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Refika Kurbanlı 1 , Kemal Gür 2 , Erol Pehlivan 1 , Damet Bayramov 1 Sultan Kurbanlı 3 , Mehmet Zengin 4 , Senar Ozcan 2 , Zehra Yılmaz 2 1 Selcuk University, Eng. and Archi. Faculty, Dept. of Chem. Engineering 2 Selcuk University, Eng. and Archi. Faculty, Dept. of Env. Engineering 3 Selcuk University, Eng. and Archi. Faculty, Dept. of Chemistry 4 Selcuk University, Agricultural Faculty, Dept. of Soil Science Abstract The oxydized lignite called "leonardite" is a source of readily available humic material. In many respects, this material is identical with soil humus having essentially the same source. The humic acids from both soil and oxydized coal (lignite) are identical in chemical and physical properties. Thus, in many respects, the oxydized lignite can be regarded as natural fertilizers and soil conditioners. Like humus, derived from decaying debris, the substances of humic acid can remediate soil structure by physically interacting with clay and sand particles. The purpose of this work, was to determine the humic acids contents of the low grade lignite samples collected from the sites of Ilgin, Ermenek and Beysehir around Konya. In addition, it was aimed to find out effects of the humic acid substances and the lignite samples on the improvement of soil aggregation and structure thus remediation of a coarse sandy loam textured soil sample collected from the coal mine sites around Ilgin town belonging to Konya Province. Introduction It is a general concept that the lignite has been known as "fuel" and source of energy just like the other kinds of coal mine. The lignite has been known to contain hydrogen (H), oxygen (O), nitrogen (N) and sulphur (S) and also inorganic matters such as potassium (K) and phosphorus (P). However the vital importance of the oxydized lignite, called leonardite, is that it is a source of readily available humic material. In various respect, the humic material of the lignite is identical with soil humus having essentially the same sources. The soil humus and lignite humus both represent the residualy organic material from the past plant generations (Reeve, 1965; Schnitzer, 1967). The humic acids from the oxidized lignite are known to be identical with in chemical and physical properties. For example, they are polycondensed aromatic substances with a high polymeric structure of molecules. The humic substances are generally characterized as weak acids because they have carboxyl (COOH) and hydroxyl (OH) groups (Mukherjee, 1961; Nikonov, 1964; Chakrabatty, 1966). This work was undertaken to extract and to determine the humic acid contents of the lignite samples collected from the coal mine sites at the vicinities of Beysehir, Ermenek and Ilgin towns of Konya Province, Turkiye. In addition, it was aimed to elucidate the influances of the humic acid substances and lignite samples amanded at two different on the soil aggregation and the modules if rupture values of a course sandy loam textured soil. Materials and Methods Materials The experimental lignite samples as mentioned previously, were taken from the coal mine sites around Beysehir, Ermenek and Ilgin towns belonging the Konya Province coal mine sites, from which the experimental lignite samples were collected, have been known to possess large deposits of low grade coal such as lignite to Konya Province. For example, the natural lignite deposits have been supposed to be around 200 million tons. Beysehir, Ermenek and Ilgin towns belonging to the Konya Province are situated at 31043'-27041', 32053'-36039' and 31055'-38017' Eastern latitudes and Northern longitudes respectively. The soil sample : For the study, the soil sample was collected from a surface mined coal site in the vicinity of Ilgin town belonging to the Konya Province in the Central Anatolia of Turkiye. For experiments, freshly collected soil samples were air-dried, sieved to pass 4 mm mesh immediately after they were brought to the laboratory and then they were steam sterilized at 100 0C for one hour. The soil of the sampling site was a coarse-sandy loam texture with the following properties; pH 7.10 (1:2.5 soil-water) organic matter 0.28 %, CEC 23.4 me/100 g, exchangeable sodium 0.24 me/100 g and the available phosphorus 5.85 ppm respectively. Water stable aggregate percantages and modulus of rupture values were determined by modifying the methods of Kemper (1965) and Reeve (1965). Methods Laboratory procedure; Collection of the lignite samples : The sample were take from the sub, middle and surface layers of the profiles of the coal mine sites in September, 2001. The samples were crushed and then screened to 80, 100 and 200 mesh sizes immediately after they were brought to the laboratory. Determinations of ash and higroscopic humidity contents : The higroscopic humidity (%) and ash (%) percentages of the air-dried lignite samples were determined prior to the fractionation and extraction of the humic acid substances (Kemper, 1965; Reeve, 1965). Determination of humic acid contents : Humic acid contents of the lignite samples were determined by the Method of Kreulen as shown in Figure 1. It can be summarized as follows: One gram of the lignite samples was weighed and then put into a 300 ml beaker. Twenty ml of 5 % NaOH and 10 ml distilled water were added to the beaker. The mixture was heated on a bright flame and boiled for three minutes. Immediately after the procedure of boiling was completed, the flask containing the boiling mixture was cooled under tap water and then the solution in the flask was centrifuged. The procedure of centrifugation was repeated several times by adding distilled water until the supertinant above the precipitation became clear in colour. The remainders of the solution were collected into another beaker and 50 ml of distilled water was added to the rest of the solution and the pH value was adjusted top H 3.0 by adding diluted HCl acid. All humic acid materials that were precipitated at the bottom of the flask was filtered, dried and weighed to determine the humic acid contents of the lignite samples. Addition of humic acid and lignite samples to the soil : The soil samples were amended with humic acid substances (at 0.25 %; 5 % levels) and the lignite samples of Beysehir, Ermenek, Ilgin (at 2 % ; 5 % levels respectively), to remediate the experimental soil. Results and Discussion The percentages of ash, relative humidy and humic acid contents of the tree layers of lignite profile belonging to the coal mine site of Ilgin were summarized in the Table 3. As it is shown in the table, ash contents varified between 7.48% and 11.0% , whereas higroscopic humidity values ranged from 18.06% to 19.38% while humic acid contents of the three layers of the Ilgin lignite profile fluctuate between 24.91% (for sublayer) and 32.40% (for toplayer). According to these figures, it was found out that the increases in the humic acid contents were negatively but significantly correlated to the increasings in the depth of the Ilgin lignite profile (Table 2,3).  On the other hand, the highest humic acid content (avarage :42%) was found in the Beysehir lignite sample and it was followed by that of the Ilgin (avarage : 38%) and the Ermenek (avarage : 30 %) lignite samples respectively as illustrated in the Table 3 and in the Figure 1, and also as stated by Sensogut (1999). On the other hand, it was elucidates that when the lignite was reacted with the ammonia, some amount of nitrogen diffused into the coal, and thus this reaction and its rate were directly related to the contents and the formation rates of the humic substance as given in the Figure 1.  As indicated previously, chemical structures of the humic acid substances were determined by the methods of chemical analysis and IR spectroscopy. (Grosskanisky, 1932; Youngs, 1963; Aitke, 1964). At the end of these determinations, it was found that, there were one or two peaks at 1600-1700 cm-1 belonging to the aromatic groups . The carboxylic groups appeared at 1600-1700 cm-1 while the "OH" bands were observed between 3400-3600 cm-1 in an infrared spectrum. On the other hand, strong peaks were recorded in both districts of an infrared spectrum of the three different lignite samples collected from the coal mine sites at the vicinities of Beysehir , Ermenek and Ilgin towns. These findings showed that all of the three lignite samples, taken from Beysehir, Ermenek and Ilgin towns, were rich enough in humic acid substances. Thus it was concluded the lignite samples of Beysehir, Ermenek and Ilgin towns could be suggested and offered to be an important and sufficent resources of raw material in order to obtain organo-mineral fertilizer in a sufficent quality as much as that needed since it has been already indicated in the literature that the vicinities of Beysehir, Ermenek and Ilgin have been known to have large deposits of low grade coals from which the experimental lignite samples were taken (Sensogut, 1999) as it is shown in the Table 1, 2, 3.  On the other hand, the addition of the lignite and humic acid materials to the experimental soil at the increasing levels induced and significantly increased the aggregate stability while significantly decreased the modulus of rupture values of the experimental soil (Table 4). Thus, it was concluded that addition of the humic acid substances and lignite materials with increasing level to the experimental soil could be used to reduce the crust formation and soil surface erosion and thus could be used to remediate the physical properties of the soil such as soil aggregation and other realted soil propeties, as a soil conditioner.  Acknowledgement We kindly would like to thank The Turkish Prime Ministry State Planning Organization Research Fund for its meaningful and important financial support for this work (Project number: 2001 K 121 130). References . Aitke, J. B., 1964. The Characteristics and Effects of Humic Acids Derived from Leonerdite. South Dakota Agricultural Experiment Station, Tech. Bull. 1015, pp.3-28. . Chakrabatty, A. K., Mukherjee, P.N. & Lahiri, A., 1966. Effect of Coal Fertilizers on Paddy and Wheat Yield, Indian J. Agon, Vol 11, No.2 pp.193. . Grosskanisky, O. & Klempt, W., 1932. Method of Producing Humous Fertilizers, German Patent 559254, Sept. 17. . Kemper, W. D., 1965. Aggregate Stability. In C. A. Black (ed.) Methods of Soil Analysis, Part. I. ASA, Madison, wis., USA., 511-519. . Mukherjee, P. N., Banarjee, A. K. & Lahiri A., 1961. Fertilizer from Coal, Fuel Research Institut, R. R. I. News, Vol 11, pp.16-29. . Mukerjee, P. N., Bhaumik, J. N. & Lahiri, A., 1965. Production of Fertilizers from Coal, Indian J. Tech., Vol 3, No:3, pp.90-92. . Pagel, H., 1960. The Effect of Humic Acid Matter on Plant Growth I; Effect on Germanination of Root Growth; Effect on Yield of Nutrient Uptake II, Albrechete Thaer Arch., Vol 4, pp.450-468, pp.493-506. . Reeve, R. C., 1965. Modulus of Rubture. In C. A. Black (ed.) Methods of Soil Analysis. Part. I. ASA Madison, Wis., USA., 466-471. . Gur, K., 1981. A Research on the activities and distributions of microfungal flora in the soils of Mus Province and their effects upon the remediation of a sandy soil by using some organic plant residues (Assoc. Prof. Dr. Thesis, in Turkish with English summary), Ataturk University Agricultural Faculty Department of Soil Science, Erzurum, Turkiye. . Sensogut, C., 1999. Spontaneous Combustion Liability of Turkish Coals. Ilgin Lignite as an Example. The Proceedings of Mining, Vol 38, No:1, pp.45-52. . Youngs, R. M. & Frost, C. M., 1963. Humic Acid from Leonardite, a Soil Conditioner and Organic Fertilizer, Am. Chem. Soc. Div. Fuel Chem. Preprints, Vol 7, No:1, pp. 12-17; North Dakota Acad. Sci., Vol 17, pp.76-82 |