Printer Friendly

Mineralogy, geochemistry, and origin of Buyukmahal manganese mineralization in the Artova ophiolitic complex, Yozgat, Turkey.

1. Introduction

The Alpine Ophiolite System (AOC) is exposed along the northwestern and eastern margins of the Yozgat region in Turkey. The Mn mineralization in the Buyukmahal is a part of this ophiolite complex. The mineralization in this area is highly firm and generally fractured and folded, developed in banded and lenticular shape, and syngenetic with radiolarite cherts. Mineralizations are chiefly NW-SW trending and small anticline structures are observed in some parts. Although mineralization in the Buyukmahal area has not been studied, Derbent and Eymir manganese deposits within the AOC were investigated recently by (Oksuz [1, 2]. These deposits were operated from time to time by local miners, but lately none of the deposits is mined out due to low reserve potential. The Eymir manganese deposit which is genetically linked to Buyukmahal mineralization occurs within radiolarite cherts of the lower Cretaceous ophiolite complex [1]. Major and trace element contents of the Eymir ore indicate that the deposit is of a hydrothermalhydrogenous type volcano sedimentary mineralization and both oxic and anoxic sedimentation conditions prevailed. The Derbent manganese mineralization, another manganese deposit in the Yozgat region, occurs as two separate ore bodies [2]. Chemical data yield that hydrothermal and hydrogenousdiagenetic processes played important role in formation of Derbent mineralization. The geochemical characteristics of these deposits are consistent with those of several other manganese mineralizations such as Waziristan, Hazara [3], Baby Bare [4], Baft Ophiolitic melange Kerman (Iran) [5], Wakasa [6], Cayirli [7], and Kasimaga [8] deposits. Particularly Waziristan (Pakistan) and Cayirli (Turkey) deposits are regarded as hydrothermal exhalative manganese deposits occurring on seafloor spreading centers associated with ophiolite units [9,10]. The Buyukmahal deposit under investigation is also thought to be a hydrothermal exhalative manganese mineralization. The aim of this study is to discuss the mineralogical and geochemical mechanisms responsible for development of manganese ore in the Buyukmahal area.

2. Geological Setting

Turkey comprising the border between Eurasia at the north and Gondwana at the south is an E-W elongating component of the Alpine-Himalayan Orogenic zone. The Alpine Orogenic system is formed by the closure of a different branch of the Tethys Ocean. During the closure of Tethys Ocean, continental parts of the Gondwana and Laurasia continents collided. Turkey as an orogenic mosaic (orogenic collage) is a part of these continental parts including remnant materials between these continentals [11]. The AOC is included to the Alpine Orogenic system. The AOC of Upper Cretaceous age shows a wide distribution and hosts several ore mineralizations.

Darmik formation of Upper Cretaceous age consists of Boyalik limestone, Akcadag sandstone, and a radiolarite member. Sarimbey volcanic assemblage (spilitic basalt, andesite unit), Artova ophiolite complex (serpentine, harzburgite, dunite, gabbro, diabase, chert), and Cretaceous limestone blocks are also observed in the area. Artova ophiolite complex is unconformably overlain by conglomerate, sandstone, mudstone, and gypsum levels of the Incik formation of terrestrial character [12] Figure 1).

Ore bodies in the study area occur as laminated, banded and lenticular forms (Figures 2(a), 2(b), 2(c) and 2(d)). The mineralization is entirely associated with radiolarite cherts and thickness of lamina and bands is in the range of 1 to 90 cm. Manganese ores are quite fractured and fissured and show an irregular structure (Figure 2(a)). Polished section determinations indicate that ore assemblage is composed of hematite and pyrolusite, whilst quartz and calcite are the gangue minerals. Pyrolusite and magnetite are the main minerals in the Buyukmahal deposit. Hematite peaks were recorded in XRD analysis but it could not be observed in ore microscopy and Raman spectroscopy determinations.

3. Material and Methods

Twenty ore samples (500 g each) were collected from the Buyukmahal manganese deposit. The whole section of the ore from top to bottom was sampled systematically. Samples were taken at 30 cm intervals.

Powders of 12 samples under 200 mesh were analyzed at ACME Laboratories. Major oxide and trace element contents were determined with ICP-ES and REEs were analyzed with the ICP-MS method. 30 g sample was powdered into 100 [MICRO]m for geochemical analysis. 0.5 g sample was processed in HCl-HN[O.sub.3]- [H.sub.2]O solution at ~95[degrees]C for 1 hour and then the amount of sample was increased 10 mL for the final filtering. Results of analysis are given in Tables 1, 2, and 3. In addition, in order to determine paragenesis and textural characteristics of mineralization, 10 polished sections were studied with ore microscopy. XRD analysis for six samples was done at TPAO (Turkish Petroleum Corporation) laboratories. A Rigaku DMAX IIIC model X-Ray diffractometer with a Cu target (2-70[degrees] 2[theta]) was used in the analyses. Ore minerals were also studied with Thermo Scientific DXR Raman Microscope at the Geological Department of the Ankara University. The Raman spectrums obtained were evaluated with Crystal Sleuth program to determine the mineral paragenesis. Chemical composition of pyrolusite was determined with microprobe analysis conducted at Montan Universitat in Leoben (Austria). The results are shown in Table 4.

4. Mineralogy

Mineral paragenesis in the study area was investigated with ore microscopy studies as well as XRD, Raman spectroscopy, and microprobe analysis for pyrolusite. Results show that pyrolusite and magnetite are the main ore minerals in the Buyukmahal area accompanied by little amount of hematite. Gangue minerals are quartz and calcite. Results of microprobe analysis performed on four points in a pyrolusite crystal are shown in Table 4.

4.1. Pyrolusite (Mn[O.sub.2]). It is mostly precipitated from low-temperature hydrothermal fluids. Pyrolusite is a common alternation mineral in oxidized marine environments. Pyrolusite and magnetite, forming the main components of the Buyukmahal area, with a whitish yellow color, are distinct with their strong anisotropic character. Pyrolusite minerals develop in small veins and characteristic with anhedral and subhedral cutaways. Ore microscopy and Raman spectroscopy images of pyrolusite are shown in Figure 3. Using the results of microprobe analysis, the structural formula of pyrolusite (onthe basisoftwo oxygen) is calculated as [Mn.sub.1.69]- [Fe.sub.0.07]-[Si.sub.0.09]-[Al.sub.0.02]-[Ca.sub.0.01] [O.sub.2] (Table 4).

4.2. Magnetite ([Fe.sub.3][O.sub.4]). Magnetite occurs as small scattered crystals or veins. Vein magnetite is observed cutting the pyrolusite (Figure 4). In single nicol magnetite is seen in brown and gray colors and in the crossed nicols it is in anisotropic character. Samples are slightly magnetic. Ore microscopy and Raman spectroscopy images of magnetite are shown in Figure 4.

5. Geochemistry

Geochemical data are used to determine the origin of mineralization (e.g., hydrothermal, hydrogenous, and diagenetic). The chemical composition of Buyukmahal deposit is Si[O.sub.2]: 85.40 to 10.32 wt%, Mn[O.sub.2]: 68.54 to 6.79 wt%, and [Fe.sub.2][O.sub.3]: 16.73 to 2.31 wt%. Fe and Mn are characteristically fractionated on precipitation from a hydrothermal solution, producing high or low Mn/Fe rations in exhalative sediments [13]. Mn/Fe rations of the deposit range from 25.89 to 0.90 wt% (Table 1). These values are conformable with those of hydrothermal exhalative manganese deposits in ophiolitic regions and recent submarine spreading centers [1,14,15].

The Si-Al discrimination diagram, proposed by Peters [16], is used to distinguish hydrothermal from hydrogenous Mn-oxide deposits. Buyukmahal ore samples are almost within the field of hydrothermal field, with only one sample within the field of hydrogenous deposits (Figure 5).

Ba contents of Waziristan [6], Hazara (Pakistan) [3], Binkrlif [17], Cayirli [7], and Kasimaga (Turkey) [8] regions are very high (415, 6304, 6892, 1229, and 2719, resp.) indicating a sedimentary contribution. High Ba content of the Buyukmahal deposit (ave. 3659) is also indicative of sedimentary origin. Modern submarine hydrothermal Mn-oxide deposits are more enriched in Cu, Zn, Ni, and Co contents in comparison to pelagic sediments. However, they are lower than hydrogenous deposits [13,18]. Choi and Hariya [6] discriminated hydrogeneous deposits and submarine hydrothermal Mn-deposits on a Ni-Zn-Co ternary diagram. On this diagram, five samples are plotted near hydrogenous fields and seven samples are close to hydrogenous field (Figure 6). In Fe-(Ni + Co + Cu) * 10-Mn triangular diagram [9, 10, 19], all samples are plotted in hydrothermal and diagenetic fields (Figure 7). Correlation data on major oxide and some trace elements contents of ore samples are given in Table 5.

The correlation coefficients indicate the presence of strong positive relations between major oxides and various trace elements ([Al.sub.2][O.sub.3]-[Fe.sub.2][O.sub.3]: r = 0.95; [Al.sub.2][O.sub.3]-Ti[O.sub.2]: r = 0.99; Ti[O.sub.2]-[Fe.sub.2][O.sub.3]: r = 0.94) and the contribution of mafic terrigenous material to the deposition environment.

Major oxide, trace, and REE geochemistry are very useful for understanding the formation conditions of ore deposits. REE contents of 12 samples collected from the Buyukmahal manganese mineralization are shown in Table 6. REE contents of the hydrothermal and hydrogenous ferromanganese and manganese deposits differ considerably and thus can provide great information on the genetic processes involved in the formation of submarine manganese and ferromanganese ores [20-23]. REE patterns of the studied deposit (Figure 8(a)) are compared with those of other hydrogenous and hydrothermal manganese deposits (Figure 8(b)). Results indicate that hydrogenous ferromanganese deposits are more enriched in REEs than their hydrothermal equivalents. Hydrogenous ferromanganese deposits show positive Ce anomaly but hydrothermal ferromanganese deposits are characteristic with negative Ce anomaly [22-24]. All samples of the Buyukmahal manganese mineralization show strong negative Ce anomalies which resemble the pattern of typical submarine hydrothermal deposits (Figure 8(a)). However, the Ce anomaly depends on the temperature of the fluid, the proximity to the hydrothermal source, and redox conditions [23, 25, 26]. Eu also shows negative anomaly in all samples, indicating contamination from the continental crust and/or sediment contribution via dehydration [27].

In hydrothermal solutions [La.sub.N]/[Nd.sub.N] ratio is 3.0-7.4 (average 4.5) and [Dy.sub.N]/[Yb.sub.N] ratio is 0.6-2.1 (average 1.2). These ratios in Mn-oxide crusts are 2.7-4.3 and 0.4-1.2, respectively [4]. These rations in hydrogenous deposits are 0.90-1.50 and 0.3-1.91, respectively [24]. The ranges of [La.sub.N]/[Nd.sub.N] and [Dy.sub.N]/[Yb.sub.N] ratios for the Buyukmahal manganese mineralization are 1.41-2.34 (average 1.82) and 0.90-1.44 (average 1.18) (Table 6). These values imply that Buyukmahal mineralization might be a hydrogenous deposit.

Y/Ho ratios in the area range from 13.06 to 31.54 (average 25.05). High Y/Ho ratios are indicative of multienvironments for the mineral deposition. In this respect, both deep marine environments and terrigenous materials may be effective for precipitation [30].

Data computed with the formula of [Ce.sub.anom] = log [3 x [Ce.sub.N]/(2 x [La.sub.N] + [Nd.sub.N])] also yield information on the origin of mineralization. For example, in the case of [Ce.sub.anom] > -0.1, Ce is said to be enriched, which reflects an anoxic character for the water body of sedimentation. If [Ce.sub.anom] < -0.1, there is a negative Ce anomaly which indicates an oxic nature for the water body of sedimentation [31]. Ce anomalies in all samples at Buyukmahal are found to be [Ce.sub.anom] < -0.1, indicating an oxic character for the sedimentation environment.

6. Discussions and Conclusions

The AOC of Upper Cretaceous age is located along the northwestern and eastern margins in Yozgat (Turkey) and is included to the Alpine Orogenic system. Mineralization in the Buyukmahal area, observed in banded and lenticular forms, occurs in a close association with radiolarite cherts and is intensely affected by the tectonism.

Based on the results of major and trace element data, mineralization in the study area was probably formed from hydrothermal solutions associated with a sea floor spreading center. However, ore minerals at Buyukmahal were not precipitated entirely from a purely hydrothermal or purely hydrogenous fluid, but certainly from a mixture of these two. For instance, Ti is generally immobile in hydrothermal solutions and could be a measure of clastic input [32]. The good correlation observed between [Al.sub.2][O.sub.3] and Ti[O.sub.2] (r = 0.99) can be attributed to the mixing of detrital materials during precipitation [6].

Fe compounds (less stable than Mn) precipitate proximal parts, whilst Mn compounds precipitate distal parts of hydrothermal vents along the sea floor spreading centers [33, 34]. Eh and/or pH of the hydrothermal solution also exert controls on the precipitation of Mn and Fe and their compounds [34-37]. Mn is more mobile relative to Fe during low Eh and/or pH conditions. The fractionation of Mn compounds from Fe compounds suggests a spatial variation in Eh and/or pH [34]. Considering Fe and Mn concentrations of the mineralization in the study area, it can be asserted that Buyukmahal deposit was formed from a hydrothermal source; in addition, considering the high Fe content, mineralization might be formed in a proximal site of the hydrothermal vent.

Although mineralization at Buyukmahal is of a hydrothermal type, it does not originate from a pure hydrothermal or pure hydrogenous source. Geochemical data support a system contributed from both sources. The mineralization was developed on a sea floor spreading center within the Alpin Ophiolite system and then obducted as part of the AOC.

http://dx.doi.org/10.1155/2014/837972

Conflict of Interests

The authors declare that there is no conflict of interests regarding the publication of this paper.

Acknowledgments

This study constitutes a part of M.S. degree thesis of Neslihan Okuyucu. The Scientific and Technical Research Council of Turkey (TUBITAK Project no. 109Y167) and the Bozok University (Grant no. B.F.F.M/2009-06) are greatly acknowledged for financial support. Dr. Ibrahim Uysal is kindly appreciated for his help in EMP analysis. The authors also thank Professor Yusuf K. Kadioglu and Cumhur O. Kilic for the Raman spectroscopy analysis.

References

[1] N. Oksuz, "Geochemical characteristics of the Eymir (Sorgun-Yozgat) manganese deposit, Turkey," Journal of Rare Earths, vol. 29, no. 3, pp. 287-296, 2011.

[2] N. (Oksiiz, "Geochemistry and the origin of manganese mineralizations in Derbent (Yozgat) Region," Bulletin of the Earth Sciences Application and Research Centre of Hacettepe Universit, vol. 32, no. 3, pp. 213-234, 2011.

[3] M. Tahir Shah and C. J. Moon, "Manganese and ferromanganese ores from different tectonic settings in the NW Himalayas, Pakistan," Journal of Asian Earth Sciences, vol. 29, no. 2-3, pp. 455-465, 2007

[4] C. E. Fitzgerald and K. M. Gillis, "Hydrothermal manganese oxide deposits from Baby Bare seamount in the Northeast Pacific Ocean," Marine Geology, vol. 225, no. 1-4, pp. 145-156, 2006.

[5] K. Heshmatbehzadi and J. Shahabpour, "Metallogeny of manganese and ferromanganese ores in baft ophiolitic Melange, Kerman, Iran," Australian Journal of Basic and Applied Sciences, vol. 4, no. 2, pp. 302-313, 2010.

[6] J. H. Choi and Y. Hariya, "Geochemistry and depositional environment of Mn oxide deposits in the Tokoro Belt, northeastern Hokkaido, Japan," Economic Geology, vol. 87, no. 5, pp. 1265-1274, 1992.

[7] A. Karakus, B. Yavuz, and S. Koiy "Mineralogy and major-trace element geochemistry of the Haymana manganese mineralizations, Ankara, Turkey," Geochemistry International, vol. 48, no. 10, pp. 1014-1027, 2010.

[8] S. Koc, O. Ozmen, and N. Oksuz, "Geochemistry characteristic of kasimaga (Keskin-Kirikkale) manganese oxide mineralizations," Mineral Research and Exploration Magazine, vol. 122, p. 107, 2000.

[9] E. Bonatti, T. Kraemer, and H. Rydell, "Classification and genesis of submarine iron-manganese deposits," in Ferromanganese Deposits on the Ocean Flor: International Decade on Ocean Exploration, D. Horn, Ed., pp. 149-166, National Science Foundation, Washington, DC, USA, 1972.

[10] D. A. Crerar, J. Namson, M. S. Chyi, L. Williams, and I. M. Feigenson, "Manganiferous cherts of the Fransiscan assemblage: I. General geology, ancient and modern analogues, and implications for hydrothermal convection at oceanic spreading centers," Economic Geology, vol. 77, pp. 519-540, 1982.

[11] A. Okay and O. Tuysuz, "Tethyan sutures of northern Turkey," in The Mediterranean Basins: Tertiary Extension Within the Alpine Orogen, B. Durand, L. Jolivet, F. Horvath, and M. Serrane, Eds., vol. 156, pp. 475-515, Geological Society, London, UK, 1999.

[12] A. E. Akcay, M. Donmez, H. Kara, A. F. Yergok, and K. Esenturk, "1/100 000 scale geological maps of Turkey, Yozgat-I33 threader," MTA Ankara, vol. 80, pp. 1-16, 2007

[13] M. T. Shah and A. Khan, "Geochemistry and origin of Mndeposits in the Waziristan ophiolite complex, north Waziristan, Pakistan," Mineralium Deposita, vol. 34, no. 7, pp. 697-704, 1999.

[14] X. Jiancheng, S. Weidong, D. Jianguo et al., "Geochemical studies on Permian manganese deposits in Guichi, eastern China. Implications for their origin and formative environments," Journal of Asian Earth Science, vol. 74, pp. 155-166, 2013.

[15] A. Sasmaz, B. Turkyilmaz, N. Ozturk et al., "Geology and geochemistry of middle eocene maden complex ferromanganese deposits from Elazig-Malatya Region, Eastern, Turkey," Ore Geology Reviews, vol. 56, pp. 352-372, 2014.

[16] T. Peters, "Geochemistry of manganese-bearing cherts associated with Alpine ophiolites and the Hawasina formations in Oman," Marine Geology, vol. 84, no. 3-4, pp. 229-238, 1988.

[17] A. H. Gultekin, "Geochemistry and origin of the Oligocene Binkily: manganese deposit, Thrace basin, Turkey," Turkish Journal of Earth Sciences, vol. 7, p. 11, 1998.

[18] D. S. Cronan, "Underwater minerals," Academic Press, London, UK, 1980.

[19] J. R. Hein, S. S. Marjorie, and L. M. Gein, "Central Pasific cobalt rich ferromanganese crusts. Historical perspective and regional variability," in Geology and Offshore Mineral Resources of the Central Pasific Basin, Sircum Pasific Council for Energy and Mineral Resources, B. H. Keating and B. R. Balton, Eds., vol. 14 of Earth science series, Springer, New York, NY, USA, 1992.

[20] J. R. Toth, "Deposition of submarine crusts rich in manganese and iron," Geological Society of America Bulletin, vol. 91, no. 1, pp. 44-54, 1980.

[21] D. E. Ruhlin and R. M. Owen, "The rare earth element geochemistry of hydrothermal sediments from the East Pacific Rise: examination of a seawater scavenging mechanism," Geochimica et Cosmochimica Acta, vol. 50, no. 3, pp. 393-400, 1986.

[22] J. D. Wonder, P. G. Spry, and K. E. Windom, "Geochemistry and origin of manganese-rich rocks related to iron-formation and sulfide deposits, western Georgia," Economic Geology, vol. 83, no. 5, pp. 1070-1081, 1988.

[23] J. R. Hein, A. Kochinsky, P. Halbach et al., "Iron and manganese oxide mineralization in the Pacific," in Manganese Mineralization: Geochemistry and Mineralogy of Terrestrial and Marine Deposits, K. Nicholson, J. R. Hein, B. Buhn, and S. Dasgupta, Eds., vol. 119, pp. 123-138, Geological Society, London, UK, 1997

[24] H. Elderfield, C. J. Hawkesworth, M. J. Greaves, and S. E. Calvert, "Rare earth element geochemistry of oceanic ferromanganese nodules and associated sediments," Geochimica et Cosmochimica Acta, vol. 45, no. 4, pp. 513-528, 1981.

[25] N. Clauer, P. Stille, C. Bonnot-Courtois, and W. S. Moore, "Nd-Sr isotopic and REE constraints on the genesis of hydrothermal manganese crusts in the Galapagos," Nature, vol. 311, no. 5988, pp. 743-745, 1984.

[26] J. R. Hein, Y. Hsueh-Wen, S. H. Gunn, A. E. Gibbs, and W. Chung-ho, "Composition and origin of hydrothermal ironstones from central Pacific seamounts," Geochimica et Cosmochimica Acta, vol. 58, no. 1, pp. 179-189, 1994.

[27] S. S. Sun and W. F. McDonough, "Chemical and isotopic systematics of oceanic basalts: implications for mantle composition and processes," in Magmatism in Ocean Basins, A. D. Saunders and M. J. Norry, Eds., pp. 313-345, Geological Society, London, UK, 1989.

[28] N. M. Evensen, P J. Hamilton, and R. K. O'Nions, "Rare-earth abundances in chondritic meteorites," Geochimica et Cosmochimica Acta, vol. 42, no. 8, pp. 1199-1212,1978.

[29] U. Von Stackelberg, "Growth history of manganese nodules and crusts of the Peru Basin," Geological Society, vol. 119, pp. 153-176, 1997.

[30] J. Nayan, J. Rongfen, and W. Ziyu, Permain Palaeogeography and Geochemical Environment in Lower Yangtze Region, Petroleum Industry Press, Beijing, China, 1994.

[31] J. Wright, H. Schrader, and W. T. Holser, "Paleoredox variations in ancient oceans recorded by rare earth elements in fossil apatite," Geochimica et Cosmochimica Acta, vol. 51, no. 3, pp. 631-644,1987.

[32] R. Sugisaki, "Relation between chemical composition and sedimentation rate of Pacific ocean-floor sediments deposited since the middle Cretaceous: basic evidence for chemical constraints on depositional environments of ancient sediments (plate tectonic orogenic model)," Journal of Geology, vol. 92, no. 3, pp. 235-259, 1984.

[33] A. G. Panagos and S. P Varanavas, "On the genesis of some manganese deposits from eastern Greece," Syngenesis and Epigenesis in the Formation of Mineral Deposits, pp. 553-561, 1984.

[34] S. Roy, "Environments and processes of manganese deposition," Economic Geology, vol. 87, no. 5, pp. 1218-1236, 1992.

[35] K. B. Krauskopf, "Separation of manganese from iron in sedimentary processes," Geochimica et Cosmochimica Acta, vol. 12, no. 1-2, pp. 61-84, 1957.

[36] J. D. Hem, "Chemical factors that influence that influence the availability of iron and manganese in aqueous systems," Geological Society of America Bulletin, vol. 83, pp. 443-450, 1972.

[37] L. Frakes and B. Bolton, "Effects of ocean chemistry, sea level, and climate on the formation of primary sedimentary manganese ore deposits," Economic Geology, vol. 87, no. 5, pp. 1207-1217, 1992.

Nursel Oksuz and Neslihan Okuyucu

Department of Geological Engineering, Faculty of Engineering & Architecture, Bozok University, 66100 Yozgat, Turkey

Correspondence should be addressed to Nursel Oksuz; nursel.oksuz@gmail.com

Received 13 May 2013; Revised 8 December 2013; Accepted 17 December 2013; Published 6 February 2014

Academic Editor: Chengshuai Liu

TABLE 1: Major oxide contents of Buyukmahal ore (%).

Sample    Si[O.sub.2]     [Al.sub.2]     [Fe.sub.2]     MgO     CaO
                          [O.sub.3]      [O.sub.3]

N1           41.93           6.28          12.21       2.30    2.41
N2           43.56           7.91          16.73       1.57    6.52
NT1          70.37           0.69           3.20       0.08    0.24
NT2          82.91           1.72           3.68       0.30    0.16
NT3          85.40           1.56           2.93       0.25    0.19
NT4          72.96           2.02           3.43       0.31    0.21
Ml           81.21           2.10           2.31       0.32    0.20
M2           25.77           4.38           7.49       2.01    5.63
M3           31.43           6.02           9.75       3.42    3.15
M4           20.83           3.41           6.89       1.25    8.85
M5           28.77           5.24           8.06       3.01    6.29
M6           10.32           2.59           2.93       0.87    1.47
Min          10.32           0.69           2.31       0.08    0.16
Max          85.40           7.91          16.73       3.42    8.85
Ave          49.62           3.66           6.63       1.31    2.94

Sample    [Na.sub.2]O     [K.sub.2]O    Ti[O.sub.2]     [P.sub.2]
                                                        [O.sub.5]

N1            0.32           1.42           0.30           0.17
N2            0.38           1.73           0.34           0.23
NT1           0.05           0.06           0.02           0.03
NT2           0.07           0.36           0.07           0.02
NT3           0.04           0.36           0.06           0.06
NT4           0.06           0.65           0.09           0.04
Ml            0.07           0.60           0.11           0.04
M2            0.25           0.58           0.21           0.17
M3            0.39           1.36           0.28           0.20
M4            0.14           0.02           0.13           0.07
M5            0.26           0.53           0.23           0.15
M6            0.09           0.40           0.08           0.13
Min           0.04           0.02           0.02           0.02
Max           0.39           1.73           0.34           0.23
Ave           0.18           0.67           0.16           0.11

Sample     MnO       Cr2        Mn      Fe     Mn/Fe     LOI    Total
                  [O.sub.3]

N1        23.59      0.01      18.27   8.54     2.14    8.60    99.57
N2        13.61      0.01      10.54   11.70    0.90    7.00    99.65
NT1       20.53      0.10      15.90   2.24     7.10    4.30    99.71
NT2       7.65       0.11      5.92    2.57     2.30    2.70    99.82
NT3       6.79       0.14      5.26    2.05     2.57    2.00    99.85
NT4       15.68      0.10      12.14   2.40     5.06    3.70    99.31
Ml        9.50       0.00      7.36    1.62     4.54    3.10    99.57
M2        41.79      0.00      32.37   5.24     6.18    10.80   99.13
M3        30.52      0.00      23.64   6.82     3.47    11.20   97.71
M4        46.89      0.00      36.32   4.82     7.54    11.00   99.51
M5        36.39      0.00      28.18   5.64     5.00    10.40   99.33
M6        68.54      0.01      53.08   2.05    25.89    11.70   99.12
Min       6.79       0.00      5.26    1.62     0.90    2.00    97.71
Max       68.54      0.14      53.08   11.70   25.89    11.70   99.85
Ave       26.79      0.04      20.75   4.64     6.06    7.21    99.36

TABLE 2: Trace elements contents of Buyukmahal ore (ppm).

Sample      Ba       Be       Co      Cs      Hf      Nb

N1        1039.0     2.0    563.2     2.8     2.3     7.4
N2         892.0     1.0    434.9     2.9     3.2    15.2
NT1        959.0     2.0     73.5     0.2     0.4     1.2
NT2        911.0     1.0     80.2     1.2     0.7     2.5
NTS       1028.0     1.0     35.9     1.1     1.0     2.5
NT4       5068.0     2.0     63.3     1.2     0.7     2.3
Ml        2612.0     2.0     50.7     2.2     0.8     2.6
M2        5408.0     3.0    147.8     0.9     1.3     2.3
MS        16855.0    2.0    134.6     2.5     2.0     5.1
M4         740.0     2.0    1432.1    0.1     0.9     1.4
M5        3355.0     4.0    417.3     1.0     1.5     3.0
M6        5036.0     5.0    975.6     0.3     0.7     0.7
Min        740.0     1.0     35.9     0.1     0.4     0.7
Max       16855.0    5.0    1432.1    2.9     3.2    15.2
Ave.      3658.6     2.3    367.4     1.4     1.3     3.9

Sample     Rb       Sr       Ta      Th       U       V

N1        52.5     296.2     0.5     7.2     2.9    498.0
N2        60.6     167.6     1.1     8.7     2.1    393.0
NT1        2.1     310.0     0.1     0.4     5.4    126.0
NT2       16.2     131.1     0.1     1.1     1.0     64.0
NTS       13.3     184.0     0.1     1.3     1.0     53.0
NT4       17.1     644.0     0.2     1.9     2.4    132.0
Ml        26.4     342.3     0.3     1.8     2.1     86.0
M2        18.3     766.1     0.2     4.3     1.8    346.0
MS        46.6    1670.1     0.4     5.7     2.0    260.0
M4         0.8     321.2     0.1     2.6     2.9    983.0
M5        16.7     512.0     0.2     4.7     2.1    311.0
M6         7.2     552.8     0.1     1.4     8.7    183.0
Min        0.8     131.1     0.1     0.4     1.0     53.0
Max       60.6    1670.1     1.1     8.7     8.7    983.0
Ave.      23.2     491.5     0.3     3.4     2.9    286.3

Sample      Zr      Mo       Cu      Pb       Zn       Ni

N1         92.6     5.9    416.0    33.4    116.0    204.7
N2        131.9    12.4    282.6    37.9     92.0    199.2
NT1        17.5    25.8    1210.0    4.6     32.0    341.0
NT2        31.4    12.3    489.8    15.3     21.0    423.4
NTS        35.4    12.5    243.6    20.2     13.0    488.0
NT4        27.1    17.1    329.2    36.1     30.0    351.3
Ml         28.5     5.9    304.6     9.7     31.0     25.9
M2         65.1     8.3    409.9    30.7    119.0    238.5
MS         83.0    10.1    374.4    38.3    128.0    255.2
M4         46.8    25.5    233.1    29.2    120.0    342.7
M5         65.6     5.6    372.8    36.6    152.0    320.0
M6         31.5    15.9    744.1    17.6    128.0    174.3
Min        17.5     5.6    233.1     4.6     13.0     25.9
Max       131.9    25.8    1210.0   38.3    152.0    488.0
Ave.       54.7    13.1    450.8    25.8     81.8    280.4

Sample     As      Cd      Sb      Bi      Ag      Au

N1        37.8     0.1     0.5     0.3    12.5     2.6
N2        43.5     0.1     0.2     0.5     5.6     0.5
NT1       29.5     0.1     2.2     0.1    10.4     5.0
NT2       17.9     0.1     1.0     0.1     0.1     2.4
NTS       13.8     0.1     0.5     0.1     0.1     1.5
NT4       17.2     0.1     0.7     0.2     8.1     1.0
Ml         7.3     0.1     0.3     0.1     0.1     1.0
M2        16.7     0.2     0.5     0.3     0.1     2.9
MS        16.2     0.2     0.3     0.4     0.1     2.1
M4        45.1     0.3     0.4     0.2     0.1     7.9
M5        11.6     0.2     0.4     0.4     0.1     2.9
M6        30.7     0.2     0.5     0.2     0.1     4.3
Min        7.3     0.1     0.2     0.1     0.1     0.5
Max       45.1     0.3     2.2     0.5    12.5     7.9
Ave.      23.9     0.2     0.6     0.2     3.1     2.8

TABLE 3: REE contents of Buyukmahal ore (ppm).

Sample     La       Ce       Pr       Nd       Sm       Eu       Gd

N1       50.90    52.50    14.47    60.30    11.14     2.75    11.60
N2       53.30    77.10    17.39    72.00    15.44     3.76    15.15
NT1       4.30     4.90     1.22     5.90     0.96     0.20     0.87
NT2      22.50    17.20     6.81    27.60     4.27     0.94     3.39
NTS      14.20    17.70     3.52    15.90     2.87     0.71     2.92
NT4      16.00    30.30     4.20    17.70     3.08     0.74     2.96
Ml       13.10    23.40     3.33    13.50     2.54     0.61     2.72
M2       39.80    37.10     9.74    40.10     7.81     1.90     7.92
MS       41.70    42.70    10.24    43.20     8.35     1.95     8.74
M4       26.60    23.60     5.53    22.00     4.27     1.04     4.24
M5       37.80    37.50     9.77    39.90     7.65     1.83     7.16
M6       30.60    26.60     6.50    25.90     4.62     1.14     4.40
Min       4.30     4.90     1.22     5.90     0.96     0.20     0.87
Max      53.30    77.10    17.39    72.00    15.44     3.76    15.15
Ave.     29.23    32.55     7.73    32.00     6.08     1.46     6.01

Sample     Tb       Dy       Ho       Er       Tm       Yb       Lu

N1        1.80     9.80     1.96     5.71     0.79     4.90     0.73
N2        2.48    13.59     2.64     7.40     1.04     6.48     0.89
NT1       0.13     0.64     0.13     0.37     0.06     0.46     0.08
NT2       0.53     2.60     0.49     1.29     0.20     1.17     0.16
NTS       0.46     2.52     0.54     1.52     0.21     1.28     0.18
NT4       0.46     2.67     0.53     1.54     0.22     1.36     0.21
Ml        0.43     2.65     0.53     1.46     0.21     1.42     0.21
M2        1.27     7.34     1.55     4.45     0.64     4.06     0.61
MS        1.39     7.86     1.61     4.87     0.70     4.38     0.67
M4        0.70     4.13     0.86     2.65     0.42     2.65     0.40
M5        1.16     6.63     1.31     3.81     0.55     3.69     0.54
M6        0.70     4.45     0.88     2.85     0.47     3.11     0.49
Min       0.13     0.64     0.13     0.37     0.06     0.46     0.08
Max       2.48    13.59     2.64     7.40     1.04     6.48     0.89
Ave.      0.96     5.41     1.09     3.16     0.46     2.91     0.43

Sample     Y       Y/Ho    [Ce.sub.anom]   [Dy.sub.N]/    [La.sub.N]/
                                            [Yb.sub.N]     [Nd.sub.N]

N1       54.60    27.86        -0.34           1.30           1.64
N2       68.30    25.87        -0.21           1.36           1.43
NT1       4.10    31.54        -0.32           0.90           1.41
NT2       6.40    13.06        -0.48           1.44           1.58
NTS      12.70    23.52        -0.26           1.28           1.73
NT4      13.30    25.09        -0.07           1.28           1.75
Ml        7.90    14.91        -0.09           1.21           1.88
M2       44.90    28.97        -0.37           1.18           1.92
MS       48.30    30.00        -0.33           1.17           1.87
M4       23.20    26.98        -0.38           1.01           2.34
M5       38.10    29.08        -0.35           1.17           1.84
M6       23.30    26.48        -0.39           0.93           2.29
Min       4.10    13.06        -0.48           0.90           1.41
Max      68.30    31.54        -0.07           1.44           2.34
Ave.     28.76    25.28        -0.30           1.19           1.81

[Ce.sub.anom] = log[3 x [Ce.sub.N]/(2 x [La.sub.N] + [Nd.sub.N])].

TABLE 4: Composition of pyrolusite (pr) samples of Buyukmahal ore.

(a)

           Si       Ti       Al       Fe       Mn       Mg

pr48      2.61     0.08     0.61     3.26    75.71     0.09
pr49      2.26     0.10     0.43     2.70    80.48     0.04
pr50      1.52     0.19     0.42     3.00    74.90     0.08
pr51      2.32     0.08     0.59     3.02    76.44     0.06
Ave.      2.18     0.11     0.51     2.99    76.88     0.07

           Ca       Na       K        Ba       Ag       Zn

pr48      0.60     0.00     0.05     0.25     0.00     0.00
pr49      0.55     0.06     0.05     0.95     0.01     0.06
pr50      0.49     0.03     0.09     0.20     0.02     0.06
pr51      0.40     0.05     0.16     0.32     0.02     0.00
Ave.      0.51     0.03     0.09     0.43     0.01     0.03

(b)

        Si[O.sub.2]   Ti[O.sub.2]   [Al.sub.2]    [Fe.sub.2]
                                     [O.sub.3]     [O.sub.3]

pr48       5.58          0.13          1.15          4.66
pr49       4.83          0.17          0.81          3.86
pr50       3.25          0.32          0.79          4.29
pr51       4.96          0.13          1.11          4.32

            MnO           MgO           CaO       [Na.sub.2]O

pr48       97.76         0.15          0.08          0.00
pr49      103.92         0.07          0.77          0.08
pr50       96.71         0.13          0.69          0.04
pr51       98.70         0.10          0.56          0.07

        [K.sub.2]O        BaO       [Ag.sub.2]O       ZnO

pr48       0.06          0.28          0.00          0.00
pr49       0.06          1.06          0.01          0.07
pr50       0.11          0.22          0.02          0.07
pr51       0.19          0.36          0.02          0.00

(c)

Number of ions calculated on the basis of 2 (O)

         Coef.      Si        Ti        Al        Fe        Mn

pr48     1.20      0.11      0.00      0.03      0.08      1.65
pr49     1.16      0.09      0.00      0.02      0.06      1.70
pr50     1.27      0.07      0.01      0.02      0.08      1.73
pr51     1.20      0.10      0.00      0.03      0.07      1.67
Ave.     1.21      0.09      0.00      0.02      0.07      1.69

          Mg        Ca        Na         K       Total

pr48     0.00      0.00      0.00      0.00      1.87
pr49     0.00      0.02      0.00      0.00      1.90
pr50     0.00      0.02      0.00      0.00      1.92
pr51     0.00      0.01      0.00      0.00      1.89
Ave.     0.00      0.01      0.00      0.00      1.90

TABLE 5: Correlation relations for major oxides.

                      Si[O.sub.2]   [Al.sub.2]    [Fe.sub.2]     MgO
                                     [O.sub.2]     [O.sub.3]

Si[O.sub.2]                1           -0.56         -0.43      -0.67
[Al.sub.2][O.sub.2]                    1.00          0.95        0.81
[Fe.sub.2][O.sub.3]                                  1.00        0.66
MgO                                                              1.00
CaO
[Na.sub.2]O
[K.sub.2]O
Ti[O.sub.2]
[P.sub.2][O.sub.5]
MnO
[Cr.sub.2][O.sub.3]

                       CaO     [Na.sub.2]O   [K.sub.2]O    Ti[O.sub.2]

Si[O.sub.2]           -0.71       -0.55         -0.17         -0.49
[Al.sub.2][O.sub.2]    0.64       0.97          0.84          0.99
[Fe.sub.2][O.sub.3]    0.63       0.92          0.82          0.94
MgO                    0.59       0.88          0.55          0.82
CaO                    1.00       0.59          0.16          0.58
[Na.sub.2]O                       1.00          0.82          0.97
[K.sub.2]O                                      1.00          0.87
Ti[O.sub.2]                                                   1.00
[P.sub.2][O.sub.5]
MnO
[Cr.sub.2][O.sub.3]

                       [P.sub.2]     MnO     [Cr.sub.2]
                       [O.sub.5]              [O.sub.3]

Si[O.sub.2]              -0.68      -0.89       0.78
[Al.sub.2][O.sub.2]      0.93        0.14       -0.65
[Fe.sub.2][O.sub.3]      0.85        0.00       -0.50
MgO                      0.81        0.36       -0.67
CaO                      0.57        0.45       -0.63
[Na.sub.2]O              0.93        0.14       -0.63
[K.sub.2]O               0.77       -0.21       -0.38
Ti[O.sub.2]              0.91        0.06       -0.64
[P.sub.2][O.sub.5]       1.00        0.33       -0.65
MnO                                  1.00       -0.59
[Cr.sub.2][O.sub.3]                             1.00

0.70 and higher values and -0.70 and lower values specify the presence
of positive or negative corelation coefficients.

TABLE 6: Correlation relations for trace elements.

        Ba       Co       Rb       Sr       U        Zr       Mo

Ba     1.00    -0.19     0.26     0.98     0.00     0.16    -0.21
Co              1.00    -0.19    -0.14     0.45     0.14     0.37
Rb                       1.00     0.21    -0.33     0.85    -0.57
Sr                                1.00     0.01     0.16    -0.17
U                                          1.00    -0.27     0.42
Zr                                                  1.00    -0.41
Mo                                                           1.00
Cu
Pb
Zn
Ni
As
Bi
Ag

        Cu       Pb       Zn       Ni       As       Bi       Ag

Ba    -0.08     0.39     0.37    -0.17    -0.34     0.37    -0.27
Co    -0.10     0.18     0.59    -0.12     0.71     0.16    -0.12
Rb    -0.37     0.54     0.23    -0.42     0.18     0.69     0.30
Sr    -0.06     0.42     0.44    -0.16    -0.30     0.39    -0.22
U      0.67    -0.35     0.25    -0.29     0.36    -0.14     0.17
Zr    -0.40     0.72     0.54    -0.28     0.42     0.90     0.16
Mo     0.47    -0.32    -0.22     0.39     0.50    -0.37     0.19
Cu     1.00    -0.61    -0.13     0.02     0.12    -0.32     0.38
Pb              1.00     0.60     0.02     0.18     0.83     0.04
Zn                       1.00    -0.32     0.31     0.72    -0.17
Ni                                1.00    -0.05    -0.26    -0.03
As                                         1.00     0.27     0.42
Bi                                                  1.00     0.05
Ag                                                           1.00

0.70 and higher values and -0.70 and lower values specify the presence
of positive or negative corelation coefficients.
COPYRIGHT 2014 Hindawi Limited
No portion of this article can be reproduced without the express written permission from the copyright holder.
Copyright 2014 Gale, Cengage Learning. All rights reserved.

Article Details
Printer friendly Cite/link Email Feedback
Title Annotation:Research Article
Author:Oksuz, Nursel; Okuyucu, Neslihan
Publication:Journal of Chemistry
Article Type:Report
Geographic Code:7TURK
Date:Jan 1, 2014
Words:6700
Previous Article:One-step synthesis of superparamagnetic [Fe.sub.3][O.sub.4]@PANI nanocomposites.
Next Article:Investigation on aromaticity index and double-bond equivalent of aromatic compounds and ionic liquids for fuel desulphurization.
Topics:

Terms of use | Privacy policy | Copyright © 2021 Farlex, Inc. | Feedback | For webmasters |