

doB

arra

ncos

Ponu

poE

l Cri

sto

Fran

cisc

an F

orm

atio

n

Tet

rits

karo

i

Kar

adzh

alK

tai

Tak

hta-

Kar

achi

Koz

haev

sk Z

haks

yT

asob

aL

os C

hivo

sC

harc

o R

edon

doB

arra

ncos

Ponu

poE

l Cri

sto

Fran

cisc

an F

orm

atio

n

Tet

rits

karo

i

Fig. 2.

Distribution of Fe, Mn, and P in hydrothermal and volcanosedimentary manganese ores.


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(Kholodov, 2002, 2003a, 2003b; 2004, 2008). Distor-tion of the carbonate equilibrium and alkalization ofwaters in the manganese carbonate formation zonestimulates the accumulation of phosphates as kurskiteor francolite.

Thus, it is clear that cooccurrence of phosphoruswith manganese ores (or parasteresis of P and Mn) con-sists of two distinct (sorptional and chemical) paragen-eses.

COOCCURRENCE OF MANGANESEORE AND PHOSPHORITE-BEARING

FACIES IN UPPER PALEOZOICAND MESOZOIC–CENOZOIC SEQUENCESOf particular interest are spatiotemporal relation-

ships between manganese ore and phosphorite-bearingfacies in Mesozoic–Cenozoic sequences of Russia andsome adjacent countries.

The facies characteristic of Eocene–Oligocene sed-imentary manganese deposits is given in (Betekhtin,1946; Strakhov, 1964; Strakhov et al., 1968; Varentsovand Rakhmanov, 1974; Rakhmanov et al., 1978, 1982;Shnyukov and Orlovskii, 1993).

It has been established that manganese ore accumu-lations are formed in the underwater deltaic, deltaicsandy–silty and silty–clayey, and carbonate shelffacies.

They are characterized by highly variable grain-sizecomposition with the maximal ore range usually shiftedas shown in Fig. 5 adopted from (Strakhov, 1968). Ore-enclosing rocks of the Laba deposit are obviously rep-resented by coarse-grained sediments (sands and evengravelstones), while they associate largely with clayeyand silty varieties in some deposits of the southernUrals.

It should be emphasized that most researchers, whostudied Oligocene manganese ores, consider them asdiagenetic formations. This is evident from the domi-nance of typical nodular mineralization forms, complexrelationships between ore accumulations and hostrocks, and some other features comprehensivelydescribed in the monograph by Kalinenko (1990).

It is evident that formation conditions of manganeseore facies in Ukraine, the Caucasus, and Mangyshlakcharacterize only some aspects of manganese mineral-ization. Nevertheless, it should be noted that ore-enclosing sediments contain diverse fossil marine mol-luscan species, solitary corals, bryozoans, crustaceans,fishes and several tens of foraminiferal forms identifiedby Nosovskii (1964) and reproduced in (Strakhov,1968).

This fact indicates that waters of the ore-bearingpart of paleobasin had normal salinity and gas regime.They were characterized by the high content of oxygenand the absence of H

2

S.Phosphorite-bearing facies are usually confined to

shallow areas of platformal and geosynclinal seas. They

are distinctly subdivided into two facies groups partic-ularly widespread in the Cretaceous and Paleogenesequences. The first group is represented by nodularphosphorites and hardgrounds in terrigenous sequencesof platforms. These deposits associate usually with sed-iments of highly variable grain-size composition: fromclays and fine-grained silts to coarse-grained sand-stones and gravelstones. They are largely confined tothe shallowest part of the shelf and intertidal zone.Kazakov (1937) estimated erroneously their formationdepths at 100–150 m. Based on the ecological analysis,Bushinskii (1954) reduced this value to 60–70 m. At thesame time, both researchers considered phosphorites astypical chemogenic or biogenic-chemogenic sedi-ments. In (Kholodov, 2008), the author of the presentcommunication demonstrated that phosphorite forma-tion largely represents a diagenetic process. Nodularand platy phosphorites are formed in zones ranging

Carbonate1.1

1.0

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0

1.1

1.0

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0

Oxide

P clarke in thesedimentary shell(Vinogradov, 1962;Ronov, 1993)

P clarke in thesedimentary shell(Vinogradov, 1962; Ronov, 1993)

Ord

zhon

ikid

ze

Mar

gane

ts

Tok

mak

Chi

atur

i

Kvi

rili

Lab

a

Man

gysh

lak

Polu

noch

noe

Fig. 3.

Distribution of P in oxide and carbonate sedimentarymanganese ores.

8


Vol. 44

No. 1

2009

KHOLODOV, NEDUMOV

from shallow shelf (60–70 m) to beach settings. Inter-tidal zone of the paleobasin is characterized by theredeposition and secondary concentration of phosphatenodules. It is noteworthy that phosphorites are mainlyformed in a normal oxygenated basin.

The second group of phosphorite-bearing faciesincludes the phosphatized bone remains of fish skele-tons and their breccias. They are commonly associatedwith manganese ores.

Phosphatized remains of fish skeletons and theirfragments are characterized by wide lateral and strati-graphic distribution in Paleogene sequences of south-ern Russia, Ukraine, the Caucasus, and Mangyshlak.They occur usually as rare isolated inclusions that arenot responsible for the lithological appearance of claysequences. In some areas, however, their accumulationsacquire the rock-forming significance. One can seeentire members and lenses of phosphatized bone detri-tus with elevated admixtures of rare and radioactive ele-ments.

Such phosphorite-bearing beds are widespread inthe Maikop sediments of Mangyshlak (Melovoe,Tomak, Taibogar, Tasmuran, Sadyrnin, and other oredeposits and occurrences) and in the Eocene–Oli-gocene boundary layers of the Ergenei area (Volgaregion), where similar mineralization has been found inthe Chernye Zemli locality near Elista (Stepanov, Tsen-tral’noe, Yashul–Troitsk, Vorob’ev, Nugrin, and otherore occurrences). They are described in (Kochenovet al., 1970; Stolyarov and Kochenov, 1995; and Stol-yarov and Ivleva, 1999a, 1999b).

Numerous descriptions of fish beds and associatedrare-metal deposits demonstrate that they were depos-ited in three different settings.

Mass burials of fishes were formed in depressions(traps) contaminated with H

2

S and located on the shelfnear arches of synsedimentary uplifts (banks, shoals, ornondeposition areas).

The clayey material characterized by the absence ofbenthic organisms accumulated iron sulfides, fish skel-

W E

Q

N

2

–

QNP

1 2 3 4 5 6 7 8

9

QN

2

–

QN

2

s

1

-–

N

2

ns

N

1

tP

brs

P

2

kv

QN

2

–

Q

N

2

s

1

–

N2nsN2s1

P3brs

1 2 3 4 5 6

7 8 9 10 11

(‡)

(b)

(c)

I

Fig. 4. The structure of deposits in the South Ukraine manganese ore basin. Modified after (Shnyukov and Orlovskii, 1993).(a) Geological cross section of the Ordzhonikidze deposit: (1) soil–vegetation and loam layer, (2) clay, (3) marly clay, (4) limestone,(5) sand, (6) coaly sand, (7) green clay, (8) weathering crust formed after crystalline rocks, (9) ore. (b, c) Geological cross sectionsof the Zelenyi Dol deposit: (1) soil–vegetation and loam layer, (2) clay with carbonate concretions, (3) clay with fauna, (4) sandyclay, (5) limestone, (6) marly clay, (7) clay, (8) sand, (9) ore, (10) silt, (11) weathering crust formed after crystalline rocks.

LITHOLOGY AND MINERAL RESOURCES Vol. 44 No. 1 2009


Tab

le 2

. D

istr

ibut

ion

of F

e, M

n, a

nd P

(%

) in

vol

cano

sedi

men

tary

man

gane

se d

epos

its

Dep

osit,

occ

urre

nce

Age

FeM

nP

Sour

ce

Kar

adzh

al, h

igh-

grad

e or

esD

evon

ian

(Fam

enni

an)

2.65

–19.

314

.6–3

8.5

0.03

–0.0

6B

etek

htin

, 194

6

The

sam

eT

he s

ame

3.57

–14.

817

.55–

26.2

20.

04K

alin

in, 1

965

Kar

adzh

al, l

ow-g

rade

ore

s"

8–22

5–14

0.04

The

sam

e

Kar

adzh

al"

3.47

28.3

0.07

Nov

okha

tski

i, 19

72

Eas

tern

Kar

adzh

al"

4.6

27.2

0.03

2K

avun

, 196

7

Wes

tern

Kar

adzh

al"

6.04

21.1

50.

018

The

sam

e

Kta

i12

.38

23.3

10.

08"

The

sam

e3.

0235

.72

0.04

Nov

okha

tski

i, 19

72

Tak

hta-

Kar

achi

Ord

ovic

ian

or S

iluri

an–D

e-vo

nian

0.84

–14.

12.

12–3

2.46

0.01

–0.4

7(0

.47

is a

n an

oma-

lous

sam

ple,

oth

ers

are

0.0

1–0.

06)

Stra

khov

et a

l., 1

968

Tet

rikt

saro

i ore

s (G

eorg

ia)

Pale

ocen

e0.

7–23

.31

7.46

–46.

760–

0.20

The

sam

e

Koz

haev

sk (

Sout

hern

Ura

ls)

Mid

dle

Dev

onia

n (G

ivet

ian)

3.44

–11.

8314

.3–4

2.81

0.04

–0.0

6B

etek

htin

, 194

6

Zha

ksy

(nor

ther

n K

azak

hsta

n)O

rdov

icia

n3.

42–9

.27

35.7

8–37

.71

0.03

–0.0

4G

avri

lov,

197

2

Tas

oba

(nor

ther

n K

azak

hsta

n)T

he s

ame

1.52

–5.5

235

.77–

41.1

20

The

sam

e

Los

Chi

vos

(Cub

a)L

ate

Cre

tace

ous–

Eoc

ene

0.35

–5.5

79.

65–5

9.57

0–0.

004

Soko

lova

, 197

6

Cha

rco

Red

ondo

(C

uba)

The

sam

e0.

76–4

.47

22.1

6–50

.76

0–0.

004

The

sam

e

Bar

ranc

os"

1.79

–5.2

919

.09–

41.2

10–

0.00

4"

Ponu

po"

0.54

–4.5

228

.66–

47.3

00–

0.00

4"

El C

rist

o"

4.06

–5.8

114

.98–

28.6

60.

004

"

Ore

s of

the

Fran

cisc

an F

orm

atio

n (U

nite

d St

ates

)L

ate

Jura

ssic

–Cre

tace

ous

0.82

–2.0

329

.0–4

7.81

0–0.

11T

alia

ferr

o an

d H

udso

n, 1

943

Sakm

ara

zone

(So

uthe

rn U

rals

)O

rdov

icia

n0.

42–2

.65

6.85

–37.

510–

2.96

Stra

khov

, 196

8

Kos

-Ist

ek (

Sakm

ara

zone

)O

rdov

icia

n1.

49–4

.26

6.97

–44.

100.

03–3

.00

Gav

rilo

v, 1

972

Gub

erly

(Sa

kmar

a zo

ne)

Ord

ovic

ian

0.64

–1.6

232

.88–

42.7

10.

01–1

.32

Gav

rilo

v, 1

972

Kar

agal

a (S

akm

ara

zone

)O

rdov

icia

n1.

93–1

0.49

11.1

0–30

.29

0.05

–1.7

1G

avri

lov,

197

2

10


KHOLODOV, NEDUMOV

etons, their fragments, coalified wood remains, andeven intact tree trunks up to 3–5 m long.

Owing to alkalization and dissolution of the carbon-ate part of skeletons, the carbonate–phosphate fish boneremains became centers of phosphorus diffusion andwere replaced by phosphates (Kholodov, 2008). Inaddition to phosphatized fragments of fish, whale, andbird bones, shark teeth, and other pseudomorph struc-tures, phosphate nodules (several centimeters across)and thin lenses usually confined to the basal parts ofbeds were also formed.

Intense phosphate precipitation could also be stimu-lated by the decomposition of fish organic matter andthe formation of organic stimulators, which enteredseawater and influenced the precipitation of phosphates(McConnell and Frajola, 1961; Bushinskii, 1967).

The second facies type is represented by the phos-phatized bone breccias that form diachronous bodiesand reflect the transgressive position of Oligocenesequences. In these bodies, significantly smaller rede-posited phosphatized bone remains are distinctly con-fined to sandy–silty fractions with gravel-sized quartzfragments. Based on the structure of ore-bearing lensesin the Melovoe deposit in Kazakhstan (Fig. 6), the rede-posited phosphate detritus forms a single apron thatconformably overlies the older sediments and is inher-ited by all subsequent ore levels. Such relationshipscould appear only due to transgression of paleobasinand only when the basal layer reflects the advancementof shoreline toward uplifts.

It should be noted that the H2S-contamination frontalso probably followed the migrating shoreline and theredeposition of fish remains in the oxic environment. Inany case, it is clear that shelf depressions were filledwith the heavy H2S-contaminated waters, while theH2S-contaminated anoxic environment gave way tooxic phases with high-energy hydrodynamics near thecoast.

In general, the mass death of fishes and, probably,mammals proceeded in the H2S-contaminated settingsat the transition between oxic and anoxic regimes. It

should be emphasized that the boundary between theH2S-contaminated and aerated waters migrated perma-nently toward the Karagiin Uplift simultaneously withthe shoreline migration.

The rapid dislocation of H2S-contaminated waters isrecorded along the profile in Fig. 6, which demonstratessulfide incrustations on erosion surfaces of Oligocenesequences.

The third facies type of fish bone breccia is mostcharacteristic of the Ergenei area with abundant strati-form lenses. They also occur on slopes of synsedimen-tary uplifts in deeper settings with less intense H2S con-tamination.

Fish beds of this area frequently contain glauconitecemented largely by carbonates instead of clayey mate-rial. In general, the facies pattern of fish bone breccia inthe Ergenei area reflects variations in the hydrosulfuric-oxic settings, the mechanism of which is insufficientlyclear and requires special studies.

It is noteworthy that the manganese ore and phos-phorite-bearing facies usually demonstrate close spa-tiotemporal association with each other.

Figure 7 illustrates spatial relationships between thephosphatized fish bone lenses of the Melovoe depositand manganese ore lenses of Mangyshlak. Despite dif-ferent ages of these deposits, they are likely character-ized by a distinct genetic link: dispersed fish remains inthe Oligocene clayey sequences form a single aureolearound both phosphorite-bearing and manganiferouslenses.

Such a close relationship between phosphorite-bear-ing facies of the “fish cemetery” type and sedimentarymanganese deposits is more distinct in Fig. 8 repro-duced from (Stolyarov and Kochenov, 1995).

The figure shows that Paleogene sections containtwo main intervals with phosphorite and manganese oreoccurrences.

The first interval corresponds to the Pshekha, Niko-pol, and Uzunbas–Kendzhala formations. It is welldeveloped in both western and eastern areas, but thelargest manganese deposits are located in Ukraine andHungary.

The second interval coincides with the Karadzhalgaand Ol’ga formations. They include the rare metal–phosphate deposits of the Mangyshlak and Buzachiareas.

It is noteworthy that both manganiferous and phos-phorite-bearing sediments always make up spatial asso-ciations located close to each other.

Analysis of the available factual material providessuggests that the central part of the study region inCiscaucasia was occupied by a spacious H2S-contami-nated sea basin during the entire Maikopian time(~10 Ma). The basin likely represented an analogue ofthe Black Sea (Arkhangel’skii and Batalina, 1929; Stra-khov, 1960a, 1960b).

SandSilt

ClayCoarse Fine

LMCh1

Ch2

N

B-T

Fig. 5. Schematic localization of manganese ores in sedi-mentary rocks of different grain size compositions. Modi-fied after (Strakhov et al., 1968). Deposits: (L) Laba, (M)Mangyshlak, (Ch1) Chiaturi, lower horizon, (Ch2) Chiaturi,upper horizon, (N) Nikopol, (B-T) Bol’shoi Tokmak.



The existence of H2S contamination in the Maiko-pian sea is confirmed by the lack of benthic fossils inthe clayey sediments and calculations of the Mo–Mnmodule (Kholodov and Nedumov, 2000). Determina-tion of proportions of these elements in 22 samplesfrom the Sulak River section revealed that H2S-contam-inated conditions were commonly dominant in this area

during the Maikopian period (Mo/Mn > 0.01) and onlysamples from the Zuramakent Horizon indicate a stableaerated regime (Mo/Mn < 0.01). The Mo–Mn modulealso behaves in a similar manner in Maikop sequencesof the Kuban region, where Mo and Mn contents weredetermined in 24 samples. It appeared that this coeffi-cient usually exceeds substantially the boundary value

1 21

2

3

4

ZhazgurlySyncline

Mys PeschanyiUplift

SegendySyncline

Beke-BashkudukAnticline

Chakygan Syncline

KaratauMeganticline

100

0

100

200

300

400

500

m

N

QN

N11 ksh N1

1ksh

P32 kr2

sd

P32 kr2

P32 kr1

P31 kn2

P31 kn1

P23 ad

P31 kl

P31 kd

P32 kr1

P31 os

P31 kl

P23 ad

NQ

P31 kn1

P31 kn2

P32 kr1

P32 kr1

SP1

SP2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15‡

16 17 18 19 20 21 22 23 24

SE

(‡)

(b)

P32 kr2

C

b

D1

2

35

P3uz

Fig. 6. Distribution of phosphorite–rare metal and manganese ores in the Mangyshlak region. Modified after (Stolyarov andKochenov, 1995). (a) Transverse section of the ore lense in the Melovoe deposit; (1) clays with scattered fish remains, (2) alternatingclays with scattered fish remains and fucoids. Numerals in the figure correspond to numbers of ore beds. (b) Geological cross sectionof the Mangyshlak ore district: (1) marl, (2) calcareous clay, (3) clay, (4) clay with admixture of silty material (up to 5%), (5) siltyclay, (6) sandy–silty rocks, (7) ostracods, (8) mollusks, (9) siderite concretions, (10) fucoids, (11) scattered fish remains, (12) alter-nating beds with fish remains and fucoids, (13) accumulations of fish remains (bones, scale) at bedding surfaces, (14) diatoms,(15) algal remains: (a) rare, (b) accumulations at bedding surfaces, (16) sulfide beds: (SP1) lower, (SP2) upper, (17) bone brecciabed, (18) finely dispersed (globular) pyrite, (19) spotty aggregates of globular pyrite, (20) aggregates of crystalline pyrite, (21, 22) bone detri-tus lenses: (21) split, (22) stratiform–lenticular, (23) manganese deposits, (24) elevated Mn concentrations. (C–D) Segment of the profile con-

structed for the Uzunbas and Kuyulus formations across the manganese deposit area. Upper Eocene: ( ad) Adaev Formation.

Lower Oligocene: ( uz) Uzunbas Formation, ( kl) Kuyulus Formation, ( 1kn) Kendzhala Formation: (kn1) lower, (kn2) upper;

Yuzhnomangyshlak Formation: ( os) Ostracoda Beds, ( kd) Kaunda Beds. Upper Oligocene, Karagiin Formation: ( kr1)

lower subformation, ( kr2) upper subformation. Lower Miocene: (N1ksh) Kashkarata Formation. (N) Neogene, undivided;(Q) Quaternary, undivided.

P32

P31

P31

P31

P31

P31

P32

P32

12


KHOLODOV, NEDUMOV

(0.01) and only the upper part of the section (Ol’ga andRitsa formations) reflects the replacement of H2S con-tamination by well-aerated conditions (Mo/Mn =0.001–0.003).

It is remarkable that signs of H2S contamination aretraced over a long period (>10 Ma) and recorded up tothe South Caspian Basin (Kochenov and Stolyarov,1995).

Like all H2S-contaminated basins, the Maikopiananoxic basin concentrated P, Mn, Si, and Fe in its water(Kholodov, 2002, 2006). Precisely these componentsare responsible for the peculiar appearance of theMaikop sediments.

Numerous depressions formed in peripheral areas ofthe Maikop Basin, particularly in zones characterizedby seawater transgression and expansion of the H2S-contaminated medium. Such depressions representedtraps with large-scale fish death and burial.

According to (Kochenov and Stolyarov, 1995), thetotal area occupied by such traps is as large as 200–260 km2 in the Mangyshlak Peninsula and 6300 km2 inthe Ergenei area. The average thickness of phosphoritelenses is 1.8 m in the first area and varies from a fewmeters to tens of meters in the second area (Stolyarovand Ivleva, 1991).

The mass death of fishes and other organismsresulted in the accumulation of huge quantities oforganic matter, bones, and cartilages in bottom sed-iments of the Maikop Basin. All this biogenic mate-rial stimulated intense extraction of phosphoruscompounds from the H2S-contaminated waters andtheir concentration (up to 25–35%) in fish beds.

As shown in (Kochenov and Zinov’ev, 1960;Kholodov, 1963; Blokh and Kochenov, 1964; McCon-nell, 1977), present-day fishes have skeletons com-posed of phosphate minerals and CaCO3. Cartilagesconnecting bones consist of hyaline or chondrine thatreadily swells in water. These components contain

low

er

Rup

elia

n

Olig

ocen

eup

per

Cha

ttian

Pshe

khia

nSo

leno

vian

Kal

myk

ian

Low

erM

ioce

neA

quita

nian

Bur

diga

lian

Seri

es,

subs

e-

Stag

e Regional stages(horizons),

TarkhanianKotsakhurian

Sakaraulan

Karadzhalginian

Upper

Lower

Upper

Lower

Upper

Lower

Underlyingcomplexes

Bulgaria

OstracodaBed

Mn Mn

Mn

Black Sea regionSouthernUkraine

Western Georgia

Tarkhanian

Chernobaev

Gornostaev

Askaniya

Seragoz

Molochan

NikopolSubformation

Bo

risf

enR

uano

vsk

Subf

orm

atio

n

Ostra-codaBeds

U, Cu, Pb

Central Ciscaucasia

Tarkhanian

Ritsa

Ol’ga Mn

Karadzhalga

ZelenchukMn

Batalmashin U

UpperMorozkino

Subformation

LowerMorozkino

Subformation

Mn

Polbino

Mn

PshekhaMn

Mn

Volga–Don

Tsagankhak

Aradyk

Nugrin

Upper

Kal

myk

low

er

Virgulinella Beds

Isiburul Beds

Sole

novs

k

Ostra-Beds

U

UpperTsimlya-

BedsMn

MnT

sim

lyan

sk

Mangyshlak,Buzachi

Kashkarata

UU

Upper

Kar

agiin

Upp

er

VirgulinellaBeds

Kulunda Beds

Yuz

hnom

angy

shla

k

Ostra-codaBeds

Kendzhala

Mn

Kuyulus

Mn

Uzunbas

NorthernUstyurt

Baigubek

Karatomak

MainasorBeds

Tam

da

ErgenicaBeds

Fe

Fe

Ash

chea

iryk

Northern Aral

region

Aral

Chagrai

Fe

Fe

Chilikta

Fe

Fe

Fe

P32 P3

2–PR P32–K2 P3

2–P21 P3

2–P1 P32 P3

2 P32

1 2 3 4 5Mn 6

U LowerTsim-

Beds;

ries

substages

Ginsk

region

nsk

lyansk

Fig. 7. Stratigraphic distribution of phosphate–rare metal, manganese, and iron ore accumulations in Ukraine, the Caucasus, andCentral Asia. Modified after (Kochenov and Stolyarov, 1995). (1–4) Metalliferous horizons: (1) manganese ores, (2) manganeseoccurrences, (3) sulfide–uranium–rare metal, (4) oolitic iron ores; (5) elevated (above clarke) Mn concentrations in carbonate clays;(6) “fish lithofacies” related to H2S contamination.



❙❙

❙❙

❙ ❙

❙❙

❙

❙❙

❙❙

❙

❙❙

❙❙❙❙

❙❙

❙❙

❙❙

❙❙

❙❙

❙

❙❙

❙❙

❙❙

❙❙

❙

❙❙❙

❙❙❙

❙❙

❙❙

❙❙

❙❙

❙❙

❙❙

❙❙

❙❙

❙❙

❙❙❙

❙❙

❙❙

❙❙

❙❙

❙❙

❙❙

❙❙

❙❙

❙

❙❙

❙❙

❙

❙❙

❙❙

❙

❙❙

❙❙

❙❙

❙

❙❙

❙❙

❙❙

❙❙

❙

❙❙

❙❙

❙❙

❙❙ ❙❙❙

❙

❙❙

❙

❙

❙

❙❙

❙❙

❙

❙❙❙❙

❙

❙❙ ❙

❙❙

❙

❙❙

❙❙

❙

Ardygel R.

Ardygel R.

Ardygel R.

TTTrrraaammm

ssshhhaaakkk

RRR...

Lemeza R.

Lemeza R.

Lemeza R.

AmirovAmirovAmirovAnticlineAnticlineAnticline

KKKaaazzz

iiiyyyaaakkk

UUUppplll

iiifffttt

UUUkkk RRR...Uk

Trou

gh

Uk

Trou

gh

Uk

Trou

gh

SSSaaallldddyyybbbaaassshhh RRR...

Si m

– Us o l ' e

Tr o u g h

Si m

– Us o l ' e

Tr o u g h

Si m

– Us o l ' e

Tr o u g h

SSSiiimmm RRR...

sodium carbonate and sodium sulfate. Organic matterof fishes is dominated by proteins, which glutamineacid, glycol, alanine, and proline after microbiologicaldecomposition (Drozdova and Kochenov, 1960). Car-bonate components and, probably, organic matter ofthese remains were replaced by phosphates.

In any case, “fish cemeteries” likely extracted sub-stantial quantities of phosphorus from bottom waters ofthe Maikopian sea. This process continued after sedi-

mentation at the diagenetic stage with the dominantparticipation of hydrogen sulfide.

Since the phosphatized fish remains of the Mangy-shlak and Ergenei areas contain negligible quantities ofMn, they likely represented a peculiar filter that sepa-rated the precipitating phosphorus and dissolved man-ganese. Relative to phosphorus, manganese was morewidespread in the basin and precipitated in the oxygen-rich medium during the alkalization of seawater withcarbonates.

1

2

3

4

5

6

Ul u

- Te l y

a k

Tr o

ug

h

Sim R

.

(‡)

Bed no. Lithology Th, m

5

45

5

24

30

40

20

120

14

13

11

12

10

9

8

7

6

1–5

m360350340330320310 1 2

NW SE

Description

Fine-clastic carbonate breccia;

Accumulation of compactly arranged blocks of variable age and origin

1–Asselian reefal limestones2–Sakmarian organogenic–detrital

3–relatively thin-platy detrital(bryozoan–crinoid–fusulinid)Artinskian limestones

Fine-clastic (1–12 cm)carbonate breccia with fusulinidsand ammonoids of the Irga Horizon(Artinskian Stage)

Block-sized breccia of differentage limestones

Blocks and large fragments ofwith Artinskian fusulinids; at the base, large block of quartzsandstones and gravelstones

1 2 3 4 5

(b)

(c)

(d)

massive limestones

Fig. 8. The geological structure and stratigraphic position of phosphorites of the Asha deposit and Ulutelyak manganese ores.(a) Schematic tectonic structure of the northern Bashkir Trough (Keller, 1945): (1) Karatau Complex, (2) uplifts and slopes of thetrough with outcrops of Artinskian rocks, (3) central part of the trough filled with Ufimian red beds, (4) stratoisohypses of the roofof the Artinskian sediments (proven and assumed), (5) reversed faults, (6) boundaries of stratigraphic complexes; (b) section of thephosphorite lens in the Asha deposit (Vodorezov et al., 1956): (1) phosphorite lens, (2) brecciated (slightly phosphatized) limestone;(c) lithostratigraphic column of the Asha deposit (Chuvashov and Yakovleva, 2007); (d) schematic structure of the manganiferouslimestone–dolomite formation of the Ulutelyak type (modified after E. Gribov): (1) oncolitic and oolitic limestones, (2) manganesecarbonate ores (manganese limestones), (3) manganiferous dolomitic marls, (4) dolomites, (5) anhydrites.

Asha

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KHOLODOV, NEDUMOV

ASSOCIATION OF DIFFERENT PHOSPHORITE DEPOSITS WITH SEDIMENTARY

MANGANESE DEPOSITS

It is well known that phosphorite deposits of mostdiverse types are frequently associated with the Meso-zoic–Cenozoic sedimentary manganese deposits.

Danilov (1982) described numerous occurrences ofnodular phosphorites in Jurassic (upper Volgian) glauc-onite sandstones of the northern Timan region, wherethey form plates in some places. The same Volgiansequences enclose beds and lenses of oolitic manga-nese ores (from 0.2 to 2.5 m thick) located slightlybelow the phosphorite horizon. Manganese mineraliza-tion is represented by rhodochrosite, manganocalcite,and psilomelane. The MnO content ranges from 23.33to 70.43%; the Fe content, from 3.5 to 37.86%.

Many manganese deposits in the Urals coincide spa-tially and stratigraphically with phosphorite depositsand occurrences.

For example, Betekhtin (1946) and Sapozhnikov(1972) described the Marsyat deposit, where nodularphosphorites occur together with manganese ores in theUpper Cretaceous sediments. Similar phosphate lensesare also established in Tertiary sequences of the Pol-unochnoe manganese deposit.

More complicated spatiotemporal relationships areobserved between granular phosphorite deposits insouthwestern Morocco and manganese deposits in theImini area (Tiferson–Bou Azzer–Bou Aggum). This oredistrict is scrutinized in (Bouladon and Jourovski,1952, 1956; Thein, 1990; and others).

In this area, stratiform manganese ore depositsoccur in the Cretaceous–Eocene arid redrock formationin association with the Turonian carbonate–dolomitesequence. Ore-bearing rocks are exposed in piedmontsof the High Atlas as sequences transgressively overly-ing the deformed Paleozoic strata, which enclose prob-ably hydrothermal manganese ore veins.

The Turonian deposits are mainly composed of psi-lomelane. Jacobsite, braunite, and hausmannite aresubordinate, while rhodochrosite is rare. The Mn con-tent in ores ranges from 10.84 to 50.84% (Table 1).

The carbonate ore-bearing sequences of the manga-nese ore district enclose thin P-rich layers. However,large phosphorite deposits are confined to the Eoceneredrock formation in Morocco and the main phospho-rite-bearing districts are located in the Jebilet Plateaunorth of Marrakesh.

In this area, up to 8–10 beds of high-quality granularphosphorites with the P2O5 content ranging from 25 to30% are mined in Eocene carbonate–dolomitesequences. The structure of the Si Unes, Maiat, ElBarudge, Ulla Abdun, Gufaf, and Tadl deposits, whichform a wide sublatitudinal band of ore occurrencesaround the Jebilet Plateau, is described in (Orlova,1951; Salivan, 1960; and others).

It is evident that manganese deposits in southwest-ern Morocco are associated with phosphorites, whichare located stratigraphically higher in the transgressivesequence of red-colored limestones, dolomites, evapor-ites, sandstones, and clays. Their undoubted spatialassociation is particularly emphasized by the abun-dance of phosphorites in the Turonian manganiferoussequences.

The Bashkir Trough area adjacent to the KaratauUplift (Urals) at the lower and middle reaches of theSim River is an additional example of the cooccurrenceof manganese ores and phosphorites. This area hoststhe Asha phosphorite and Ulutelyak manganese depos-its.

The geological structure of this region is shown inFig. 8a adopted from (Keller, 1945). The main structureof the region is the Karatau Fault that extends from thesoutheast to northwest and separates the Proterozoicmetamorphosed sequences of complex folds of Karatau(Urals) from the system of gentle synclines and upliftscomposed of Permian sediments of the Uralian Fore-deep and Russian Platform.

The central part of the region is occupied by theKazayak Uplift and Karatau structural salient com-posed of Artinskian carbonate rocks. Their conjunctionis marked by the Zmeinogorsk and Lipovyi reefs. Likemany other reefal buildups of the Uralian Foredeep,they are characterized by oil and gas occurrences (Kuz-netsov, 2000).

The uplifts are surrounded by depressions: Ulute-lyak Depression in the west and Uk Trough, whichgrades into the spacious Sim–Usol’e Trough filled withUfimian redrocks, in the east.

The entire system of these tectonic structures risesto northeast: dip angles of Permian strata near the Kara-tau Salient amount to 50–70°. In the NW direction, theybecome gradually gentler and even flat in some places.

The Asha phosphorite deposit is located in the high-est part of the region in southern outskirts of Asha nearthe Lipovyi reef. The deposit discovered in 1953 isdescribed in (Vodorezov et al., 1956; Chalyshev, 1968;Volkov, 1974; Chuvashov and Yakovleva, 2007). It rep-resents a block–breccia sequence of the Artinskian,Sakmarian, and Upper Carboniferous ore-bearing rocksup to 320 m thick. The sequence consists of alternatingintervals of carbonate fragments (up to 10–20 cmacross) and block horizons of carbonate bed fragments(up to 10–15 m or more in size). Figure 8b demon-strates the lithological cross section of the Mount Kula-kovaya area (Chuvashov and Yakovleva, 2007), wherethe lower part is dominated by limestones with theArtinskian and Sakmarian fauna, while the upper layersenclose Upper Carboniferous fossils.

We can probably agree with these authors, whobelieve that the block facies “… lack primary sedi-ments; their formation is related to the large-scaledestruction and subsequent accumulation of a thicksection of Upper Carboniferous bedded limestones and



Lower Permian (Asselian, Sakmarian, and Artinskian)reefal and bedded limestones” (Chuvashov and Yakov-leva, 2007, p. 60).

Phosphorites appear at different levels of the blockhorizon. According to (Vodorezov et al., 1956), phos-phorites of the highest commercial significance occurin the lower brecciated horizon resting unconformablyon the eroded surface of the steeply dipping and slightlyphosphatized Artinskian limestones (Fig. 8c). Thephosphorite-bearing sediments are up to 10–20 m thick.They distinctly replace the brecciated carbonatesequences or bedded limestones. In addition, they arecharacterized by very uneven basal surface, which iscomplicated by pockets, depressions, and cracks filledwith phosphate material.

The abundance of signs of the metasomatic replace-ment of limestones suggests that phosphorites of theAsha deposit are typical karst formations. This assump-tion of Vodorezov et al. (1956) is based on followingobservations: the complete or partial replacement ofcarbonate blocks, their fragments, and clayey–carbon-ate cement; the filling of pores, cavities, and fractureswith phosphates; the formation phosphate fringesaround the corroded carbonate fragments; and severalother signs of the wide development of phosphate meta-somatism.

The Ulutelyak manganese deposit is located in thesynonymous syncline 16–20 km southwest of the Ashaphosphorite deposit and 20–22 km northeast of Ufa.

Manganese ores in this deposit associate with UpperPermian sediments. Figure 8d illustrates the schematicdistribution of ores in the deposit, where they are con-fined to two intervals of the section overlying the Artin-skian and Kungurian gypsiferous formations.

The thickness of ore beds varies from 6 to 10 m; theMn content, from 3 to 18% (Varentsov and Rakhmanov,1974).

Ore bodies of this deposit clearly demonstrate thefollowing vertical zoning (Betekhtin, 1946): the erodeduneven surface of rocks is overlain by a bed of alternat-ing laminated manganese carbonate ores and lime-stones resting upon, while the upper parts of beds aredominated by SiO2-rich vernadite ores.

The deposit is characterized by wide developmentof karst process. Watersheds are covered by karst fun-nels. According to V.N. Kuleshov (private communica-tion), some areas of the deposit are marked by the abun-dance of block facies and the presence of limestoneblocks that complicate the stratiform patterns of man-ganese orebodies.

It is clear that cooccurrence of Asha phosphoritesand Ulutelyak manganese ores is not incidental. Thefollowing facts should be taken into considerationwhen explaining this phenomenon.

The Permian and even Triassic sediments of theUralian Foredeep are almost always enriched in phos-phorus and manganese (Bezrukov, 1939; Chalyshev,

1968; Chuvashov and Yakovleva, 2007). For example,the P2O5 content in carbonate sediments of the Artin-skian Stage ranges from 1 to 18%; the MnO content,from traces to 1.65%. Even the Ufimian redrocks con-tain 0.6–5% of P2O5 and up to 1.15% of MnO.

Analysis of the available data allows the Asha phos-phorites and Ulutelyak manganese ores to be classed astypical epigenetic sediments that originated at the lateststages of the ore-forming process.

Noteworthy is the close association of this processwith the formation of block facies and the subsequentkarstification. The latter process has been reported fromthe Ufa area in (Varsanof’eva, 1916; Gvozdetskii,1954; and others). It was established that karst funnels,holes, caves, and collapse lakes are closely related tothe Artinskian and Kungurian gypsiferous sequencesand are probably superimposed on the formation of car-bonate blocks and breccias owing to the developmentof the Karatau Uplift.

It is conceivable that cooccurrence of phosphoriteand manganese deposits in the above case is controlledby the activity of infiltration waters, which could derivelarge quantities of P and Mn from the enclosing Per-mian formations. The abundance of organic matter ofthe oil series in the Permian sequence played a signifi-cant role in karstification. Some part of the organic mat-ter was transported from deeper parts of the section,whereas another part was concentrated in the Permianreefal massifs. In addition, sulfates made up a substan-tial portion of halogenic sequences. Microbiologicalsulfate reduction in groundwaters could produce signif-icant quantities of hydrogen sulfide and karstificationof carbonate sequences. Combined with water infiltra-tion, all these processes could stimulate the formationof commercial phosphorite and manganese ore depositsthat were separated in both vertical and lateral direc-tions.

CONCLUSIONS

(1) Cooccurrences (parastereses) of chemical ele-ments, minerals, sedimentary rocks, facies, and forma-tions should be discriminated from their parageneses.Only geological objects associated with a singlegenetic process should be considered as parageneses.

(2) Phosphorus is concentrated in sedimentary man-ganese ores and is virtually missing in hydrothermaland volcanosedimentary manganese deposits.

(3) Cooccurrence of phosphorus and sedimentarymanganese ores can clearly be divided into twoparageneses. Accumulation of phosphorus in manga-nese hydroxide ores is largely determined by sorption,while its concentration in carbonate ores is likelyrelated to the ability of both chemical elements to pre-cipitate in the alkaline carbonate medium.

(4) In addition to spatiotemporal relationships,cooccurrence (parasteresis) of manganese ore andphosphorite-bearing facies in the Oligocene sediments

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of southwestern Eurasia is an indicator of their com-mon genesis, since ore-forming processes in this regionare presumably determined by the initial joint concen-tration of elements in the H2S-contaminated Oligocenebasin and their subsequent fractionation at the bio-chemical and carbonate–alkaline barriers.

(5). Parasteresis of phosphorites in the Asha depositand manganese ores in the Ulutelyak deposit was pro-moted by the general intensification of the P–Mngeochemical background of the region, the develop-ment of sulfate-reducing and karstification in lime-stones, and the activity of infiltration waters. These pro-cesses stimulated the fractionation of components andthe formation of commercial deposits.

ACKNOWLEDGMENTS

This work was supported by the Russian Foundationfor Basic Research, project no. 05-05-64033.

REFERENCESArkhangel’skii, A.D. and Batalina, M.A., Cognition of theEvolution History of the Black Sea, Izv. Akad. Nauk SSSR,Ser. Geol., 1929, no. 8, pp. 691–706.Betekhtin, A.G., The Chiatura Deposit and Its CommercialCharacteristic, Tr. TsNIGRI, 1936, no. 60.Betekhtin, A.G., Promyshlennye margantsevye rudy SSSR(Commercial Manganese Ores of the USSR), Moscow:Akad. Nauk SSSR, 1946.Betekhtin, A.G., Concept of the Paragenesis of Minerals, Izv.Akad. Nauk SSSR, Ser. Geol., 1949, no. 2, pp. 15–20.Betekhtin, A.G., Mineralogiya (Mineralogy), Moscow:GIGL, 1950.Bezrukov, P.L., Geological Investigations of the ArtinskianPhosphorites on the Western Slope of the Urals, in Agronom-icheskie rudy SSSR (Agronomical Ores of the USSR), Lenin-grad: GONTI, 1939, vol. 5, pp. 16–24.Blokh, A.M. and Kochenov, A.V., Admixtures in Bone Phos-phate of Fossil Ores, in Geologiya mestorozhdenii redkikhelementov (Geology of Rare Earth Element Deposits), Mos-cow: Nedra, 1964, no. 24, pp. 107–153.Bouladon, J. and Jurovski, G., Manganese, in Geologie desgites, Alger, 1952, Ser. 3, pp. 44–80.Bouladon, J. and Jurovski, G., Les gites manganese duMarocco d’une description des sediments du Pricambrien, inAbstracts of Papers, Symposium sobreyeasimentos de man-ganese, Africa, Mexico, 1956, vol. 2, pp. 217–219.Breithaupt, J.F., Die paragenesis der mineralen, Freiberg,1849.Bushinskii, G.I., Litologiya melovykh otlozhenii Dneprovo-Donetskoi vpadiny (Lithology of Cretaceous Rocks in theDnieper–Donets Basin), Moscow: Akad. Nauk SSSR, 1954.Bushinskii, G.I., Inhibitors and Stimulators in Lithogenesis,Litol. Polezn. Iskop., 1967, vol. 9, no. 4, pp. 116–120.Chalyshev, V.N., Phosphate Potential of Permian and TriassicDeposits in the Northern Uralian Foredeep, Litol. Polezn.Iskop., 1968, vol. 10, no. 2, pp. 62–74.Chuvashov, B.I. and Yakovleva, L.P., Late Paleozoic Phos-phorite-Bearing Basin in the Southern Urals: Development

History, Main Types of Phosphate Occurrences, and TheirFacies and Stratigraphic Position, Litol. Polezn. Iskop., 2007,vol. 42, no. 1, pp. 45–63 [Lithol. Miner. Resour. (Engl.Transl.), 2007, vol. 42, no. 1, pp. 40–55].Danilov, I.S., Distribution of Manganese Minerals in WesternAreas of the Nikopol Deposit, in Geologiya i geokhimiyamargantsa (Geology and Geochemistry of Manganese),Moscow: Nauka, 1982, pp. 158–167.Dolidze, D.B., Machabeli, G.A., Tabagari, V.I., andGuadze, G.S., Lithogenesis of Oligocene ManganiferousRocks in the Kvirili Depression and Direction of FurtherProspecting-Exploration Works, in Novye dannye po mar-gantsevym mestorozhdeniyam SSSR (New Data on Manga-nese Deposits in the USSR), Moscow: Nauka, 1980, pp. 75–83.Drozdova, T.V. and Kochenov, A.V., Organic Matter of FossilFish Bones, Geokhimiya, 1960, no. 8, pp. 230–240.Fersman, A.E., Izbrannye trudy (Selected Works), Moscow:Akad. Nauk SSSR, 1953, vol. 3.Gavrilov, A.A., Eksgalyativno-osadochnoe rudonakopleniemargantsa (na primere Urala i Kazakhstana) (Sedimentary-Exhalative Manganese Ore Accumulation with Reference toUrals and Kazakhstan), Moscow: Nedra, 1972.Geologicheskii slovar’ (Geological Glossary), Moscow:Nedra, 1973, vol. 2, p. 456.Gryaznov, V.I., Genesis of Manganese Ores in the NikopolBasin and Method for the Forecast of the Marine Sedimen-tary Manganese Deposits, in Margantsevye mestorozhdeniyaSSSR (Manganese Deposits in the USSR), Moscow: Nauka,1967, pp. 135–147.Gryaznov, V.I. and Chervonookaya, L.V., Geochemistry ofPhosphorus in Marine Sedimentary Manganese Deposits, inMargantsevye mestorozhdeniya SSSR (Manganese Depositsin the USSR), Moscow: Nauka, 1967, pp. 170–179.Gvozdetsky, N.G., Karst (Karst), Moscow: GIGL, 1954.Hooper, F., Genesis and the Fate of Organic PhosphorusCompounds in Water Systems, in Phosphorus and Its Envi-ronment, Amsterdam: Elsevier, 1974. Translated under thetitle Fosfor v okruzhayushchei srede, Moscow: Mir, 1977,pp. 204–232.Kalinenko, V.V., Geokhimiya i rudonosnost' morskikh otloz-henii rannego miotsena Severnogo Kavkaza (Geochemistryand Ore Potential of the Early Miocene Marine Sediments inthe Northern Caucasus), Moscow: Nauka, 1990.Kalinenko, V.V., Shumikhina, N.V., and Gusarova, A.I.,Manganiferous Rocks of the Laba Deposit and Distributionof Vanadium, Chromium, Nickel, Cobalt, and CopperTherein, in Margantsevye mestorozhdeniya SSSR (Manga-nese Deposits of the USSR), Moscow: Nauka, 1967,pp. 242–258.Kalinin, V.V., Some Features of the Structure and Composi-tion of Iron and Manganese Ores in the Karadzhal Deposit,in Margantsevye mestorozhdeniya SSSR (Manganese Depos-its of the USSR), Moscow: Nauka, 1967, pp. 305–310.Kavun, V.I., Main Regularities in the Localization of Manga-nese Ores in the Karadzhal Ore Field, in Margantsevyemestorozhdeniya SSSR (Manganese Deposits of the USSR),Moscow: Nauka, 1967, pp. 294–305.Kazakov, A.V., Phosphorite-Bearing Facies and Genesis ofPhosphorites, in Geologicheskie issledovaniya agronom-icheskikh rud SSSR, (Geological Studies of AgronomicalOres of the USSR) Tr. NIUIF, 1937, no. 142, pp. 36–48.



Keller, B.M., Tectonics of the Ural Karatau and the KazanOil Zone, Byull. Mosk. O-va Ispyt. Prir., 1945, nos. 5–6,pp. 52–73.Kheraskov, N.P., Geological Rock Associations: Experienceof Identification, Byull. Mosk. O-va Ispyt. Prir., Otd. Geol.,1952, vol. 27 (6), pp. 31–52.Khodak, Yu.A., Comparative Geochemical Characteristic ofthe Nikopol and Magnitogorsk Manganese Ore Formations,in Ekzogennye poleznye iskopaemye (Exogenic MineralResources), Moscow: Nauka, 1976, pp. 129–141.Kholodov, V.N., Rare and Radioactive Elements in Phos-phates, Tr. IMGRE, 1963, no. 17, pp. 164–188.Kholodov, V.N., The Role of H2S-Contaminated Basins inSedimentary Ore Formation, Litol. Polezn. Iskop., 2002,vol. 37, no. 5, pp. 451–474 [Lithol. Miner. Resour. (Engl.Transl.), 2002, vol. 37, no. 5, pp. 393–411].Kholodov, V.N., Geochemistry of Phosphorus and Origin ofPhosphorites: Communication 1. Role of Terrigenous Mate-rial in the Hypergene Phosphorus Geochemistry, Litol.Polezn. Iskop., 2003a, vol. 38, no. 4, pp. 361–375 [Lithol.Miner. Resour. (Engl. Transl.), 2003a, vol. 38, no. 4, pp. 314–331].Kholodov, V.N., Geochemistry of Phosphorus and Origin ofPhosphorites: Communication 2. Source of Phosphorus inContinents and Genesis of Marine Phosphorites, Litol.Polezn. Iskop., 2003b, vol. 38, no. 6, pp. 563–584 [Lithol.Miner. Resour. (Engl. Transl.), 2003b, vol. 38, no. 6, pp. 477–494].Kholodov, V.N., Phase Transformations of Phosphates dur-ing Sedimentation and Genesis of Phosphorites, Geol. Rudn.Mestorozhd., 2004, vol. 46, no. 3, pp. 250–270 [Geol. OreDeposits (Engl. Transl.), 2004, vol. 46, no. 3, pp. 218–234].Kholodov, V.N., Geokhimiya osadochnogo protsessa(Geochemistry of Sedimentary Processes), Moscow: GEOS,2006.Kholodov, V.N., Origin of Cenomanian Nodular Phospho-rites in the Dnieper–Donets Depression (PaleographicAspect), Litol. Polezn. Iskop., 2006, vol. 41, no. 5, pp. 451–467 [Lithol. Miner. Resour. (Engl. Transl.), 2006, vol. 41,no. 5, pp. 401–416].Kholodov, V.N., Origin of Cenomanian Nodular Phospho-rites in the Dnieper–Donets Depression (GeochemicalAspect), Litol. Polezn. Iskop., 2008, vol. 43, no. 1, pp. 3–24[Lithol. Miner. Resour. (Engl. Transl.), 2008, vol. 43, no. 1,pp.].Kholodov, V.N. and Butuzova, G.Yu., Phosphorus in theHydrothermal Process, Litol. Polezn. Iskop., 1999, vol. 34,no. 3, pp. 350–368 [Lithol. Miner. Resour. (Engl. Transl.),1999, vol. 34, no. 3, pp. 195–209].Kholodov, V.N. and Nedumov, R.I., Application of theMolybdenum Module for Reconstruction of the Gas Compo-sition of Water in the Cretaceous Atlantic, Dokl. Akad. Nauk,2000, vol. 400, no. 2, pp. 1–4 [Dokl. Earth Sci. (Engl.Transl.), 2005, vol. 400, no. 1, pp. 116–118].Khvorova, I.V., Voznesenskaya, T.A., Zolotarev, B.P., et al.,Formatsii Sakmarskogo allokhtona (Formations of the Sak-mara Allochthon), Moscow: Nauka, 1978.Kochenov, A.V. and Zinov’ev, V.V., Distribution of RareEarth Elements in the Fish Phosphate Remains from Maiko-pian Rocks, Geokhimiya, 1960, no. 8, pp. 120–145.Kochenov, A.V., Mstislavskii, M.M., and Stolyarov, A.S.,Fossil Metalliferous Deposits of Fish Bone Detritus, in Sos-

toyanie i zadachi sovetskoi litologii (State and Objectives ofthe Soviet Lithology), Moscow: Nauka, 1970, vol. 11,pp. 165–171.Kuznetsov, V.G., Paleozoiskoe rifoobrazovanie na territoriiRossii i sopredel’nykh stran (Paleozoic Rifting in the Rus-sian Territory and Adjacent Countries), Moscow: GEOS,2000.MacConnel, D., Biomineralogy of Phosphates and Physio-logical Mineralization, in Phosphorus and Its Environment,Amsterdam: Elsevier, 1974. Translated under the title Fosforv okruzhayushchei srede, Moscow: Mir, 1977, pp. 402–482.MacConnel, D., Frajola, W.J. Bone: An Introduction to Phys-iology of Skeletal Tissue. Chicago: Univ. Chicago, 1961.Nosovskii, M.F., Oligocene, in Nikopol’skii margantserudnyibassein (The Nikopol Manganese Basin), Moscow: Nedra,1964, pp. 52–68.Novokhatskii, I.P., Paleozoic Banded Iron Formations ofKazakhstan, in Geologiya i genezis dokembriiskikh zhelez-isto-kremnistykh i margantsevykh formatsii mira (Geologyand Genesis of Precambrian Ferruginous–Siliceous andManganiferous Formations in the World), Kiev: NaukovaDumka, 1972, pp. 164–174.Orlova, E.V., Fosforitonosnye basseiny zarubezhnykh stran(Phosphorite-Bearing Basins in Foreign Countries), Mos-cow: GIGL, issue 19, 1951.Pustovalov, L.V., Petrografiya osadochnykh porod (Petrog-raphy of Sedimentary Rocks), Moscow: Gosgeoltoptekhiz-dat, 1940, vol. 1/2.Ronov, A.B., Stratisfera ili sloistaya obolochka Zemli (koli-chestvennoe issledovanie) (Stratisphere or Stratified Shell ofthe Earth: Quantitative Studies), Moscow: Nauka, 1993.Roy, S., Manganese Deposits, London: Acad. Press, 1981.Translated under the title Mestorozhdeniya margantsa, Mos-cow: Mir, 1986.Rozhnov, A.A., Geological Features of Manganese Mineral-ization in the Western Dzhail’ma Trough and Position ofManganese Mineralization in Iron and Base Metal Occur-rences in the Region, in Margantsevye mestorozhdeniyaSSSR (Manganese Deposits in the USSR), Moscow: Nauka,1967, pp. 311–325.Salivan, H., Les phosphorites de Chaux sedimentaires duMarocco, in Notes Marocanes Soc. Geogr. 14, Rabat, 1960,pp. 7–20.Sapozhnikov, D.G., Osnovy prognoza osadochnykh rudnykhmestorozhdenii (Principles of the Forecasting of Sedimen-tary Ore Deposits), Moscow: Nauka, 1972.Severgin, V.M., Pervye osnovaniya mineralogii ili estestven-noi istorii iskopaemykh tel (First Principles of Mineralogy orNatatural History of Fossil Bodies), St. Petersburg, 1798,part 1/2.Severgin, V.M., Novaya sistema mineralov, osnovannaya nanaruzhnykh otlichitel’nykh priznakakh (New System of Min-erals Based on External Distinctive Features), St. Petersburg,1816.Shatsky, N.S., Phosphorite-Bearing Formations and Classifi-cation of Phosphorite Deposits, in Soveshchanie po osadoch-nym porodam (Conference on Sedimentary Rocks), Mos-cow: Akad. Nauk SSSR, 1955, vol. 2, pp. 7–99.Shnyukov, E.F. and Orlovskii, G.N., Manganese, Ferroman-ganese, and Manganese–Iron Ore Deposits and Occurrences,in Margantsevye rudy Ukrainy (Manganese Ores inUkraine), Kiev: Naukova Dumka, 1993, pp. 12–116.

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Shterenberg, L.E., Nesterova, I.L., Karaseva, G.I., andCherkasova, E.V., Specific Features of the Distribution of Ni,Co, Cu, V, Cr in Manganese Ores and Host Rocks of the Chi-atura Deposit, in Margantsevye mestorozhdeniya SSSR(Manganese Deposits in the USSR), Moscow: Nauka, 1967,pp. 199–214.Sokolova, E.A., Margantsenosnost’ vulkanogenno-osadoch-nykh formatsii (Manganese Potential of VolcanosedimentaryFormations), Moscow: Nauka, 1982.Sokolova, E.A., Problem of the Genesis of Stratiform Depos-its in Cuba, with Reference to Manganese Deposits in Cuba),Litol. Polezn. Iskop., 1976, vol. 18, no. 2, pp. 99–117.Stolyarov, A.S. and Ivlieva, E.I., Solenovian Rocks of theLower Oligocene in the Ciscaucasia, Volga–Don, andMangyshlak Region (Central Part of the Eastern Paratethys):Communication 1. Main Lithological and Structural Fea-tures, Litol. Polezn. Iskop., 1999a, vol. 34, no. 3, pp. 288–318[Lithol. Miner. Resour. (Engl. Transl.), 1999a, vol. 34, no. 3,pp. 259–276].Stolyarov, A.S. and Ivlieva, E.I., Solenovian Rocks of theLower Oligocene in the Ciscaucasia, Volga–Don, andMangyshlak Region (Central Part of the Eastern Paratethys):Communication 2. Facies-Paleogeographic Deposition Envi-ronments, Litol. Polezn. Iskop., 1999b, vol. 34, no. 4,pp. 420–432 [Lithol. Miner. Resour. (Engl. Transl.), 1999b,vol. 34, no. 4, pp. 370–380].Stolyarov, A.S. and Kochenov, A.V., Metal Potential ofMaikopian Rocks of the Mangyshlak Region, Litol. Polezn.Iskop., 1995, vol. 37, no. 2, pp. 161–173.Strakhov, N.M., Osnovy teorii litogeneza (Fundamentals ofthe Theory of Lithogenesis), Vol. 1. Types of Lithogenesisand Their Distribution on the Earth’s Surface), Moscow:Akad. Nauk SSSR, 1960a.Strakhov, N.M., Osnovy teorii litogeneza (Fundamentals ofthe Theory of Lithogenesis), Vol. 2. Regularities of Compo-sition and Distribution of Humid Sediments), Moscow:Akad. Nauk SSSR, 1960b.Strakhov, N.M., Parageneses of Authigenic Minerals in Sed-imentary Ores and Responsible Factors, Litol. Polezn. Iskop.,1964, no. 4, pp. 43–65.Strakhov, N.M., Shterenberg, L.E., Kalinenko, V.V., andTikhomirova, E.S., Geokhimiya osadochnogo margant-sevorudnogo protsessa (Geochemistry of Sedimentary Man-ganese Mineralization), Moscow: Akad. Nauk SSSR, 1968.Strakhov, N.M., Varentsov, I.M., Kalinenko, V.V., et al., Cog-nition of the Mechanism of Sedimentary Manganese Miner-alization, in Margantsevye mestorozhdeniya SSSR (Manga-nese Deposits in the USSR), Moscow: Nauka, 1967, pp. 34–56.Tabagari, D.V., Distribution and Composition of ManganeseOres Genetic Types in the Chiatura Deposit, in Novye dannyepo margantsevym mestorozhdeniyam SSSR (New Data on

Manganese Deposits in the USSR), Moscow: Nauka, 1980,pp. 80–94.Takabatake, A., A Genesis of Manganiferous Iron Deposits inJapan, in Symp. XX Sess. Int. Geol. Congr. (Sobre esimen-tales de manganese) Mexico, 1958, vol. 4, pp. 205–211.Taliaferro, N.L. and Hudson, F.C., Genesis of ManganeseDeposits of the Coast Range of California, 1943, no. 125.Thein, J., Turonian Paleogeography of High Atlas Mountains(Marocco) and North Atlantic, Disch. Geol. Geselschaff,1988, pp. 261–287.Thein, J., Paleogeography and Geochemistry of the Cenom-ano-Turonian Formation in the Manganese District of Imini(Marocco), Geol. Rev, 1990, no. 5, pp. 257–291.Tikhomirova, E.S. and Cherkasova, E.V., Distribution ofTrace Elements in Ores of the Mangyshlak ManganeseDeposit, in Margantsevye mestorozhdeniya SSSR (Manga-nese Deposits in the USSR), Moscow: Nauka, 1967,pp. 258–274.Van Veser, J.R., Phosphorus Compounds, in Phosphorus andIts Environment, Amsterdam: Elsevier, 1974. Translatedunder the title Fosfor v okruzhayushchei srede, Moscow:Mir, 1977, pp. 195–204.Varentsov, I.M. and Rakhmanov, V.P., Manganese Deposits,in Rudnye mestorozhdeniya SSSR (Ore Deposits in theUSSR), Moscow: Nedra, 1974, vol. 1, pp. 109–164.Varsanof’eva, V., Karst Phenomena in the Western Ufim Pla-teau, Zemlevedenie (Soil Science), 1916, vol. 23, part 3/4,pp. 35–60.Vernadsky, V.I., Paragenesis of Chemical Elements in theEarth’s Crust (Address at the Opening of the Geology andMineralogy, December 28, 1909), in Dnevnik XII s’’ezdarusskikh estestvoispytatelei i vrachei (1909–1910) (Diary ofXII Conference of Russian Naturalists and Doctors (1909–1910)), Moscow: Tipogr. Lesnera Sobko, 1910, Section 1,pp. 79–91.Vernadsky, V.I., Istoriya mineralov zemnoi kory (History ofMinerals in the Earth’s Crust), Peterburg, 1923, vol. 1, no. 1.Vinogradov, A.P., Average Content of Chemical Elements inthe Main Types Igneous Rocks of the Earth’s Crust,Geokhimiya, 1962, no. 7, pp. 105–130.Vodorezov, G.I., Varlamov, N.P., and Mul’menko, M.A., TheAsha Phosphorite Deposit in the Ural Region, in Voprosygeologii agronomicheskikh rud (Problems of the Geology ofAgrochemical Ores), Moscow: Akad. Nauk SSSR, 1956,pp. 103–119.Volkov, B.N., Phosphorite-Bearing Rocks in GeoanticlinalFormations of the Variscan Stage of the Beloretsk–ZalairSynclinorium and Bel’skii Trough in the Southern Urals, inFormatsionnyi metod v prognoze i izuchenii mestorozhdeniigornokhimicheskogo syr’ya (The Formation Method for theForecast and Study of Mining-Chemical Mineral Deposits),Moscow: Nedra, 1974, pp. 61–74.

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