Lithology and Mineral Resources, Vol. 40, No. 1, 2005, pp. 48–55. Translated from Litologiya i Poleznye Iskopaemye, No. 1, 2005, pp. 56–64. Original Russian Text Copyright © 2005 by Zanin, Tsykin, Dar’in.
Phosphorites of the Arkheologicheskaya Cave (Khakassia, East Siberia) Yu. N. Zanin1, R. A. Tsykin2, and A. V. Dar’in3 1Institute
of Petroleum Geology, Siberian Division, Russian Academy of Sciences, pr. Akademika Koptyuga 3, Novosibirsk, 630090 Russia e-mail:
[email protected] 2 Krasnoyarsk State Academy of Nonferrous Metals and Gold, pr. Krasnoyarskii rabochii 95, Krasnoyarsk, 660025 Russia 3 Institute of Geology, Siberian Division, Russian Academy of Sciences, pr. Akademika Koptyuga 3, Novosibirsk, 630090 Russia Received March 1, 2004
Abstract—Phosphorites are sufficiently widespread in caves (Hutchinson, 1950; Maksimovich, 1963, 1966). Their formation is mainly attributed to the interaction of decomposition products of bat guano with cavity wall rocks. The guano is also sometimes considered cavity phosphorites (Maksimovich, 1966). This is, of course, incorrect. There are a few descriptions of cavity formations composed of inorganic phosphates that can be considered real phosphorites. The most scrutinized descriptions of phosphorites are related to caves in Java Island (Narchemashvili and Sokolov, 1963) and iron ore deposit areas in the Bomi Hill and Bamuta regions in western Liberia (Axelrod et al., 1952). The Java Island phosphorites include F-free (carbonate)-apatite and alumophosphates that are composed of crandallite, as suggested by the chemical composition presented in (Narchemashvili and Sokolov, 1963). The major phosphate minerals in cavity phosphorites of Liberia are leucophosphite, phosphosiderite, and strengite (Axelrod et al., 1952). The presence of cave phosphorites has also been reported from different regions of the world (Hutchinson, 1950; Maksimovich, 1963). However, their detailed description has not been presented in the literature so far.
MATERIALS Karst phosphorite deposits and occurrences are widespread in Siberia (Bliskovskii, 1967; Krasil’nikova and Shmel’kova, 1966; Krasil’nikova et al., 1968; Spanderashvili, 1962; Vekshin et al., 1990; Zanin, 1967, 1968, 1969, 1975, 1989; Zanin et al., 2000a; and others). All cases reported in the literature are related to supergene phosphorite lodes in depression-type cavities formed as a result of the solution and redeposition of Precambrian–Early Cambrian marine (primarily phosphate-bearing) rocks and phosphorites. Phosphorites of the Arkheologicheskaya Cave discovered with the participation of one of the authors of the present communication (Tsykin, 1979; Tsykin et al., 1983) represent the first finding of cavity phosphorites in Siberia, in general, and South Siberia, in particular. Karst formations, including more than 160 cavities, are widespread in South Siberia (Tsykin et al., 1983). The Arkheologicheskaya Cave is located at the base of the right flank of the Malaya Syya River valley 1.8 km away from the place where it merges as the left tributary of the Belyi Iyus River (Fig. 1). During the dry period, the Malaya Syya River channel near the Arkheologicheskaya Cave is characterized by the absence of water owing to its filtration along channel fissures and cavities. The cave area is composed Upper
Riphean rocks (basalts, andesites, and their tuffs) Vendian–Lower Cambrian limestones and dolomites, and Middle Cambrian rocks (sandstones and siltstones) that are locally overlain by Middle Ordovician trachytes and trachyandesites. The section is crowned with Lower Devonian effusives (Fig. 1). The Arkheologicheskaya Cave is confined to Lower Cambrian massive and massive-bedded gray limestones with archaecyathides and trilobites. The cave is characterized by the following dimensions: total length 205 m, depth 23 m, and volume 14500 m3. It consists of two inclined grottos and short manholes. The first (entry) grotto plunges, whereas the second grotto ascends at an angle of 20°–25°. The cave bottom is covered with debris mainly consisting of gravitational and organogenic material (human and animal bones). The entry grotto contains numerous bones shattered by ancient inhabitants of the cave. It is interesting that the grottos are located 12 m below the Malaya Syya River channel level. Therefore, they can be flooded during high water. However, signs of flooding are absent. The brown phosphorite crusts (coprolites), obviously related to the bat guano that represents the major source of cavity phosphorites (Hutchinson, 1950; Maksimovich, 1963), are found on rock boulders and cavity walls and roof.
0024-4902/05/4001-0048 © 2005 åÄIä “Nauka /Interperiodica”
PHOSPHORITES OF THE ARKHEOLOGICHESKAYA CAVE 80°
85°
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90° Krasnoyarsk 55°
Kemerovo Abakan
Novosibirsk
Belyi Iyus R.
55°
Novokuznetsk Barnaul 0
150
O2ks
300
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ε2bz
ε1
450 km 85°
V-ε1tr ε1
R3kl
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6
O2ks
2
γδ ε3t
7
ε2bz
3
8
ε1
4
9
V-ε1tr
5
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γδ ε3t
Fig. 1. Location and geological plan of the Arkheologicheskaya Cave area. (1) Quaternary alluvium; (2) trachyandesite and trachyte (Kashkulak Formation, Middle Ordovician); (3) sandstone and siltstone (Bezymyannaya Formation, Middle Cambrian); (4) limestone sequence (Lower Cambrian); (5) calcareous dolomite (Tarzhul Formation, Vendian–Lower Cambrian); (6) basalt, andesite, and their tuffs (Kul’byurgstyug Formation, Upper Riphean); (7) granite and granodiorite (Tigertysh Complex, Upper Cambrian); (8) basalt (Lower Devonian); (9) faults; (10) location of the Arkheologicheskaya Cave.
RESEARCH METHODS
RESULTS AND DISCUSSION
The petrographic study of phosphorites from the Arkheologicheskaya Cave was performed using the polarization and scanning (JSM-35) microscopes. We carried out a comprehensive analysis of the rocks, including the whole-rock chemical analysis (the XRF method) and the determination of ëé2 (volumetric method) and SO3 (gravimetric method). Trace elements (Cd, Pb, Cu, Cr, Ni, Co, and V) were determined by the atomic absorption method with a Sp-9 device using the standard samples SGKhM-3, SSL-2, and SLK-2 (reproducibility error was better than 10%). Some other trace elements (U, Th, Sc, As, Sr, Sb, Cs, and Rb) were analyzed by the INAA method. Its analytical parameters and reliability are described in (Gavshin and Zakharov, 1996). The contents of Y, Zr, Nb, I, and Br were determined by the XRF method at the Siberian Center for Synchrotron Radiation based on apparatus and methods described in (Baryshev et al., 2002; Dar’in et al., 2003). The quantitative determination of element contents was based on the external standard method. For comparison, we used the following standard rock samples: ST-1a (trap rock), SA-1 (mudstone), SG-2 (granite), SI-1 (limestone), BIL-1 (Baikalian mud), and BCR-32 (phosphorite). The normalized coefficients for the calculation of element contents, uncertified in the standards mentioned above, were obtained by the interpolation of respective values for the adjacent element groups.
Phosphorites of the Arkheologicheskaya Cave morphologically represent a porous but sufficiently hard material. They look like a homogeneous mass of brown color under a polarizing microscope. Under a scanning microscope, one can see tubular structures (external diameter 16–18 µm, internal diameter 10 µm) and numerous tubular fragments (Fig. 2). We believe that the tubes are capsules of cyanobacterial filaments. Such microbial tubular structures are rather common in phosphorites. However, they were only once detected in coprolite phosphorites (Zanin et al., 2002b).
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Results of the chemical analysis of the Arkheologicheskaya Cave phosphorite suggest its monomineral composition (Table 1). The nonphosphatic admixture does not exceed 5%. The phosphate mineral is characterized by a virtually complete absence of F and relatively low Na2O and S contents. The ëé2 content is also relatively low (1.65%). However, the phosphate mineral should be considered carbonate-apatite based on the ëé2 content of more than 1% (McConnell, 1973) or carbonate-hydroxyapatite (dallite) based on the absence of fluorine. For the sake of comparison, Table 1 presents results of the analysis of the supergene carbonate-hydroxyapatite from Christmas Island, Pacific ocean (Sample CI-1) and Caceres Province, Estremadura, Spain (Sample 4724), the supergene (karstic) carbonate-fluorapatite from the Obladjan No. 1
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ZANIN et al.
Fig. 2. Tubular structures (capsules of cyanobacterial filaments) in phosphorites from the Arkheologicheskaya Cave. SEM image, magn. 1200.
deposit (Khakassia), the marine carbonate-fluorapatite from the Polpino deposit, East European Platform (Sample 4571), and the standard phosphorite sample BCR-32 from Morocco. It is evident that only the Caceres phosphorite is characterized by lower ëé2 contents. The carbonate-ion content in the sedimentary apatite structure depends on the alkalinity of the mineral-forming realm (Ames, 1959; Romo, 1954). Under conditions of guano decomposition, the phosphate mineral-forming environment was probably slightly alkaline. Therefore, the carbonate-ion content in the cavityhosted carbonate-apatite was low. The studied carbonate-apatite is depleted in CO2 relative to the marine carbonate-apatite (Table 1, Sample 4571, BCR-32), in which the CO2 content is 5–6% (Bliskovskii, 1983) and may be as much as 7% in monomineral fractions. This depletion is typical of the majority of supergene phosphorites (Zanin, 1975). The Na and S content is generally equal to or more than 1% in marine phosphorites, which were not significantly altered during the weathering and/or catagenesis, and never achieves this value in supergene calcium phosphates (Zanin, 1975). This is typical of the Arkheologicheskaya Cave phosphorite and other supergene phosphorites (Table 1). The decrease of S and Na in the structure of supergene carbonate-apatites, relative to the marine ones, is caused by differences in the hydrochemical composition of the host water. In contrast to supergene phosphorites, which frequently contain the F-free carbonatehydroxyapatite, the marine variety is usually characterized by the presence of the F-bearing carbonate-apatite. For example, the F-free or low-F phosphorites have
been repeatedly observed in the supergene phosphorites of oceanic islands (Jacob et al., 1933; Hutchinson, 1950; Trueman, 1971; Zanin, 1975; and others). As was mentioned above, cave phosphorites from Java Island do not contain fluorine (Narchemashvili and Sokolova, 1963). We have also noted the virtual absence of fluorine in the supergene phosphorite crust of the Caceres Province, Spain (Zanin, 1975). According to Jacob et al. (1933), the initially F-free island and continental calcium phosphates could gradually be saturated with this element. For example, the vertebrate animal bones, which were initially composed of carbonate-hydroxyapatite, undoubtedly concentrated fluorine with time (Bushinskii, 1956). Obviously, the young age of coprolite phosphorites in the Arkheologicheskaya and other caves, as well as the weak contact of these phosphorites with water, which could supply fluorine, promoted the preservation of their primary F-free composition. The Arkheologicheskaya Cave phosphorite is also enriched in organic carbon (4%) generally missing in the karstdepression phosphorite, e.g., in the Obladjan phosphorite. The ç2O+ content reaches 4–5% in carbonatehydroxyapatites (with a similar spectrum of the major components) from other ore occurrences (Zanin, 1975). One can assume that the H2O+ content is generally similar in the Arkheologicheskaya phosphorite. The trace element composition of phosphorites is presented in Table 2. The table also shows the trace element composition of the karst-depression phosphorites in the Obladjan deposit (Khakassia) and marine phosphorites (Morocco), as well as the averaged trace element composition of phosphorites, in general, based on (Altschuler, 1980). It is evident that phosphorites from the Arkheologicheskaya Cave and Obladjan deposit have similar trace element compositions. However, the Arkheologicheskaya Cave is commonly characterized by lower contents of trace elements. In particular, the U content is very low (1.8 ppm). In the recently published work by Baturin and Kochenov (2001), which is based on approximately 1000 determinations of U in the phosphorite, U contents of the order of 1–2 ppm are rare. The reason for the low U content in phosphorites is discussed in (Altshuler et al., 1958; Cook, 1972; Dar’in and Zanin, 1988; Howard, Hough, 1979; Il’in and Volkov, 1994; Zanin et al., 2000b; and others). When the marine phosphorite enters the supergene zone, the U content decreases owing to the oxidation and transformation of the tetravalent U, which is known to be capable of isomorphously replacing Ca in the carbonate-apatite structure, into the hexavalent variety (Altschuler et al., 1958). Baturin and Kochenov (2001) believe that the introduction of the hexavalent U modification into the crystal structure of apatite is hardly possible. In an oxidizing environment, the hexavalent U modification is characterized by a high migration capacity (Shvartsev, 1998) and, therefore, is more mobile than phosphorus (Batulin et al., 1965). Moreover, this uranium has a very low sorptional capacity in
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Table 1. Chemical composition of phosphorites from the Arkheologicheskaya Cave and some other supergene and marine phosphorite occurrences Content, % Supergene minerals Components
Sample Ts-1, Arkheologicheskaya Cave, Khakassia
SiO2 Al2O3 TiO2 Fe2O3 (tot) CaO MgO MnO Na2O K2O P2O5 CO2 SO3 (sulfate) S (sulfide) F Corg H2O+
2.09 2.80 0.1 0.39 48.66 0.48 0.04 <0.3 0.36 31.52 1.65 0.65 n.d. 0.004 4.0 n.a.
H2O– L.O.I. Total I O corres. F O corres. S Total II
absent 7.21* 99.95 – 0.13 99.82
Khakassia, Obladjan deposit (n = 16)
Marine phosphorites
Sample 4724, Estremadura, Caceres Province, Spain
9.51 3.53 0.19 1.85 46.18 1.99 0.13 0.32 0.12 31.01 3.08 0.02 n.a. 2.24 n.d. 2.25 (H2O+ + H2O–)
102.42 0.95 – 101.47
Sample CI-1, Christmas Island, Pacific Ocean
0.10 0.14 n.d. 0.14 54.34 n.d. n.d. 0.48 0.06 40.50 1.11 n.a. n.a. 0.02 n.a. 2.10
2.10 0.90 n.d. 0.57 51.68 1.00 n.d. 0.61 0.03 38.00 2.53 0.45 n.a. 0.23 n.a. 2.30
0.80 n.a. 99.93 – – 99.93
0.60 n.a. 101.00 0.10 0.09 100.81
Standard Sample 4571, Polpino deposit, phosphorite East European sample BCR-32 Platform (Morocco) 0.29 0.18 n.a. 0.27 53.18 0.3 0.017 1.08 0.18 33.2 5.23 1.05 n.a. 3.98 n.a. 2.50 0.34 n.a. 101.80 1.69 0.21 99.90
2.09** 0.55** 0.01 0.23** 51.76* 0.40** 0.02 0.74 0.06 32.98** 5.1** 1.84** n.a. 4.04** n.a. 0.86 0.45 n.a. 101.13 1.70 0.37 99.06
* Without the consideration of Corg, CO2, and SO3; ** certified values; (n.d.) not detected; (n.a.) not analyzed.
the strong acid medium (Batulin et al., 1965). All these features correspond to physicochemical conditions of the bat-inhabited caves where the oxidizing medium at the initial stage of guano decomposition was promoted by the strong acid regime that predated the phosphorite formation. The uranium, which is highly mobile under such conditions, was removed by the cave water, probably, even before the onset of carbonate-apatite formation in a slightly alkaline medium, resulting in the drastic depletion of this mineral in uranium. Now, let us consider the Cd content in the Arkheologicheskaya phosphorite. The occurrence of this element in phosphorites is attributed to various mechanisms, such as isomorphous substitution in the crystal structure of carbonate-apatite, sorption by organic matter and iron hydroxides, or isomorphous substitution in sphalerite. The substitution of Zn for Cd in the sphalerLITHOLOGY AND MINERAL RESOURCES
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ite and its relation with organic matter, which is often present in phosphorites, is an undoubted and universally accepted phenomenon. However, the absence of sulfide sulfur in the studied phosphorite rules out the possible interrelation of Cd with sphalerite. The introduction of Cd into the carbonate-apatite structure, the major mineral of phosphorites, is a popular concept (Jarvis, 1994). However, the validity of this concept has been questioned by some authors in recent years (Il’in and Kiperman, 2001; Il’in, 2002). These authors argue that the biophile property of Cd becomes very significant in the phosphorites. Consequently, the whole Cd is bound with the organic matter (occasionally, with iron oxides) rather than the carbonate-apatite. Data on the Arkheologicheskaya phosphorite compel us to be careful with such inference, which is not supported by the available data. The high organic carbon (4%) and low No. 1
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Table 2. Trace element composition of phosphorites from the Arkheologicheskaya Cave and some other supergene and marine phosphorite occurrences Occurrence
Content, ppm Cd
Pb
Arkheologicheskaya Cave 5.1 6 Obladjan deposit, Altai– 6.4 27 Sayan region Standard phosphorite sam- 21 8 ple BCR-32 (Morocco)* Average in phosphorites 18 50 (Altschuler, 1980) Interval of average conn.d.– n.d.– tents (Altschuler, 1980) 40–200 180 Occurrence Arkheologicheskaya Cave Obladjan deposit, Altai– Sayan region Standard phosphorite sample BCR-32 (Morocco)* Average in phosphorites (Altschuler, 1980) Interval of average contents (Altschuler, 1980)
Cu
Cr
Ni
Co
V
Sc
As
Sr
95 69
45 56
12 82
6 3.8
23 114
2.9 n.d.
4.5 21
219 434
35
260
32
1
160
n.d.
10
n.d.
n.d.
75
125
53
7
100
11
23
n.d.
n.d.
6–80
n.d.– 5000
n.d.
n.d.– 350
7–400– 7–250 n.d.–35 30–260 1000
5–18
Rb 12 2.5
Content, ppm Sb
Cs
U
Th
Y
Zr
Nb
I
Br
Ba
0.6 1.7
0.89 1.1
1.8 82
1.37 1.0
13.6 n.d.
35.2 n.d.
0.8 n.d.
2.8 n.d.
24.1 n.d.
135 n.d.
3
n.d.
125
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
120
n.d.
260
70
n.d.
n.d.
n.d.
350–500
n.d.
n.d.
30–260
n.d.
n.d.
n.d.
n.d.
56–1450– 3000
33
20–1100 17–210
* Uncertified approximate values; (n.d.) no data.
Table 3. REE composition of phosphorites from the Arkheologicheskaya Cave and some other phosphorite occurrences Content, ppm Occurrence La
Ce
Nd
Sm
Eu
Gd
Tb
Yb
8.5
14.0
7.4
1.65
0.40
1.5
0.25
23.8
29.3
19.8
5.1
0.8
6.7
35
68
11.5
3.45
Arkheologicheskaya Cave Altai–Sayan region (Bliskovskii, 1983)
Standard phosphorite sample 115 BCR-32, Morocco (Altschuler et al., 1986)* Content interval (Altschuler, 1980)
25–300 14–160 18–200
3–51
1–20
Lu
Total REE
0.67
0.095
34.46
0.5
1.7
0.4
88.1
19.4
3.25
14.2
2.45
272.25
4–20
1–6
2–24
0.5–7 117–1470
* Data of the US Geological Survey.
Cd (5.1 ppm) contents in the studied phosphorites suggest that they should be referred to the group of relatively Cd-poor variety (Table 2). Moreover, the Cd contents in the Arkheologicheskaya phosphorite and the adjacent karst-hosted Corg-free phosphorite from the Obladjan deposit (6.4 ppm) are very similar. Thus, we have more grounds to support the earlier concept of the Cd introduction into the crystal structure of carbonateapatite.
Table 3 presents data on the REE content in different phosphorites. Data on the Arkheologicheskaya phosphorite and the karst-depression phosphorite in the Altai–Sayan region are adopted from (Bliskovskii, 1983). Data on the Moroccan phosphorite standard BCR-32 are based on reports of the US Geological Survey (Altschuler et al., 1986). It is worth mentioning that phosphorites from both the Arkheologicheskaya Cave and karst depressions in the Altai–Sayan region are
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characterized by a low total REE content. However, these low REE contents are not unique. Similar and even lower REE contents have been recorded in the phosphorite from the shelf/continental margins of Namibia, Peru, Sechura Desert (Peru), and other sites (McArthur and Wolsh, 1984). According to these authors, since the REEs were concentrated in the phosphorite after its formation, the older phosphorite is more enriched in the REEs than the younger one. This explanation is quite valid for the Arkheologicheskaya phosphorite as well. Figure 3 presents the shale-normalized (Piper, 1974) REE distribution plot for the studied phosphorites. It is evident that, relative to the marine phosphorite (Moroccan phosphorite standard BCR-32), phosphorites from the Arkheologicheskaya Cave and karst depressions in the Obladjan deposit have a less prominent Ce anomaly. According to Ronov et al. (1967), Ce is oxidized to the tetravalent state, which is more stable than the trivalent modification, under oxidizing conditions in the low-alkaline and alkaline environments. Since the physicochemical conditions of phosphorite formation in both the Arkheologicheskaya Cave and karst deposits of the Altai–Sayan region were low-alkaline and undoubtedly oxidizing, the mechanism mentioned above can also be accepted for explaining the weak Ce anomaly in the REE spectrum of the phosphorites. Another specific feature of the shale-normalized REE distribution in the phosphorites lies in the weak negative anomaly of HREE (Yb and Lu). In contrast, the marine phosphorites (except the Late Precambrian– Early Cambrian representatives) are characterized by the positive Yb and Lu anomaly. Figure 3 clearly shows that the positive anomaly of these elements is typical of not only the Moroccan marine phosphorite, but also the karst phosphorite in the Altai–Sayan region. The negative Yb and Lu anomaly is typical of the ancient (Precambrian–Early Cambrian) phosphorites owing to the respective REE composition of the marine basin water of that time (Ilyin, 1998) or the extraction of these elements from the crystal structure of carbonate-apatite during the catagenesis of virtually all ancient phosphorites (Zanin et al., 2002). However, the weak negative anomaly of HREE in the phosphorites is typical of not only the Arkheologicheskaya Cave, but also some young phosphorites from the Peru shelf and other regions (McArthur and Wolsh, 1984). Like the Arkheologicheskaya and Obladjan phosphorites, the young phosphorites are characterized by the low total REE content, although this anomaly is not universal. From the ecological point of view, the contents of highly toxic U and Cd are very low in the relevant phosphorites. This conclusion is also valid for the additional ecologically hazardous elements, such as heavy metals, Sr, As, and Th. The analysis of these hazardous trace elements in the phosphorites from the Obladjan deposit (Zanin et al., 2000a) showed that these phosphorites can be used as fertilizers in the form of phosphorite flour over hundreds and thousands of years. Taking into LITHOLOGY AND MINERAL RESOURCES
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101 3 100
10–1
2
1 La
Ce
Nd
Sm
Eu
Gd
Tb
Yb
Lu
Fig. 3. The shale-normalized (Piper, 1974) REE distribution plots for phosphorites from (1) the Arkheologicheskaya Cave, (2) karst depressions in the Altai–Sayan region, and (3) Morocco (Sample BCR-32). Curves (1) and (2) are based on (Bliskovskii, 1983).
consideration the content of fluorine, which is virtually absent in the Arkheologicheskaya phosphorite, the minimal possible (from the point of view of ecological safety) period of utilization of the Obladjan phosphorite as fertilizer is 33 yr. CONCLUSIONS (1) Phosphorites of the Arkheologicheskaya Cave probably formed from the bat guano. They are characterized by the presence of tubular structures with an external diameter of 5–10 µm and internal diameter up to 8 µm. These tubes are considered capsules of cyanobacterial filaments. Such tubular structures were previously recorded in definitely coprolite phosphorites from Paleogene sediments of Lake Zaisan (Zanin et al., 2002b). These observations have fundamental significance, because some authors regard the phosphorite grains with tubular structures as products of the destruction of the phosphatized microbial mats. One cannot rule out this mechanism of phosphorite grains. At the same time, such phosphorite grains can undoubtedly represent coprolites. Precisely this mechanism of phosphate grain formation was suggested by Samoilov (1912) and Bushinskii (1966). (2) We believe that the incorporation of Cd in the crystal structure of carbonate-apatite is also possible. This mechanism is questioned by some authors in recent years. (3) The studied phosphorites are marked by a very low content of the ecologically hazardous elements. This favorable geochemical feature makes it possible to utilize them as fertilizer in the form of phosphorite flour. The authors emphasize the extremely low content in the studied phosphorites formed under specific conditions. Therefore, it is expedient to carry out special prospecting for cave phosphorites in the region. No. 1
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ACKNOWLEDGMENTS The authors are grateful to L.D. Ivanova, A.D. Kireev, A.S. Parkhomenko, I.M. Fominykh, and R.N. Myasnikova for analytical works and to E.A. Zhegallo for consultations in the identification of the phosphatized microbial structures in phosphorites. This work was supported by the Russian Foundation for Basic Research, project nos. 04-05-64075. REFERENCES Altschuler, Z.S., The Geochemistry of Trace Elements in Marine Phosphorites. Part 1: Characteristic Abundances and Enrichment, Marine Phosphorites – Geochemistry, Occurrence, Genesis. SEPM Spec. Publ., 1980, no. 29, pp. 19–30. Altschuler, Z.S., Clarke, R.S., and Young, E.J., Geochemistry of Uranium in Apatite and Phosphorite, US Geol. Surv. Prof. Pap. 314-D, 1958, pp. 45–90. Altschuler, Z.S., Prévôt, L., and Zanin, Yu.N., Report on Phosphorite Standard BCR-32, Newsletter of the IGCP Project 156 “Phosphorite”, 1986, no. 17, pp. 13–17. Ames, L.L., The Genesis of Carbonate Apatites, Econ. Geol., 1959, vol. 54, no. 5, pp. 829–841. Axelrod, E.C., Carron, M.K., Milton, C., and Thayer, T.P., Phosphate Mineralization at Bomi Hill and Bamuta, Liberia, W. Africa, Am. Mineral., 1952, vol. 37, no. 11/12, pp. 883–909. Baryshev, V.B., Zolotarev, K.V., Kobeleva, N.A., et al., Poverkhnost’. Rentgen. Sinkhrotron. Neutron. Issled., 2002, no. 11, pp. 56–59. Batulin, S.G., Golovin, E.A., Zelenova, O.I., et al., Ekzogennye epigeneticheskie mestorozhdeniya urana (Exogenic-Epigenetic Uranium Deposits), Perel’man, A.I., Ed., Moscow: Atomizdat, 1965. Baturin, G.N. and Kochenov, A.V., Uranium in Phosphorites, Litol. Polezn. Iskop., 2001, vol. 36, no. 4, pp. 353–373 [Lithol. Miner. Resour. (Engl. Transl.), 2001, vol. 36, no. 4, pp. 303–321]. Bliskovskii, V.Z., Phosphorite-Bearing Weathering Crust in the Bol’shie Dzhebarty Deposit (Eastern Sayan), Litol. Polezn. Iskop., 1967, vol. 2, no. 4, pp. 33–42. Bliskovskii, V.Z., Veshchestvennyi sostav i obogatimost’ fosforitnykh rud (Mineral Composition and Concentrability of Phosphorite Ores), Moscow: Nedra, 1983. Bushinskii, G.I., Calcium Phosphates of Phosphorites, Voprosy geologii agronomicheskikh rud (Geology of Agronomic Ores), Moscow: Akad. Nauk SSSR, 1956, pp. 49–64. Bushinskii, G.I., Drevnie fosfority Azii i ikh genezis (Ancient Phosphorites in Asia and Their Genesis), Moscow: Nauka, 1966. Cook, P.J., Petrology and Geochemistry of the Phosphate Deposits of Northwest Queensland, Australia, Econ. Geol., 1972, vol. 67, pp. 1193–1213. Dar’in, A.V. and Zanin, Yu.N., Two Modes of the Behavior of Minor Elements in Supergene Transformations of Phosphorites, Geokhimiya, 1988, vol. 26, no. 1, pp. 49–58. Dar’in, A.V., Zolotarev, K.V., Kalugin, I.A., and Maksimova, N.V., Poverkhnost’ Rentgen. Sinkhrotron. Neutron. Issled., 2003, no. 12, pp. 45–48.
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