ISSN 0024-4902, Lithology and Mineral Resources, 2009, Vol. 44, No. 1, pp. 118. Pleiades Publishing, Inc.

., 2009. Original Russian Text V.N. Kholodov, R.I. Nedumov, 2009, published in Litologiya i Poleznye Iskopaemye, 2009, No. 1, pp. 322.

Association of Manganese Ore and Phosphorite-Bearing Facies in Sedimentary Sequences: Communication 1. Parastereses and Parageneses of Phosphorus and Manganese in MesozoicCenozoic and Upper Paleozoic Rocks
V. N. Kholodov and R. I. Nedumov
Geological Institute, Russian Academy of Sciences, Pyzhevskii per. 7, Moscow, 119017 Russia e-mail: rostislavn@yandex.ru
Received May 19, 2008

AbstractIt is shown that cooccurrences (parastereses) of chemical elements, minerals, sedimentary rocks, facies, and formations should be distinguished from their parageneses, which represent geological formations related to a single geological process. It has been established that phosphorus is concentrated in sedimentary manganese ores and is not accumulated in volcanosedimentary and hydrothermal deposits. Parageneses of Mn and P in sedimentary deposits are characterized. Parastereses of manganese ore and phosphorite-bearing facies in Oligocene rocks of southwestern Eurasia, Mesozoic and Upper Paleozoic sections of the Urals, and MesozoicCenozoic sequences of Morocco are considered. DOI: 10.1134/S0024490209010015

The concept of spatial association (parasteresis) of minerals in different regions of the Earth originated in the terminal 18thinitial 19th centuries. The idea of spatial association of some minerals was rst proposed by the Russian Academician V.M. Severgin (17981816), who studied regularities of their spatial distribution in Russia. He demonstrated that the occurrence frequency of minerals varies notably at the Earths surface and formulated the concept of mineral contiguity, i.e., the ability of minerals to form associations. The same idea appeared later in works by pupils of the famous German scientist A. Werner. One of them, an outstanding mineralogist from Freiberg Breithaupt (1849), who emphasized the signicance of the concepts of mineral contiguity, proposed the term paragenesis1 and described numerous examples of their spatial association. Since that time, the term paragenesis is widely used in the mineralogical literature. The works by V.I. Vernadsky and A.E. Fersman widened substantially its essence. As is known, these researchers developed the principles of geochemistry. Naturally, they included chemical elements into the notion of paragenesis. Vernadsky (1910, 1923), who developed the theory of 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 genesis).

that determined the formation of certain mineral bodies, associations, and generations, on the one hand, and as the mineral bodies, associations, and generations, on the other hand. According to Vernadsky, isomorphism is of great signicance in the formation of geochemical parageneses. He dened 18 typomorphic series, which determined the cooccurrence of chemical elements. In Geochemical and Mineralogical Methods of Prospecting for Mineral Resources published in 1940, Academician A.E. Fersman proposed the following denition of the notion of paragenesis: paragenesis is a cooccurrence of minerals (or elements) in a certain geochemical system related to a certain geochemical process (Fersman, 1953). It should be emphasized that both Vernadsky and Fersman accepted the persistence of cooccurrence (the main feature of paragenesis) as a criterion of similar genesis. Despite the discrimination of smaller categories (associations and generations of elements or minerals), they considered occurrence frequency and genesis as different aspects of the same phenomenon. In (Pustovalov, 1940), the notion of paragenesis gained a wider interpretation: it included not only chemical elements and minerals, but also sedimentary rocks. Postulating that mechanical and chemical differentiation of matter represents the main regularity in sedimentary rock formation, Pustovalov wrote: the normal sedimentary process is characterized by the succession of certain types of sedimentary rocks, which replace each other in both lateral and vertical direc1

KHOLODOV, NEDUMOV

tions, resulting in the formation of regular associations determined by the character of surcial differentiation in each sedimentation zone. This provides grounds for dening the paragenesis of sedimentary rocks. He wrote further: the dominant accumulation of genetically related sediment types at the Earths surface follows a certain succession in line with sedimentary differentiation; replacement of the dominant sediment types is repeated periodically according to the general rhythm of the Earths geological development; therefore, we have grounds for dening the paragenesis of sedimentary sequences (Pustovalov, 1940, p. 381). Accepting such a wide denition of paragenesis proposed by Pustovalov, we should note the following fact: vagueness and uncertainty of this notion are amplied when we pass from formations of a low organization level (chemical elements) to those of a higher level (sedimentary rocks, sequences, formations, and others). Pustovalovs ideas of the paragenesis of sedimentary rocks were supported and further developed by some tectonists (primarily, N.P. Kheraskov and N.S. Shatsky). In the fundamental work by Kheraskov (1952), the sedimentary formation was dened as paragenesis of sedimentary rocks. He wrote: Rocks represent a paragenesis of minerals; formations, a paragenesis of rocks. Similarly as rocks characterized on the basis of their mineral composition and structure (texture), formations should be described and classied according to their composition and structure (Kheraskov, 1952, p. 37). In the later work dedicated to phosphorite-bearing formations, Shatsky developed in fact the same ideas: Geological formations are assemblages or associations of rocks, separate elements (rocks, beds, and sediments) of which are paragenetically correlated in both temporal (interlayering and succession) and spatial aspects (facies zones and others). He wrote further: Formations represent natural assemblages, complexes, and parageneses of rocks rather than arbitrary sets of rocks and facies, as supposed by some researchers (Shatsky, 1955, p. 8). It is interesting that according to Shatsky and Kheraskov, identication of specied formations requires the purely empirical discrimination of similar associations of rocks or facies that are developed universally in different regions of our planet. Academician Betekhtin (1949, 1950) proposed a quite different interpretation of the notion of paragenesis. He was rst to show that the permanent cooccurrence of minerals not necessarily indicates their similar origin. He noted, for example, that iron and copper suldes always occur together with iron oxides and malachite in hydrothermal veins. However, a detailed analysis of the sequence of mineral formation reveals the following fact. Iron and copper suldes represent an early generation related to the interaction of metals with

hydrogen sulde; the suldes were subsequently oxidized, and the inuence of carbon dioxide results in the formation of malachite. Thus, we are dealing with two different (in terms of time and dominant chemical reactions) processes. Hence, the association of permanently occurring minerals includes two parageneses: paragenesis of suldes and paragenesis of oxides and carbonates. Thus, according to Betekhtin, the empirically dened assemblage of minerals, chemical elements, or sedimentary rocks cannot be considered a genetic unity or paragenesis. According to the authors of article devoted to paragenesis in (Geologicheskii Slovar, 1973), such cooccurrence should be called parasteresis.2 Only the comprehensive study of spatiotemporal relationships between components of parasteresis makes it possible to outline genetically different associations or parageneses. It is clear that empirical discrimination of associations of chemical elements, minerals, or sedimentary rocks (parastereses) represent a rst stage of the research, while observations of spatiotemporal relationships, discrimination between generations, and genetic interpretations (parageneses) crown the study of geochemistry, mineralogy, sedimentology, facies, and formations. Concluding this brief historical review and passing to the description of manganese ore and phosphatebearing faces, we should emphasize that this article is only devoted to general characteristics of the cooccurrence of manganese ores and phosphates. More complicated issues of their paragenesis are discussed here only partly and only for cases furnished with a sufcient amount of factual material. Cooccurrence of Mn and P in sedimentary rocks is a well-known phenomenon. It is considered in many works (Betekhtin, 1946; Rozhnov, 1967; Gryaznov and Chervonookaya, 1967; Gavrilov, 1972; Varentsov and Rakhmanov, 1974; Danilov, 1982; Roy, 1986; and others). Recently, it became clear that issue of the parasteresis of Mn and P includes several aspects: (1) regularities of phosphorus distribution in Upper Paleozoic, Mesozoic, and Cenozoic sedimentary manganese deposits; (2) spatiotemporal relationships between manganese ore and phosphate-bearing facies in the Upper Paleozoic and MesozoicCenozoic sequences; (3) cooccurrence of deposits of old pelletal phosphorites with sedimentary ferromanganese ores and sedimentary manganese deposits in the Lower Paleozoic and Precambrian sequences.
2

The term consists of two Greek words: para (near) and stereo (volumetric, spatial); i.e., it indicates spatial association. Vol. 44 No. 1 2009

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ASSOCIATION OF MANGANESE ORE AND PHOSPHORITE-BEARING FACIES

We shall attempt to discuss these aspects in two articles. REGULARITIES OF PHOSPHORUS DISTRIBUTION IN THE UPPER PALEOZOIC, MESOZOIC, AND CENOZOIC SEDIMENTARY MANGANESE DEPOSITS It is well known that Mesozoic and Cenozoic sedimentary manganese ores are always enriched in phosphorus. As was shown in (Betekhtin, 1930, 1946), phosphorus is a harmful admixture in manganese ore. Therefore, like the Fe content, the P content always determines the quality of this mineral resource. Table 1 based on data of many researchers demonstrates the distribution of P and Fe in ores from different sedimentary deposits of Russia and some other countries. Provided that the average or clarke P content in sedimentary rocks is estimated at 0.093% (Vinogradov, 1962) and the average P content in stratisphere is estimated at 0.078% (Ronov, 1993), it becomes clear that the quantity of phosphates buried in bottom sediments together with Mn is tens or even hundreds of times higher than its clarke concentrations. It should be emphasized that the quantity of P involved in the sedimentary process exceeds substantially that in hydrothermal and volcanosedimentary manganese ores. Table 2 presents published data characterizing the distribution of Fe, Mn, and P in hydrothermal and sedimentary exhalative deposits of different countries. The analysis reveals that volcanic-associated manganese deposits are always enriched in Fe, slightly depleted in Mn, and extremely depleted in P (Figs. 1, 2). Decit of P in hydrothermal and volcanosedimentary ores was rst suggested by Rozhnov (1967) and Gavrilov (1972) and subsequently conrmed by Sokolova (1982). This inference is substantiated by the comparison of diagrams (Figs. 1, 2) and is consistent with the following fact: phosphorus participates actively as apatite in the magmatic process, but it is involved rarely in hydrothermal and volcanogenic exhalative processes. This issue is scrutinized in our previous works (Kholodov and Butuzova, 1999; Kholodov, 2002, 2003a, 2003b, 2006). The Guberly, Kos-Istek, and Karagala manganese deposits associated with Ordovician volcanosedimentary formations of the Sakmara allochthon (Urals) represent exceptions among hydrothermal exhalative deposits: the P content in them amounts to 23% (locally, 1118%). This is, however, explained by superimposition of the hydrothermal volcanogenic manganese mineralization on sedimentary phosphorite formation widely developed in Ordovician organic-rich siliceous phtanite sequences (Gavrilov, 1972; Khvorova et al., 1978). Similar situation was likely characteristic of the Upper Paleozoic manganese deposits in the Czech
LITHOLOGY AND MINERAL RESOURCES Vol. 44

Republic and some volcanosedimentary deposits in Japan, where signicant quantities of phosphorus were accumulated (Takabatake, 1956). These areas were characterized by the superimposition of sedimentary phosphorite formation and volcanosedimentary manganese deposition. The geological setting in these deposits resembles that in the Caradocian uraniumrare metalphosphate deposits of northern Kazakhstan, which are considered by many researchers (S.D. Levina, L.V. Khoroshilov, and others) as hydrothermally altered sedimentary deposits. Their origin is attributed to a multistage process, which commenced with the formation of old nodular-stratiform phosphate bodies, and the subsequent hydrothermal redeposition (Kholodov and Butuzova, 1999). Hydrothermal and volcanosedimentary manganese deposits are characterized by high-quality ores with a very low content of phosphates. It should also be noted that volcanosedimentary and hydrothermal manganese deposits frequently contain elevated admixtures of Cu, Pb, Zn, As, Ba, Be, W, and other elements (Rozhnov, 1967; Strakhov et al., 1967, 1968; Varentsov and Rakhmanov, 1974; Roy, 1981). Combined with the decit of P, this feature imparts a unique geochemical appearance to ores of this group and even serves as a genetic signature of endogenic ores. Of particular interest is the behavior of phosphorus in sedimentary oxide and carbonate ores. Table 1 demonstrates that almost each sedimentary deposit contains oxide ores usually composed of pyrolusite, psilomelane, cryptomelane, todorokite, and birnessite, as well as carbonate ores represented by rhodochrosite and manganiferous carbonates. Analysis of the behavior of P in these two different mineral types of manganese ores reveals that average values of percentage variations of P contents are approximately equal (Fig. 3). In other words, elevated P concentrations are characteristic of both mineralogically different groups and they represent a single cooccurrence (parasteresis) of high contents of phosphates and manganese ores. However, observations of occurrence forms of phosphates in manganese deposits in the South Ural Basin (Gryaznov and Chervonookaya, 1967; Khodak, 1976; Shnyukov and Orlovskii, 1993) suggest that phosphorus is precipitated and xed in oxide and carbonate ores by different ways. It should primarily be noted that phosphorus occurs in both manganese ores varieties as phosphatized bone breccia, accessory apatite, phosphate admixture in large psilomelane beans and concretions, vivianite, and phosphate fringes on clay minerals. The rst group of phosphate inclusions is represented by clasts and small crystals of accessory apatite, as well as fragments of phosphatized mammal and reptilian bone remains. They were mechanically deposited in the manganese ore bed and were derived from the
No. 1 2009

KHOLODOV, NEDUMOV

Table 1. Distribution of Fe, Mn, and P (%) in sedimentary manganese deposits Deposit, occurrence Zelenyi Dol (Ukraine) Ordzhonikidze (Ukraine) average oxide ores carbonate ores oxide ores oxidecarbonate ores average Marganets (Ukraine) average oxide ores carbonate ores oxide ores oxidecarbonate ores carbonate ores oxide ores oxidecarbonate ores carbonate ores Tokmak (Ukraine) oxide ores carbonate ores oxide ores oxidecarbonate ores carbonate ores Chiaturi (Georgia) oxide ores carbonate ores oxide ores carbonate ores oxide ores carbonate ores Kvirili (Georgia) oxide ores carbonate ores Laba (Russia) average oxide ores carbonate ores oxide ores carbonate ores Mangyshlak (Kazakhstan) oxide ores carbonate ores Polunochnoe (Russia) oxide ores oxidecarbonate ores carbonate ores Fe 0.862.05 0.357.44 1.413.30 2.632.84 2.133.10 2.50 0.73.5 0.357.44 1.413.30 0.57 1.071.53 1.31 2.602.88 2.253.23 2.45 4.358.90 2.456.29 2.2410.13 0.11.2 24 0.331.73 0.261.42 0.821.46 0.591.62 1.095.2 3.416.8 1.984.25 1.802.25 1.046.03 1.802.25 1.225.15 1.306.34 tr.3.57 4.164.88 3.053.60 4.14.70 Mn 619.9 45.9154.99 6.9673.76 7.0033.86 19.422.58 22.2034.87 25.60 3055 6.973.76 7.033.86 51.2 18.344.4 23.70 22.7626.22 20.4728.87 21.71 35.68 24.65 11.6645.87 10.2952.31 8.8832.56 4258 630 11.5760.61 3.5532.22 29.349.3 14.425.2 11.239.3 8.124.3 13.4526.13 21.1828.85 12.3634.63 21.4828.85 14.8233.30 7.2346.90 tr.23.08 20.7432.17 20.721.88 27.1427.18 P 0.222 0.1520.78 0.071.04 0.080.24 0.1730.226 0.1370.220 0.212 0.160.35 0.071.01 0.080.24 0.02 0.250.31 0.09 0.150.17 0.140.20 0.38 0.32 0.18 0.180.54 0.160.27 0.090.25 0.100.22 0.200.30 00.2 00.58 0.140.16 0.030.39 0.100.47 0.140.54 tr.0.19 0.0140.03 tr.0.65 0.0140.03 tr.0.06 tr.0.91 tr.0.79 0.110.6 0.19 0.150.17 Source Shnyukov and Orlovskii, 1993 Betekhtin, 1946 Gryaznov, 1967 The same Shnyukov et al., 1993 The same " Betekhtin, 1946 Gryaznov, 1967 The same Varentsov and Rakhmanov, 1974 The same " Shnyukov et al., 1993 The same " Gryaznov and Chervonookaya, 1967 The same Shnyukov et al., 1993 The same " Betekhtin, 1946 The same Shterenberg et al., 1967 The same Tabagari, 1980 The same Dolidze et al., 1980 The same Betekhtin, 1946 Kalinenko et al., 1967 The same Kalinenko, 1990 The same Tikhomirova and Cherkasova, 1967 The same Betekhtin, 1946 The same "
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LITHOLOGY AND MINERAL RESOURCES

ASSOCIATION OF MANGANESE ORE AND PHOSPHORITE-BEARING FACIES Table 1. (Contd.) Deposit, occurrence Marsyat (Russia) Ulutelyak (Russia) total content total content oxide ores carbonate ores Imini (Morocco) Bu Aggun (Morocco) oxide ores oxidecarbonate ores carbonate ores Saint Bebe (Morocco) oxide ores carbonate ores
Note: () no data.

Fe 410 1.011.63 1.972.43 0.422.79 0.991.02 1.52.3 00.1 0 0.5 0.05 0.05

Mn 2535 6.208.27 5.589.39 19.9720.95 3.712.56 47.5156.57 46.7552.40 10.07 31.30 46.750.84 1.67

P 0.20.6 0.051.05 0.050.06 0.030.06 0.010.23 0.010.23 0.010.23 0.010.14 0.010.14 The same

Source

The same " " " Bouladon and Jurovski, 1956 Thai, 1990 The same " " "

JurassicCretaceous weathering crust underlying the ore bed (Fig. 4). As was shown in (Kholodov, 2006), this weathering crust was composed of material eroded from the apatite-bearing gabbroanorthosite massifs in the Ukrainian crystalline shield. The crust contained numerous high-grade apatite and titanomagnetite placer deposits
Iron % 10 9 8 7 6 5 4 3 2 1 0
Ordzhonikidze Marganets Tokmak Chiaturi Kvirili Depression Laba Mangyshlak Polunochnoe Marsyat Ulutelyak Imini

(Irsha placer group, Novopoltavsk rare-metalapatite placer group, and others), in addition to clayey eluvium. Erosion of these terrigenous accumulations and washout of numerous phosphate bone remains promoted the universal enrichment of ore-bearing beds in the South Ukraine Basin by phosphate fragments.
Phosphorus % 1.1 1.0

16.8

Manganese

% 80 70 60 50 40 30 20 10 0
Ordzhonikidze Marganets Tokmak Chiaturi Kvirili Depression Laba Mangyshlak Polunochnoe Marsyat Ulutelyak Imini

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0

Ordzhonikidze Marganets Tokmak Chiaturi Kvirili Depression Laba Mangyshlak Polunochnoe Marsyat Ulutelyak Imini

Fig. 1. Distribution of Fe, Mn, and P in sedimentary manganese ores. LITHOLOGY AND MINERAL RESOURCES Vol. 44 No. 1 2009

6 Iron
12.4 23.3 19.3 14.1 11.8

KHOLODOV, NEDUMOV Manganese Phosphorus % 1.1 1.0 % 80 70 60 50 40 30 20 10 0

Karadzhal Ktai Takhta-Karachi Tetritskaroi Kozhaevsk Zhaksy Tasoba Los Chivos Charco Redondo Barrancos Ponupo El Cristo Franciscan Formation Karadzhal Ktai Takhta-Karachi Tetritskaroi Kozhaevsk Zhaksy Tasoba Los Chivos Charco Redondo Barrancos Ponupo El Cristo Franciscan Formation

% 10 9 8 7 6 5 4 3 2 1 0

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0

Karadzhal Ktai Takhta-Karachi Tetritskaroi Kozhaevsk Zhaksy Tasoba Los Chivos Charco Redondo Barrancos Ponupo El Cristo Franciscan Formation

Fig. 2. Distribution of Fe, Mn, and P in hydrothermal and volcanosedimentary manganese ores.

The second and third groups include typical authigenic either diagenetic or sedimentary phosphate minerals formed in the Oligocene basin. The second group consists of phosphates forming large psilomelane concretions (nodules), vivianite inclusions, and phosphate rims on clay minerals. They are most typical of manganese oxide ores related to colloidal processes of sorption or chemosorption. It should be remembered that orthophosphate, a widespread form of phosphates in marine and interstitial waters, is characterized by the negative charge; iron trioxide, by the positive one. It means that interstitial waters are more favorable for the formation of vivianite in manganese ore beds. It is more difcult to explain the formation of other phosphorous compounds because both manganese oxide and silica are characterized by negative charges, which hamper their precipitation together with orthophosphate. This issue can likely be explained by the recent discovery of an additional form of phosphorus occurrence as polyphosphates in seas and oceans. The polyphosphates appeared to be widespread and closely associated with biological processes in marine settings. According to (Hooper, 1974; Van Veser, 1974; and others), polyphosphates represent complex compounds consisting of phosphate chains, in which phosphate compounds are interconnected with oxygen bridges

and multiply repeated. They are dened by the general formula n + 1PnO3n + 1, where M is metal, hydrogen ion, and others. The characteristic feature of polyphosphates is their ability to carry both positive and negative charges. Like structures of clay minerals, the head and tail of such complex molecules may be characterized by positive and negative charges, respectively. Such a property is responsible for the ability of polyphosphates to precipitate together with clay minerals. It is conceivable that polyphosphates are present in psilomelanes (complex colloids). In any case, the main process in manganese ore zones with dominant manganese and Fe hydroxides is the coprecipitation of complex colloid compounds. The third group of phosphate accumulations includes phosphate minerals associated with manganese carbonate ores. In addition to rhodochrosite (MnCO3), siderite (FeCO3), and sideroplesite (Mg,Fe(CO3), they contain widespread kurskite or francolite. The last mineral is dened by the formula Ca10[PO4]6[F2(OH)2(CO3)O] or Ca10-n/2(PO4)6-m(CO3)mF2, where m < n. In fact, it represents apatite with PO4 in the lattice replaced by carbonate. It can likely be stated that all minerals of this group formed in the same chemical precipitation settings. It should be mentioned that phosphates in the sedimentation zone dissolve readily under slightly acid conditions and precipitate in slightly alkaline settings
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ASSOCIATION OF MANGANESE ORE AND PHOSPHORITE-BEARING FACIES

(Kholodov, 2002, 2003a, 2003b; 2004, 2008). Distortion of the carbonate equilibrium and alkalization of waters in the manganese carbonate formation zone stimulates the accumulation of phosphates as kurskite or francolite. Thus, it is clear that cooccurrence of phosphorus with manganese ores (or parasteresis of P and Mn) consists of two distinct (sorptional and chemical) parageneses. COOCCURRENCE OF MANGANESE ORE AND PHOSPHORITE-BEARING FACIES IN UPPER PALEOZOIC AND MESOZOICCENOZOIC SEQUENCES Of particular interest are spatiotemporal relationships between manganese ore and phosphorite-bearing facies in MesozoicCenozoic sequences of Russia and some adjacent countries. The facies characteristic of EoceneOligocene sedimentary manganese deposits is given in (Betekhtin, 1946; Strakhov, 1964; Strakhov et al., 1968; Varentsov and Rakhmanov, 1974; Rakhmanov et al., 1978, 1982; Shnyukov and Orlovskii, 1993). It has been established that manganese ore accumulations are formed in the underwater deltaic, deltaic sandysilty and siltyclayey, and carbonate shelf facies. They are characterized by highly variable grain-size composition with the maximal ore range usually shifted as shown in Fig. 5 adopted from (Strakhov, 1968). Oreenclosing rocks of the Laba deposit are obviously represented by coarse-grained sediments (sands and even gravelstones), while they associate largely with clayey and silty varieties in some deposits of the southern Urals. It should be emphasized that most researchers, who studied Oligocene manganese ores, consider them as diagenetic formations. This is evident from the dominance of typical nodular mineralization forms, complex relationships between ore accumulations and host rocks, and some other features comprehensively described in the monograph by Kalinenko (1990). It is evident that formation conditions of manganese ore facies in Ukraine, the Caucasus, and Mangyshlak characterize only some aspects of manganese mineralization. Nevertheless, it should be noted that oreenclosing sediments contain diverse fossil marine molluscan species, solitary corals, bryozoans, crustaceans, shes and several tens of foraminiferal forms identied by Nosovskii (1964) and reproduced in (Strakhov, 1968). This fact indicates that waters of the ore-bearing part of paleobasin had normal salinity and gas regime. They were characterized by the high content of oxygen and the absence of H2S. Phosphorite-bearing facies are usually conned to shallow areas of platformal and geosynclinal seas. They
LITHOLOGY AND MINERAL RESOURCES Vol. 44

Ordzhonikidze

Marganets

Chiaturi

Kvirili Laba

Mangyshlak

Fig. 3. Distribution of P in oxide and carbonate sedimentary manganese ores.

are distinctly subdivided into two facies groups particularly widespread in the Cretaceous and Paleogene sequences. The rst group is represented by nodular phosphorites and hardgrounds in terrigenous sequences of platforms. These deposits associate usually with sediments of highly variable grain-size composition: from clays and ne-grained silts to coarse-grained sandstones and gravelstones. They are largely conned to the shallowest part of the shelf and intertidal zone. Kazakov (1937) estimated erroneously their formation depths at 100150 m. Based on the ecological analysis, Bushinskii (1954) reduced this value to 6070 m. At the same time, both researchers considered phosphorites as typical chemogenic or biogenic-chemogenic sediments. In (Kholodov, 2008), the author of the present communication demonstrated that phosphorite formation largely represents a diagenetic process. Nodular and platy phosphorites are formed in zones ranging
No. 1 2009

Polunochnoe

Tokmak

Carbonate 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 Oxide 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0

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

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

KHOLODOV, NEDUMOV () W
Q N2Q N P

1 9

4 (b)

Q N2Q N2s1-N2ns N1t Pbrs P2kv

(c)
Q N2Q N2s1N2ns N2s1

P3brs

1 7

2 8

3 9

4 10

5 11

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

from shallow shelf (6070 m) to beach settings. Intertidal zone of the paleobasin is characterized by the redeposition and secondary concentration of phosphate nodules. It is noteworthy that phosphorites are mainly formed in a normal oxygenated basin. The second group of phosphorite-bearing facies includes the phosphatized bone remains of sh skeletons and their breccias. They are commonly associated with manganese ores. Phosphatized remains of sh skeletons and their fragments are characterized by wide lateral and stratigraphic distribution in Paleogene sequences of southern Russia, Ukraine, the Caucasus, and Mangyshlak. They occur usually as rare isolated inclusions that are not responsible for the lithological appearance of clay sequences. In some areas, however, their accumulations acquire the rock-forming signicance. One can see entire members and lenses of phosphatized bone detritus with elevated admixtures of rare and radioactive elements.

Such phosphorite-bearing beds are widespread in the Maikop sediments of Mangyshlak (Melovoe, Tomak, Taibogar, Tasmuran, Sadyrnin, and other ore deposits and occurrences) and in the EoceneOligocene boundary layers of the Ergenei area (Volga region), where similar mineralization has been found in the Chernye Zemli locality near Elista (Stepanov, Tsentralnoe, YashulTroitsk, Vorobev, Nugrin, and other ore occurrences). They are described in (Kochenov et al., 1970; Stolyarov and Kochenov, 1995; and Stolyarov and Ivleva, 1999a, 1999b). Numerous descriptions of sh beds and associated rare-metal deposits demonstrate that they were deposited in three different settings. Mass burials of shes were formed in depressions (traps) contaminated with H2S and located on the shelf near arches of synsedimentary uplifts (banks, shoals, or nondeposition areas). The clayey material characterized by the absence of benthic organisms accumulated iron suldes, sh skelVol. 44 No. 1 2009

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Table 2. Distribution of Fe, Mn, and P (%) in volcanosedimentary manganese deposits Age Devonian (Famennian) The same " " " " 12.38 3.02 Ordovician or SilurianDevonian 0.8414.1 2.1232.46 35.72 0.04 23.31 0.08 " Novokhatskii, 1972 6.04 21.15 0.018 The same 4.6 27.2 0.032 Kavun, 1967 3.47 28.3 0.07 822 514 0.04 The same Novokhatskii, 1972 3.5714.8 17.5526.22 0.04 Kalinin, 1965 2.6519.3 14.638.5 0.030.06 Betekhtin, 1946 Fe Mn P Source

Deposit, occurrence

Karadzhal, high-grade ores

The same

Karadzhal, low-grade ores

Karadzhal

Eastern Karadzhal

Western Karadzhal

Ktai

LITHOLOGY AND MINERAL RESOURCES

The same

Takhta-Karachi

0.010.47 Strakhov et al., 1968 (0.47 is an anomalous sample, others are 0.010.06) 00.20 0.040.06 0.030.04 0 The same Betekhtin, 1946 Gavrilov, 1972 The same

ASSOCIATION OF MANGANESE ORE AND PHOSPHORITE-BEARING FACIES

Vol. 44

Tetriktsaroi ores (Georgia) Middle Devonian (Givetian) Ordovician The same Late CretaceousEocene The same " " " 0.764.47 1.795.29 0.544.52 4.065.81 0.822.03 0.422.65 1.494.26 0.641.62 1.9310.49 0.355.57 1.525.52 3.429.27 3.4411.83 14.342.81 35.7837.71 35.7741.12 9.6559.57 22.1650.76 19.0941.21 28.6647.30 14.9828.66 29.047.81 6.8537.51 6.9744.10 32.8842.71 11.1030.29

Paleocene

0.723.31

7.4646.76

No. 1

Kozhaevsk (Southern Urals)

Zhaksy (northern Kazakhstan)

2009

Tasoba (northern Kazakhstan)

Los Chivos (Cuba)

00.004 00.004 00.004 00.004 0.004 00.11 02.96 0.033.00 0.011.32 0.051.71

Sokolova, 1976 The same " " " Taliaferro and Hudson, 1943 Strakhov, 1968 Gavrilov, 1972 Gavrilov, 1972 Gavrilov, 1972

Charco Redondo (Cuba)

Barrancos

Ponupo

El Cristo

Ores of the Franciscan Formation (United States) Late JurassicCretaceous Ordovician Ordovician Ordovician Ordovician

Sakmara zone (Southern Urals)

Kos-Istek (Sakmara zone)

Guberly (Sakmara zone)

Karagala (Sakmara zone)

10 Sand L M Ch1 N B-T Ch2 Silt

Coarse Fine

KHOLODOV, NEDUMOV Clay

Fig. 5. Schematic localization of manganese ores in sedimentary rocks of different grain size compositions. Modied after (Strakhov et al., 1968). Deposits: (L) Laba, (M) Mangyshlak, (Ch1) Chiaturi, lower horizon, (Ch2) Chiaturi, upper horizon, (N) Nikopol, (B-T) Bolshoi Tokmak.

etons, their fragments, coalied wood remains, and even intact tree trunks up to 35 m long. Owing to alkalization and dissolution of the carbonate part of skeletons, the carbonatephosphate sh bone remains became centers of phosphorus diffusion and were replaced by phosphates (Kholodov, 2008). In addition to phosphatized fragments of sh, whale, and bird bones, shark teeth, and other pseudomorph structures, phosphate nodules (several centimeters across) and thin lenses usually conned to the basal parts of beds were also formed. Intense phosphate precipitation could also be stimulated by the decomposition of sh organic matter and the formation of organic stimulators, which entered seawater and inuenced the precipitation of phosphates (McConnell and Frajola, 1961; Bushinskii, 1967). The second facies type is represented by the phosphatized bone breccias that form diachronous bodies and reect the transgressive position of Oligocene sequences. In these bodies, signicantly smaller redeposited phosphatized bone remains are distinctly conned to sandysilty fractions with gravel-sized quartz fragments. Based on the structure of ore-bearing lenses in the Melovoe deposit in Kazakhstan (Fig. 6), the redeposited phosphate detritus forms a single apron that conformably overlies the older sediments and is inherited by all subsequent ore levels. Such relationships could appear only due to transgression of paleobasin and only when the basal layer reects the advancement of shoreline toward uplifts. It should be noted that the H2S-contamination front also probably followed the migrating shoreline and the redeposition of sh remains in the oxic environment. In any case, it is clear that shelf depressions were lled with the heavy H2S-contaminated waters, while the H2S-contaminated anoxic environment gave way to oxic phases with high-energy hydrodynamics near the coast. In general, the mass death of shes and, probably, mammals proceeded in the H2S-contaminated settings at the transition between oxic and anoxic regimes. It

should be emphasized that the boundary between the H2S-contaminated and aerated waters migrated permanently toward the Karagiin Uplift simultaneously with the shoreline migration. The rapid dislocation of H2S-contaminated waters is recorded along the prole in Fig. 6, which demonstrates sulde incrustations on erosion surfaces of Oligocene sequences. The third facies type of sh bone breccia is most characteristic of the Ergenei area with abundant stratiform lenses. They also occur on slopes of synsedimentary uplifts in deeper settings with less intense H2S contamination. Fish beds of this area frequently contain glauconite cemented largely by carbonates instead of clayey material. In general, the facies pattern of sh bone breccia in the Ergenei area reects variations in the hydrosulfuricoxic settings, the mechanism of which is insufciently clear and requires special studies. It is noteworthy that the manganese ore and phosphorite-bearing facies usually demonstrate close spatiotemporal association with each other. Figure 7 illustrates spatial relationships between the phosphatized sh bone lenses of the Melovoe deposit and manganese ore lenses of Mangyshlak. Despite different ages of these deposits, they are likely characterized by a distinct genetic link: dispersed sh remains in the Oligocene clayey sequences form a single aureole around both phosphorite-bearing and manganiferous lenses. Such a close relationship between phosphorite-bearing facies of the sh cemetery type and sedimentary manganese deposits is more distinct in Fig. 8 reproduced from (Stolyarov and Kochenov, 1995). The gure shows that Paleogene sections contain two main intervals with phosphorite and manganese ore occurrences. The rst interval corresponds to the Pshekha, Nikopol, and UzunbasKendzhala formations. It is well developed in both western and eastern areas, but the largest manganese deposits are located in Ukraine and Hungary. The second interval coincides with the Karadzhalga and Olga formations. They include the rare metal phosphate deposits of the Mangyshlak and Buzachi areas. It is noteworthy that both manganiferous and phosphorite-bearing sediments always make up spatial associations located close to each other. Analysis of the available factual material provides suggests that the central part of the study region in Ciscaucasia was occupied by a spacious H2S-contaminated sea basin during the entire Maikopian time (~10 Ma). The basin likely represented an analogue of the Black Sea (Arkhangelskii and Batalina, 1929; Strakhov, 1960a, 1960b).
Vol. 44 No. 1 2009

LITHOLOGY AND MINERAL RESOURCES

ASSOCIATION OF MANGANESE ORE AND PHOSPHORITE-BEARING FACIES () SE 4 3 2 1 1 2

11

Zhazgurly Syncline

Mys Peschanyi Uplift

Segendy Syncline

Beke-Bashkuduk Anticline

m 100 0 100
1 ksh N1

Chakygan Syncline Karatau Meganticline

Q N
2 P3 kr1

(b)
N 5
2 kr P3 2 2 kr sd P3 2 2 P3 kr1 2 kr P3 1 1 os P3 1 kl P3

3
1 P3 kd

N
1ksh N1 2 P3 kr2

SP2

2 1

200 300

1 kn P3 2

SP1
1 kn P3 1

2 P3 kr1

D
3 ad P2

1 kl P3

400 500 1 2

1 kn P3 2 3 P2 ad 1 kn P3 1

P3uz

4 16

5 17

6 18

7 19

8 20

9 21

10 22

11 23

12 24

13

14

15

Fig. 6. Distribution of phosphoriterare metal and manganese ores in the Mangyshlak region. Modied after (Stolyarov and Kochenov, 1995). (a) Transverse section of the ore lense in the Melovoe deposit; (1) clays with scattered sh remains, (2) alternating clays with scattered sh remains and fucoids. Numerals in the gure correspond to numbers of ore beds. (b) Geological cross section of the Mangyshlak ore district: (1) marl, (2) calcareous clay, (3) clay, (4) clay with admixture of silty material (up to 5%), (5) silty clay, (6) sandysilty rocks, (7) ostracods, (8) mollusks, (9) siderite concretions, (10) fucoids, (11) scattered sh remains, (12) alternating beds with sh remains and fucoids, (13) accumulations of sh remains (bones, scale) at bedding surfaces, (14) diatoms, (15) algal remains: (a) rare, (b) accumulations at bedding surfaces, (16) sulde beds: (SP1) lower, (SP2) upper, (17) bone breccia bed, (18) nely dispersed (globular) pyrite, (19) spotty aggregates of globular pyrite, (20) aggregates of crystalline pyrite, (21, 22) bone detritus lenses: (21) split, (22) stratiformlenticular, (23) manganese deposits, (24) elevated Mn concentrations. (CD) Segment of the prole constructed for the Uzunbas and Kuyulus formations across the manganese deposit area. Upper Eocene: ( P 3ad) Adaev Formation. Lower Oligocene: ( P 3uz) Uzunbas Formation, ( P 3kl) Kuyulus Formation, ( P 31kn) Kendzhala Formation: (kn1) lower, (kn2) upper; Yuzhnomangyshlak Formation:
2 1 ( P 3os) 1 1 1 2

Ostracoda Beds,

1 ( P 3kd)

Kaunda Beds. Upper Oligocene, Karagiin Formation: ( P 3kr1)

lower subformation, ( P 3kr2) upper subformation. Lower Miocene: (N1ksh) Kashkarata Formation. (N) Neogene, undivided; (Q) Quaternary, undivided.

The existence of H2S contamination in the Maikopian sea is conrmed by the lack of benthic fossils in the clayey sediments and calculations of the MoMn module (Kholodov and Nedumov, 2000). Determination of proportions of these elements in 22 samples from the Sulak River section revealed that H2S-contaminated conditions were commonly dominant in this area
LITHOLOGY AND MINERAL RESOURCES Vol. 44

during the Maikopian period (Mo/Mn > 0.01) and only samples from the Zuramakent Horizon indicate a stable aerated regime (Mo/Mn < 0.01). The MoMn module also behaves in a similar manner in Maikop sequences of the Kuban region, where Mo and Mn contents were determined in 24 samples. It appeared that this coefcient usually exceeds substantially the boundary value
No. 1 2009

12
Regional stages (horizons), substages Tarkhanian Kotsakhurian Sakaraulan Karadzhalginian Upper upper Chattian Kalmykian Askaniya Lower
Series, subseries

KHOLODOV, NEDUMOV
Stage

Black Sea region

Bulgaria Southern Ukraine Tarkhanian Chernobaev Gornostaev Western Georgia

Central Ciscaucasia Tarkhanian Ritsa Olga Mn Karadzhalga Ginsk

Mn

VolgaDon region

Mangyshlak, Buzachi

Northern Ustyurt

Northern Aral region

AquitanianBurdigalian

Lower Miocene

Tsagankhak Aradyk Nugrin Upper Kalmyk lower Karagiin

U
Upper

Aral Kashkarata Upper

U Fe

Zelenchuk

Baigubek Chagrai Karatomak

Fe

Batalmashin U Upper Morozkino Subformation

Virgulinella Beds Isiburul Beds Solenovsk OstraBeds

U

Virgulinella Beds Kulunda Beds Ostracoda Beds Kendzhala Mn Kuyulus Ashcheairyk Tamda Mainasor Beds Ergenica Beds Fe Fe

Oligocene lower Rupelian Solenovian

Upper

Seragoz Ostracoda Molochan Beds

Yuzhnomangyshlak

Lower Morozkino Subformation Polbino Mn Mn

Chilikta
Fe

Lower

Ostracoda Bed

Upper Mn

Nikopol Subformation Mn
Ruanovsk Subformation

Mn
U

Tsimlyansk

Pshekhian

Pshekha Mn
U, Cu, Pb

Upper Tsimlyansk Beds

Fe

Mn Mn

B o r i sf en

Fe

Lower

Mn

Lower Tsimlyansk Beds;

Mn

Uzunbas

Underlying complexes

P3 2 1

P3 2PR 2

P3 2K 2

1 P3 2P 2

P3 2P 1 4

P3 2
Mn

P3 2 5

P3 2 6

Fig. 7. Stratigraphic distribution of phosphaterare metal, manganese, and iron ore accumulations in Ukraine, the Caucasus, and Central Asia. Modied after (Kochenov and Stolyarov, 1995). (14) Metalliferous horizons: (1) manganese ores, (2) manganese occurrences, (3) suldeuraniumrare metal, (4) oolitic iron ores; (5) elevated (above clarke) Mn concentrations in carbonate clays; (6) sh lithofacies related to H2S contamination.

(0.01) and only the upper part of the section (Olga and Ritsa formations) reects the replacement of H2S contamination by well-aerated conditions (Mo/Mn = 0.0010.003). It is remarkable that signs of H2S contamination are traced over a long period (>10 Ma) and recorded up to the South Caspian Basin (Kochenov and Stolyarov, 1995). Like all H2S-contaminated basins, the Maikopian anoxic basin concentrated P, Mn, Si, and Fe in its water (Kholodov, 2002, 2006). Precisely these components are responsible for the peculiar appearance of the Maikop sediments. Numerous depressions formed in peripheral areas of the Maikop Basin, particularly in zones characterized by seawater transgression and expansion of the H2Scontaminated medium. Such depressions represented traps with large-scale sh death and burial.

According to (Kochenov and Stolyarov, 1995), the total area occupied by such traps is as large as 200 260 km2 in the Mangyshlak Peninsula and 6300 km2 in the Ergenei area. The average thickness of phosphorite lenses is 1.8 m in the rst area and varies from a few meters to tens of meters in the second area (Stolyarov and Ivleva, 1991). The mass death of shes and other organisms resulted in the accumulation of huge quantities of organic matter, bones, and cartilages in bottom sediments of the Maikop Basin. All this biogenic material stimulated intense extraction of phosphorus compounds from the H2S-contaminated waters and their concentration (up to 2535%) in sh beds. As shown in (Kochenov and Zinovev, 1960; Kholodov, 1963; Blokh and Kochenov, 1964; McConnell, 1977), present-day shes have skeletons composed of phosphate minerals and CaCO3. Cartilages connecting bones consist of hyaline or chondrine that readily swells in water. These components contain
Vol. 44 No. 1 2009

LITHOLOGY AND MINERAL RESOURCES

ASSOCIATION OF MANGANESE ORE AND PHOSPHORITE-BEARING FACIES (c)

Bed no. Lithology Th, m
14 5

13

Description Fine-clastic carbonate breccia;

13 45

()
12 5

Accumulation of compactly arranged blocks of variable age and origin

1Asselian reefal limestones 2Sakmarian organogenicdetrital

1 2 3

4 5 6

11

yb

24

as

h R.

massive limestones 3relatively thin-platy detrital (bryozoancrinoidfusulinid) Artinskian limestones

Kaziya k Up lift

Tr ou gh

Uk

Sal

10

R. Sim
9 30

Asha
8

ly

Uk R.
7 40

lu

ro

T U so l' e

ro

r amsh

a k R.

im

R.

Le

me

za

R. S

im

m 360 350 340 330 320 310

NW

(b)

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 the trough with outcrops of Artinskian rocks, (3) central part of the trough lled with Umian red beds, (4) stratoisohypses of the roof of the Artinskian sediments (proven and assumed), (5) reversed faults, (6) boundaries of stratigraphic complexes; (b) section of the phosphorite 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 manganiferous limestonedolomite formation of the Ulutelyak type (modied after E. Gribov): (1) oncolitic and oolitic limestones, (2) manganese carbonate ores (manganese limestones), (3) manganiferous dolomitic marls, (4) dolomites, (5) anhydrites.

sodium carbonate and sodium sulfate. Organic matter of shes is dominated by proteins, which glutamine acid, glycol, alanine, and proline after microbiological decomposition (Drozdova and Kochenov, 1960). Carbonate components and, probably, organic matter of these remains were replaced by phosphates. In any case, sh cemeteries likely extracted substantial quantities of phosphorus from bottom waters of the Maikopian sea. This process continued after sediLITHOLOGY AND MINERAL RESOURCES Vol. 44

Amirov Anticline

Fine-clastic (112 cm) carbonate breccia with fusulinids and ammonoids of the Irga Horizon (Artinskian Stage)

-T

Ar

dy ge lR .

20

Block-sized breccia of different age limestones Blocks and large fragments of with Artinskian fusulinids; at the base, large block of quartz sandstones and gravelstones

15

120

SE

(d)

mentation at the diagenetic stage with the dominant participation of hydrogen sulde. Since the phosphatized sh remains of the Mangyshlak and Ergenei areas contain negligible quantities of Mn, they likely represented a peculiar lter that separated the precipitating phosphorus and dissolved manganese. Relative to phosphorus, manganese was more widespread in the basin and precipitated in the oxygenrich medium during the alkalization of seawater with carbonates.
No. 1 2009

14

KHOLODOV, NEDUMOV

ASSOCIATION OF DIFFERENT PHOSPHORITE DEPOSITS WITH SEDIMENTARY MANGANESE DEPOSITS It is well known that phosphorite deposits of most diverse types are frequently associated with the MesozoicCenozoic sedimentary manganese deposits. Danilov (1982) described numerous occurrences of nodular phosphorites in Jurassic (upper Volgian) glauconite sandstones of the northern Timan region, where they form plates in some places. The same Volgian sequences enclose beds and lenses of oolitic manganese ores (from 0.2 to 2.5 m thick) located slightly below the phosphorite horizon. Manganese mineralization is represented by rhodochrosite, manganocalcite, and psilomelane. The MnO content ranges from 23.33 to 70.43%; the Fe content, from 3.5 to 37.86%. Many manganese deposits in the Urals coincide spatially and stratigraphically with phosphorite deposits and occurrences. For example, Betekhtin (1946) and Sapozhnikov (1972) described the Marsyat deposit, where nodular phosphorites occur together with manganese ores in the Upper Cretaceous sediments. Similar phosphate lenses are also established in Tertiary sequences of the Polunochnoe manganese deposit. More complicated spatiotemporal relationships are observed between granular phosphorite deposits in southwestern Morocco and manganese deposits in the Imini area (TifersonBou AzzerBou Aggum). This ore district is scrutinized in (Bouladon and Jourovski, 1952, 1956; Thein, 1990; and others). In this area, stratiform manganese ore deposits occur in the CretaceousEocene arid redrock formation in association with the Turonian carbonatedolomite sequence. Ore-bearing rocks are exposed in piedmonts of the High Atlas as sequences transgressively overlying the deformed Paleozoic strata, which enclose probably hydrothermal manganese ore veins. The Turonian deposits are mainly composed of psilomelane. Jacobsite, braunite, and hausmannite are subordinate, while rhodochrosite is rare. The Mn content in ores ranges from 10.84 to 50.84% (Table 1). The carbonate ore-bearing sequences of the manganese ore district enclose thin P-rich layers. However, large phosphorite deposits are conned to the Eocene redrock formation in Morocco and the main phosphorite-bearing districts are located in the Jebilet Plateau north of Marrakesh. In this area, up to 810 beds of high-quality granular phosphorites with the P2O5 content ranging from 25 to 30% are mined in Eocene carbonatedolomite sequences. The structure of the Si Unes, Maiat, El Barudge, Ulla Abdun, Gufaf, and Tadl deposits, which form a wide sublatitudinal band of ore occurrences around the Jebilet Plateau, is described in (Orlova, 1951; Salivan, 1960; and others).

It is evident that manganese deposits in southwestern Morocco are associated with phosphorites, which are located stratigraphically higher in the transgressive sequence of red-colored limestones, dolomites, evaporites, sandstones, and clays. Their undoubted spatial association is particularly emphasized by the abundance of phosphorites in the Turonian manganiferous sequences. The Bashkir Trough area adjacent to the Karatau Uplift (Urals) at the lower and middle reaches of the Sim River is an additional example of the cooccurrence of manganese ores and phosphorites. This area hosts the Asha phosphorite and Ulutelyak manganese deposits. The geological structure of this region is shown in Fig. 8a adopted from (Keller, 1945). The main structure of the region is the Karatau Fault that extends from the southeast to northwest and separates the Proterozoic metamorphosed sequences of complex folds of Karatau (Urals) from the system of gentle synclines and uplifts composed of Permian sediments of the Uralian Foredeep and Russian Platform. The central part of the region is occupied by the Kazayak Uplift and Karatau structural salient composed of Artinskian carbonate rocks. Their conjunction is marked by the Zmeinogorsk and Lipovyi reefs. Like many other reefal buildups of the Uralian Foredeep, they are characterized by oil and gas occurrences (Kuznetsov, 2000). The uplifts are surrounded by depressions: Ulutelyak Depression in the west and Uk Trough, which grades into the spacious SimUsole Trough lled with Umian redrocks, in the east. The entire system of these tectonic structures rises to northeast: dip angles of Permian strata near the Karatau Salient amount to 5070. In the NW direction, they become gradually gentler and even at in some places. The Asha phosphorite deposit is located in the highest part of the region in southern outskirts of Asha near the Lipovyi reef. The deposit discovered in 1953 is described in (Vodorezov et al., 1956; Chalyshev, 1968; Volkov, 1974; Chuvashov and Yakovleva, 2007). It represents a blockbreccia sequence of the Artinskian, Sakmarian, and Upper Carboniferous ore-bearing rocks up to 320 m thick. The sequence consists of alternating intervals of carbonate fragments (up to 1020 cm across) and block horizons of carbonate bed fragments (up to 1015 m or more in size). Figure 8b demonstrates the lithological cross section of the Mount Kulakovaya area (Chuvashov and Yakovleva, 2007), where the lower part is dominated by limestones with the Artinskian and Sakmarian fauna, while the upper layers enclose Upper Carboniferous fossils. We can probably agree with these authors, who believe that the block facies lack primary sediments; their formation is related to the large-scale destruction and subsequent accumulation of a thick section of Upper Carboniferous bedded limestones and
Vol. 44 No. 1 2009

LITHOLOGY AND MINERAL RESOURCES

ASSOCIATION OF MANGANESE ORE AND PHOSPHORITE-BEARING FACIES

15

Lower Permian (Asselian, Sakmarian, and Artinskian) reefal and bedded limestones (Chuvashov and Yakovleva, 2007, p. 60). Phosphorites appear at different levels of the block horizon. According to (Vodorezov et al., 1956), phosphorites of the highest commercial signicance occur in the lower brecciated horizon resting unconformably on the eroded surface of the steeply dipping and slightly phosphatized Artinskian limestones (Fig. 8c). The phosphorite-bearing sediments are up to 1020 m thick. They distinctly replace the brecciated carbonate sequences or bedded limestones. In addition, they are characterized by very uneven basal surface, which is complicated by pockets, depressions, and cracks lled with phosphate material. The abundance of signs of the metasomatic replacement of limestones suggests that phosphorites of the Asha deposit are typical karst formations. This assumption of Vodorezov et al. (1956) is based on following observations: the complete or partial replacement of carbonate blocks, their fragments, and clayeycarbonate cement; the lling of pores, cavities, and fractures with phosphates; the formation phosphate fringes around the corroded carbonate fragments; and several other signs of the wide development of phosphate metasomatism. The Ulutelyak manganese deposit is located in the synonymous syncline 1620 km southwest of the Asha phosphorite deposit and 2022 km northeast of Ufa. Manganese ores in this deposit associate with Upper Permian sediments. Figure 8d illustrates the schematic distribution of ores in the deposit, where they are conned to two intervals of the section overlying the Artinskian and Kungurian gypsiferous formations. The thickness of ore beds varies from 6 to 10 m; the Mn content, from 3 to 18% (Varentsov and Rakhmanov, 1974). Ore bodies of this deposit clearly demonstrate the following vertical zoning (Betekhtin, 1946): the eroded uneven surface of rocks is overlain by a bed of alternating laminated manganese carbonate ores and limestones resting upon, while the upper parts of beds are dominated by SiO2-rich vernadite ores. The deposit is characterized by wide development of karst process. Watersheds are covered by karst funnels. According to V.N. Kuleshov (private communication), some areas of the deposit are marked by the abundance of block facies and the presence of limestone blocks that complicate the stratiform patterns of manganese orebodies. It is clear that cooccurrence of Asha phosphorites and Ulutelyak manganese ores is not incidental. The following facts should be taken into consideration when explaining this phenomenon. The Permian and even Triassic sediments of the Uralian Foredeep are almost always enriched in phosphorus and manganese (Bezrukov, 1939; Chalyshev,
LITHOLOGY AND MINERAL RESOURCES Vol. 44

1968; Chuvashov and Yakovleva, 2007). For example, the P2O5 content in carbonate sediments of the Artinskian Stage ranges from 1 to 18%; the MnO content, from traces to 1.65%. Even the Umian redrocks contain 0.65% of P2O5 and up to 1.15% of MnO. Analysis of the available data allows the Asha phosphorites and Ulutelyak manganese ores to be classed as typical epigenetic sediments that originated at the latest stages of the ore-forming process. Noteworthy is the close association of this process with the formation of block facies and the subsequent karstication. The latter process has been reported from the Ufa area in (Varsanofeva, 1916; Gvozdetskii, 1954; and others). It was established that karst funnels, holes, caves, and collapse lakes are closely related to the Artinskian and Kungurian gypsiferous sequences and are probably superimposed on the formation of carbonate blocks and breccias owing to the development of the Karatau Uplift. It is conceivable that cooccurrence of phosphorite and manganese deposits in the above case is controlled by the activity of inltration waters, which could derive large quantities of P and Mn from the enclosing Permian formations. The abundance of organic matter of the oil series in the Permian sequence played a signicant role in karstication. Some part of the organic matter was transported from deeper parts of the section, whereas another part was concentrated in the Permian reefal massifs. In addition, sulfates made up a substantial portion of halogenic sequences. Microbiological sulfate reduction in groundwaters could produce significant quantities of hydrogen sulde and karstication of carbonate sequences. Combined with water inltration, all these processes could stimulate the formation of commercial phosphorite and manganese ore deposits that were separated in both vertical and lateral directions. CONCLUSIONS (1) Cooccurrences (parastereses) of chemical elements, minerals, sedimentary rocks, facies, and formations should be discriminated from their parageneses. Only geological objects associated with a single genetic process should be considered as parageneses. (2) Phosphorus is concentrated in sedimentary manganese ores and is virtually missing in hydrothermal and volcanosedimentary manganese deposits. (3) Cooccurrence of phosphorus and sedimentary manganese ores can clearly be divided into two parageneses. Accumulation of phosphorus in manganese hydroxide ores is largely determined by sorption, while its concentration in carbonate ores is likely related to the ability of both chemical elements to precipitate in the alkaline carbonate medium. (4) In addition to spatiotemporal relationships, cooccurrence (parasteresis) of manganese ore and phosphorite-bearing facies in the Oligocene sediments
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of southwestern Eurasia is an indicator of their common genesis, since ore-forming processes in this region are presumably determined by the initial joint concentration of elements in the H2S-contaminated Oligocene basin and their subsequent fractionation at the biochemical and carbonatealkaline barriers. (5). Parasteresis of phosphorites in the Asha deposit and manganese ores in the Ulutelyak deposit was promoted by the general intensication of the PMn geochemical background of the region, the development of sulfate-reducing and karstication in limestones, and the activity of inltration waters. These processes stimulated the fractionation of components and the formation of commercial deposits. ACKNOWLEDGMENTS This work was supported by the Russian Foundation for Basic Research, project no. 05-05-64033. REFERENCES
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