International Journal of Geosciences
Vol.05 No.01(2014), Article ID:42358,7 pages
10.4236/ijg.2014.51009
Determination of Indicator Plants for Boron in the Kırka (Eskişehir/Turkey) Boron Deposit Area
Zeynep Özdemir1*, Semiha Zorlu2, Mustafa Akyıldız2, Fulya Yücesoy Eryılmaz1
1Department of Geology Engineering, Mersin University, Mersin, Turkey
2Department of Geology Engineering, Çukurova University, Adana, Turkey
Email: *zozdemir@mersin.edu.tr, *zeyrut@gmail.com, ksemiha@hotmail.com, akyildizm@cu.edu.tr, fyucesoy@mersin.edu.tr
Copyright © 2014 Zeynep Özdemir et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. In accordance of the Creative Commons Attribution License all Copyrights © 2014 are reserved for SCIRP and the owner of the intellectual property Zeynep Özdemir et al. All Copyright © 2014 are guarded by law and by SCIRP as a guardian.
ABSTRACT
The amount of elements in plants is important for biogeochemical explorations. Some plants which were accumulated extremely elements, are called indicator plants. In this study, the 11 plant species and soil samples were collected boron deposits area in Kırka (
Keywords
Biogeochemistry; Boron; Indicator Plant; Kırka (Eskişehir/Turkey)
*Corresponding author.
1. Introduction
The Turkish borate deposits (Bigadiç, Sultançayırı, Kestelek, Emet and Kırka) are approximately 75% - 85% of the world reserves that contain some borate minerals such as coleminite, ulexite borax, etc. The Kırka (Eskişehir/ Turkey) deposit which is one of the most important bo- rate minerals, is the largest boron deposit not only in Turkey but also in the world (Figure 1) [1,2].
In the literature, many geochemical and geophysical methods have been used to explore the new mining deposits. The resistivity and seismic methods are used in the gravity and magnetic geophysical researches, particularly for borate deposits created by sedimentary filling. On the other hand, the drilling method with geological mapping is one of the most suitable methods in order to explore the new mining deposits in the world [3,4].
Recently, the biogeochemical prospecting methods are successfully used for detection of the new mining deposits. These methods include the determination elements in different organs of plants such as leaves, twigs or roots and soil. In generally, the relationship between the amount of elements in plant and soil is used for determine the indicator plants. In the literature, several indicator plants are found for Au and Fe, Mn, Zn, Cu, and other elements [4-20].
Boron is metalloid and essential for plant functions. When presented in suboptimal or in excess amount, it may become nutritional deficiency or toxic [21,22]. However, some plant species extremely accumulated or tolerated boron. It was reported that only the Eurotia ceratoides, Limonium suffruticosum and Salsola nitraria species in Russia were accumulated boron [5].
In this study, the amount of the boron is determinated in plant and soil samples in Kırka (Eskisehir-Turkey) borate deposits and investigated plant-soil relationships for each plant species organs. The indicator plant species which are found could be used as guidelines in order to determine the borate deposits and environmental monitoring in future studies.
2. Geology and Location of Borate Deposits
There are three coeval assemblages in the west of Central Anotolia (from West to East) in the youngest Alpine magmatism (Miocene to Quaternary). They are the Western Anatolian Volcanic assemblage, the N-S trending Kırka-Afyon-Isparta Alkaline Volcanic assemblage and the Central Anatolian Volcanic Provinces [23]. All of the Turkish borate deposits are classified as volcanic related deposits. The borate deposits in Bigadiç, Sul- tançayırı (Balıkesir), Kestelek (Bursa), Emet (Kütahya) and Kırka (Eskişehir) were created in the playa-lake sediments during Miocene volcanism. The borate minerals are formed within the sequence consisting of conglomerate, sandstone, claystone, shale, marl, limestone and tuff intercalation [24].
Figures 1 and 2 show that Kırka B deposits area were composed of the lithology from old to young, respectively the Zahrendere Travertine Formation (composed of yellow-white limestone), the Lepçekdere Formation (claystone, limestone, borate in marl), the Salihiye Formation (opal in limestone), the Karaören Formation (clayey tuff, claystone, limestone and opal) and the Kırka Formation (tuff, claystone, limestone, borate and opal) [25].
The Kırka borate deposit (Miocene,
3. Materials and Methods
The natural plant species and representative soil samples were collected from the Boron mining areas especially in Kırka and Bigadiç, Emet borate deposits. The surface soil samples were collected in the depth range of 15 - 20 cm and stored in plastic bags. The plant species were identified from study [26], and then plant samples were separated into twigs, leaves, spikes and barks.
Digested of Plant Samples: the plant samples were washed with water and than dried in the oven-dried at 80˚C for 24 h. The 0.20 g of the dry grounded plant samples were placed into the porcelain crucible and fired up to 550˚C in the muffle furnace with a heating rate of 50˚C/h for 7 h. Then, the ashes were taken and evaporated with 2 ml 0.1 M HCl (1/3) at 45 - 50˚C by using a hot-plate. The residue was dissolved in 25 ml of deionized water and filtrated by using filter papers [27,28].
Extraction Boron from Soil Samples: The soil samples were oven-dried at 80˚C for 10 h and than were ground and then sieved under 80 mesh. The 5.00 g of dried soil samples and 20.00 ml of extraction solutions (0.01 M Mannitol + 0.01 M CaCl2) were shake for 16 h into shaker. The mixture was filtrated using filter paper and the boron determinate in soil extract solutions [27,29,30].
Boron Analysis: The B concentrations in the digested plant and soil extract solutions were determined according to the method suggested [27-30]. The 12.5 ml of the extract plant and soil extract solutions were transferred into a 25 ml flask, The 2.5 ml ammonium acetate tampon solution with the pH of 8 and the 2.5 ml of 0.3% 3,4- Dihydroxyazomethine-H solution in 1% ascorbic acid and the solution completed to 25 ml by deionised water. The solution are mixed and kept for 90 min. in dark and then the absorbance of the solution was measured at 420 nm by Genesys 20 model Spectrophotometer.
The 20 mg∙ml−1 stock standard boron solutions were prepared by dissolving sodium borate. Then, some of these stock solutions with different volume were taken and diluted with distillated water in order to prepare diluted solutions with certain concentrations (from 2 mg∙ml−1 to 8 mg∙ml−1). The absorbance of these freshly diluted solutions was measured and then the calibration graph was obtained.
The measurements of the water samples taken from waste water pool (in the surface water) in the Kırka and the Emet deposit areas were performed directly.
Other Element Analysis: Determination of Sr, Li, Cu, Zn, Mn, Co, and Ni in soil samples were analyzed by Flame Atomic Absorption Spectrophotometer [31].
4. Results and Discussions
The plant species such as Gypsophila perfoliata L., Pinus nigra Arn, Chrysopogon gryllus (L.) Trin., Juniperus oxicedrus L. subsp., Juniperus foetidissima Willd., Apera intermedia Hackel, Quercus trojana P.B. Webb, Puccinellia intermedia (Schur) Janchen, Alyssum sibiricum Willd, Genista aucheri Boiss and Euphorbia hirsuta L. are grown widely in Kırka and Emet, Bigadiç borate deposits. A few plant, soil and water samples were taken from Emet and Bigadiç (not water) in order to comparate with Kırka area. The maximum, minimum and the average B values of all plant and soil samples which were taken from these deposits are given in Table 1 for leaves, twigs, spikes and barks.
The B values of soil samples taken from the Kırka borate deposit varies between 1 ppm and 723 ppm, while the B values of the soil samples taken from Emet and Bigadiç varies between 1 ppm to 130 ppm. The B values of the natural soil samples are in the range of 0.10 - 80
Figure 1.Location map of study area.
Received February 22, 2013; revised March 25, 2013; accepted April 21, 2013
Figure 2.Geological map of the Kırka (Eskişehir) area (simplified from Gök et al., 1979).
Table 1. Boron concentrations in various plants and their organs and in soils from Kırka (Eskişehir) boron deposits.
ppm [5,21,32,33]. The B values of the three borate deposits are higher than the values of the natural soil samples. Thus, these values can be accepted as anomaly values.
On the other hand, the boron in the water samples of Kırka borate deposits area at 1, 2, 4, 14 and 50 stations are 272 ppm, 326 ppm, 510 ppm, 295 ppm, 195 ppm, re- spectively (Figures 1 and 2). The boron value of the water samples of Emet borate deposit at one station is 590 ppm. The value of B is 10 ppb in the natural water [5]. The B values of the water samples taken from borate deposit areas are higher than the values of the natural water samples, and these values can be accepted anomaly values.
Predominantly, the high B content of the soils is reflected in the parts of the plant species. The B values of the plant species are ranged from 31 ppm to 1197 ppm and the B values of the natural plant samples are ranged from 0.1 ppm to 1 ppm. However, these values are up to 230 ppm in the contaminated area [5,21,32,33]. The B values of the plant species of the borate deposits region are higher than the natural plant samples. Therefore, these values can be accepted anomaly values.
The B content of the soil and the plant samples given in Table 1 was plotted. It was observed that the correlation between B in the part of the plants (G. perfoliata ( r < 0.413 for twigs, r < 0.423 for leaves), C. gryllus (r < 0.707 for twigs, r < 0.666 for leaves and r < 0.878 for barks), J. oxicedrus (r < 0.380 for twigs, r < 0.468 for leaves), J. foetidissima (r < 0.997 for twigs), Q. trojana (r < 0.372 for twigs, r < 0.372 for leaves), A. sibiricum (r < 0.666 for twigs, r < 0.666 for leaves) and E. hirsute (r < 0.413 for twigs, r < 0.433 for leaves, for n > 3) and soil were not significant at 95% (P > 0.05) confidence level. Because the slope of the regression (r) line of the experimental is lowest than theoretical regression (r) line. Furtermore, J. foetidissima (for leaves), and A. intermedia (for twigs and leaves) are insufficient samples, for n < 3.
In contrast to that a statistically significant plant/soil relationship was observed for the B in the twigs of G. aucheri, in the twigs of P. intermedia, and in the leaves of P. nigra and presented in Figures 3-5, respectively. The slope of the regression (r) lines was 0.8581 (for 26 samples), 0.7274 (for 17 samples) and 0.6805 (for 16 samples), respectively. All of the relationships are highly significant (99% confidence level, P < 0.01).
The sensitivity of the P. nigra, G. aucheri and P. intermedia plant species is shown in Figure 6. It is clear in Figure 6 that P. nigra is the most sensitive and G. aucheri is more sensitive than P. intermedia. Therefore, it is better to prefer to start with the most sensitive one for biogeochemical prospecting in the future. Morever, bioconcentration factor (BF, B plant/Bsoil); P. nigra 16.0 > G. aucheri 6.3 > P. intermedia 0.9.
Figure 3.The relationship between the concentration of B in the soil and B in the Genista aucheri twigs.
Figure 4.The relationship between the concentration of B in the soil and B in the Puccinellia intermedia twigs.
Figure 5. The relationship between the concentration of B in the soil and B in the Pinus nigra leaves.
The inter-elemental relationship between the B concentration of the indicator plants and some other elements (B, Sr, Li, Cu, Zn, Mn, Co and Ni) of the soil was
Figure 6. The correlation between the B contents of the Puccinellia intermedia (twigs), Genista aucheri (twigs), Pinus nigra (leaves) and the soil.
shown in Table 2.
As it was seen in Table 2, there was relationships of B concentration in the twigs of G. aucheri, in the twigs of P. intermedia, in the leaves of P. nigra and the Sr, Li, Cu, Zn, Mn, Co and Ni elements in the soil are not significant (95% confidence level, P > 0.05). Therefore, B in the plants has been independent to Sr, Li, Cu, Zn, Mn, Co and Ni in the soil. In addition, it is obvious that the B concentration in the indicator plants depends on the B concentration in the soil.
5. Conclusions
In the present study, the elemental contents of the plants (G. perfoliata, P. nigra, C. gryllus, J. oxicedrus, J. foetidissima, A. intermedia, Q. trojana, P. intermedia, A. sibiricum, G. aucheri, E. hirsuta), soil, and water taken mainly from Kırka and also from Emet and Bigadiç borate deposit areas are chemically analyzed. The B concentrations in the samples were compared with the B concentrations of the natural plant, soil and water. It was investigated that the B concentrations of all the samples regardless whether it is plant or soil or water are anomaly. However, it was observed that there was a relation between the B concentration of only the twigs of G. aucheri, the twigs of P. intermedia and the leaves of P. nigra plants and the B concentration of the soil (Figures 7(a)-(c), respectively). Therefore, these plant species are determined as indicator plants. Besides, the B concentration of these indicator plants is independent to the concentration of the Sr, Li, Cu, Zn, Mn, Co, and Ni elements in the soil. This means that the indicator plant can take B from the soil regardless it has these elements or not.
It is concluded that the B content in the twigs of G. aucheri, in the twigs of P. intermedia and in the leaves of P. nigra yielded good indications for biogeochemical prospecting and could be successfully used as environ-
Table 2. Results of correlation analysis for inter-elemental relationships between soil and plants.
S: highly significant (p < 0.01). NS: not significant (P > 0.05).
(a)
(b)
(c)
Figure 7. The photographs of the plant species; (a) Genista aucheri, (b) Puccinellia intermedia, and (c) Pinus nigra.
mental monitor for environmental pollution studies.
Acknowledgements
The TÜBİTAK is acknowledged for financial support (project number is 104Y009). The authors would like to thank Prof. Dr. B. Yıldız (Balıkesir University, Turkey) and Assist. Prof. Dr. R. Binzet (Adıyaman University, Turkey) for determination of the plant sample names and Dr. S. Erat (ETH-Zurich, Switzerland) for helpful technical discussions.
REFERENCES
[1] C. Helvaci and F. Orti, “Zoning in the Kırka Borate Deposit, Western Turkey: Primary Evaporitic Fractionation or Diagenetic Modifications?” The Canadian Minerologist, Vol. 42, No. 4, 2004, pp. 1179-1204. http://dx.doi.org/10.2113/gscanmin.42.4.1179
[2] N. Arslan, A. Çiçek and C. Akkan, “Accumulation of Heavy Metals by Earthworms in Boron-Contaminated Area (Kırka-Eskişehir),” Zoology in the Middle East, Vol. 51, Suppl. 2, 2010, pp. 111-116. http://dx.doi.org/10.1080/09397140.2010.10638463
[3] M. Köksoy, “Uygulamalı Jeokimya,” Hacettepe Univer- sity Publication, Ankara, 1991, p. 366 [in Turkish].
[4] R. R. Brooks, C. E. Dunn and G. E. M. Hall, “Biological System in Mineral Exploration and Processing,” Elles Horwood Limitid, Bel Air, 1995, p. 538.
[5] A. W. Rose, H. E. Hawkes and J. S. Webb, “Geochemi- stry in mineral Exploration,” 2nd Edition, Academic Press, New York, 1979, p. 657.
[6] A. L. Kovalevskii, “Biogeochemical Prospecting for Ore Deposits in the U.S.S.R, Journal of Geochemical,” Ex- ploration, Vol. 21, No. 1-3, 1984, pp. 63-72.
[7] A. Sağiroğlu and Z. Özdemir, “Biogeochemical Prospec- tion,” Geological Engineering, Vol. 51, 1997, pp. 1-17.
[8] P. A. Floyd, C. Helvaci and S. K. Mittwede, “Geochemi- cal Discrimination of Volkanic Rocks Associated with Borate Deposits: An Exploration Tool?” Journal of Geo- chemical Exploration, Vol. 260, No. 3, 1998, pp. 185- 205.
[9] Z. Özdemir, “Biogeochemical Studies at the Musalı and Silifke-Anamur Area in Mersin, Turkey,” Geochemistry International, Vol. 241, No. 9, 2003, pp. 1-6.
[10] Z. Özdemir, “Pinus brutia as a Biogeochemical Medium to Detect İron and Zinc in Soil Analysis, Cromite Depo- sits of the Area Mersin, Turkey,” Chemie der Erde, Vol. 265, No. 1, 2005, pp. 79-88.
[11] M. Babaoğlu, S. Gezgin, B. Sade and H. Dural, “Gypso- phila sphaerocephala Fezl ex Tchihat.: A. Boron Hyper- accumulator Plant Species That May Phytoremediate Soils with Toxic B Levels, TUBITAK,” Turkish Journal of Botany, Vol. 28, No. 3, 2004, pp. 273-278.
[12] W. H. Schlesınger, “Biogeochemistry,” In: H. D. Holland and K. K. Turekıan, Eds., Treatise on Geochemistry, 8th Edition, Elsevier, London, 2006, p. 702,
[13] H. Turan, Z. Özdemir and S. Zorlu, “İnvestigation of Biogeochemical Anomalies for Cu, Zn, Fe, Mn, and Ni in Çiftehan (Ulukışla-Niğde) Area,” Istanbul Earth Science Review, Vol. 219, No. 2, 2006, 131-140 [in Turkish with English Abstract].
[14] M. J. Batista, M. M. Abreu and P. M. Serrano, “Biogeo- chemistry in Neves Corvo Mining Region, Iberian Pyrite Belt, Portugal,” Journal of Geochemical Exploration, Vol. 292, No. 2-3, 2007, pp. 159-176.
[15] C. E. Dunn, “Biogeochemistry in Mineral Exploration,” Handbook of Exploration and Environmental Geochemi- stry, Vol. 9, Elsevier, London, 2007, p. 462.
[16] E. Demir and Z. Özdemir, “Kazanlı (Mersin) Bölgesinde Cr, Fe, Ni ve Co Nun Çevreye Etkisi ve bir Biyojeo- kimyasal Çalışma,” Mersin Symposium, Mersin, 19-22 November 2008, pp. 146-159 [in Turkish],
[17] T. Unver, O. Bozkurt and M. S. Akkaya, “Identification of Differentially Expressed Transcripts from Leaves of the Boron Tolernt Plant Gypsophila perfoliata L.,” Plant Cell Reports, Vol. 227, No. 8, 2008, pp. 1411-1422.
[18] Z. Özdemir, “Bitkilerle Maden Bulunabilir Mi? Biyojeo- kimyasal (Bitki Jeokimyası) Prospeksiyon Nedir?” Jour- nal of Mining and Earth Science, Vol. 21, No. 3, 2009, pp. 14-19 [in Turkish].
[19] Z. Özdemir and E. Demir, “Nickel Accumlating Species of Alyssum murale Waldst. & Kit from Fındıkpınarı-Er- demli/Mersin Area,” Geology Engineering, Vol. 234, No. 1, 2010, pp. 57-70 [in Turkish with English abstract].
[20] A. R. Stiles, D. Bautista, E. Atalay, M. Babaoğlu and N. Terry, “Mechanisms of Boron Tolerance and Accumula- tion in Plants: A Physiological Comparison of the Ex- tremely Boron-Tolerant Plant Species, Puccinellia distans, with the moderately Boron-Tolerant Gysophila arrostil,” Environmental Science & Technology, Vol. 244, No. 18, 2010, pp. 7089-7095. http://dx.doi.org/10.1021/es1016334
[21] W. Bergman, “Nutritional Disorders of Plants, Develop- ment, Visual and Analytical Diagnosis,” Gustav Fischer Verlag, Jena, 1992, p. 741.
[22] R. O. Nable, G. S. Banuelos and J. G. Paull, “Boron Toxi- city,” Plant and Soil, Vol. 2193, No. 1-2, 1992, pp. 181- 198. http://dx.doi.org/10.1023/A:1004272227886
[23] Y. Savaşçin and T. Oyman, “Tectono-Magmatic Evolu- tion of Alkaline Volcanis at the Kırka-Afyon-Isparta Structural Trend, SW Turkey,” Turkish Journal of Earth Sciences, Vol. 27, 1997, pp. 201-214 [in Turkish].
[24] C. Helvacı, “The Geological Situation and Economical Importance of Turkey Borate Deposits and Borate Policy. 5,” Symposium of Industrial Minerals, İzmir, 2004, pp. 11-27 [in Turkish with English Abstract].
[25] S. Gök, A. Çakir and A. Dündar, “Survey of Kırka Towns and Surrounding Area Borate Deposits and other Indus- trial Minerals,” Mineral Research and Exploration Insti- tute of Turkey (MTA) Report No: 6768 [Unpublished, in Turkish with English Abstract], 1979.
[26] P. H. Davis, “Flora of Turkey and the East Aegean Islands,” Vol. 1-9, Universty Press, Edinburgh, pp. 1965- 1985.
[27] A. Alkan, “Resistance of Different Cereal Species and Wheat and Barley Cultivars to Boron Toxicity and Fac- tors Affecting Expression of High Boron Resistance,” PhD Thesis, Çukurova University, Adana, [Unpublished, in Turkish with English Abstract], 1998.
[28] L. Zaijun, C. Zhengwei and T. Jian, “The Determination of Boron in Food and Seed by Spectrophotometry Using a New Reagent 3,4-Dihydroxyazomethine-H,” Food Che- mistry, Vol. 294, No. 2, 2006, pp. 310-314. http://dx.doi.org/10.1016/j.foodchem.2005.01.019
[29] L. R. Spouncer, R. O. Nable and B. Cartwright, “A Pro- cedure for the Determination of Soluble Boron in Soils Ranging Widely in Boron Concentrations, Sodicity and pH,” Communications in Soil Science and Plant Analysis, Vol. 223, No. 5-6, 1992, pp. 441-453
[30] F. T. Bingham, “Boron,” In: A. L. Page, R. H. Miller and D. R. Keeney, Eds., Methods of Soil Analysis, Part 2, Madison, 1982, pp. 431-447.
[31] R. R. Brooks, A. J. M. Baker and F. Malaisse, “Copper Flowers,” National Geographic Research and Explora- tion, Vol. 8, 1992, pp. 338-351.
[32] H. Özbek, Z. Kaya, M. Gök and H. Kaptan, “Toprak Bi- limi, Çukurova,” University Publication 73, 1993, p. 816 [in Turkish],
[33] B. Kacar and A. V. Katkat, “Bitki Besleme,” 4th Edition, Nobel Publication, No. 849, Ankara, 2009, p. 657 [in Tur- kish].