Environmental Engineering and Management Journal

February 2012, Vol.11, No. 2, 297-305

http://omicron.ch.tuiasi.ro/EEMJ/

Gheorghe Asachi Technical University of Iasi, Romania

IMPROVING SOIL QUALITY BY ADDING MODIFIED ASH

Ramona Carla Ciocinta1, Maria Harja2, Daniel Bucur1, Lacramioara Rusu3, Marinela Barbuta4, Corneliu Munteanu5
1

"Ion Ionescu de la Brad" University of Agricultural Sciences and Veterinary Medicine of Iasi, Faculty of Agriculture, 3, Mihail Sadoveanu Alley, 700490 Iasi, Romania 2 Gheorghe Asachi Technical University of Iasi, Faculty of Chemical Engineering and Environmental Protection, 73 Prof .dr. doc. D. Mangeron Blvd., 700050 Iasi Romania 3 Vasile Alecsandri University of Bacau, Faculty of Engineering, 157 Mreti Blvd., 600115 Bacau, Romania 4 Gheorghe AsachiTechnical University of Iasi, Faculty of Civil Engineering and Building Services, 43 Prof. dr. doc. D. Mangeron Blvd, 700050, Iasi Romania 5 Gheorghe Asachi Technical University of Iasi, Faculty of Mechanical Engineering, 67 Prof. dr. doc. D. Mangeron Blvd, 700050 Iasi Romania

Abstract
Fly ash and fly ash based zeolites are inorganics used for improving soil quality. In the current paper, the hydrothermal modification of fly ash was studied. Three methods have been employed for this purpose. The first method involved the use of an autoclave, where synthesis has been performed at a temperature of 120 0C and a treatment time of 4 to 8 hours. Within the second method, the modification of the ash at a temperature of 600 0C by fusion was carried-out. In this method, a mixture of ash and KOH was subjected to treatment for a period of 1-2 hours. The last method, more feasible from ecological and economical point of view, consisted in using a microwave oven for modifying the fly ash. The synthesized materials were characterised with respect to microstructure (electronic microscopy SEM), chemical and mineralogical composition (EDAX, X rays diffraction, FT-IR). EDAX analysis evidenced the absence of several heavy metals that have no role in the life cycle of the living organisms such as Hg, Cd and Pb, in both ash and zeolite. By analysing the obtained data, one may observe the destruction of the ash network and crystallization of the new phase, especially in the case of treatment by diffusion at ratios of 1/3. The XRD analysis confirms the presence of zeolite (K-chabazite). Good results were also obtained in the case of using microwaves treatment for zeolite synthesis; also the time of treatment significantly decreased in this case. Key words: characterization, fly ash, synthesis, soil, zeolites
Received: September, 2011; Revised final: February, 2012; Accepted: February, 2012

1. Introduction Lately, the surface of land used for agricultural purposes decreased as a result of fertility loss, compactness reduction, acidification and chemical pollution (Ailinci et al., 2011; Bucur et al., 2007, 2011). For achieving high agricultural yields, several measures for improving the physical, chemical and biological characteristics of soils should be taken. In Iasi County, there are 376,513 hectares (ha) of

agricultural land from which 55.2 hundred ha are affected by salinity, 62.9 hundred ha exhibit moisture excess and 15.8 hundred ha are affected by flood (Ailinci, 2007). The soil acidity inhibits the development of the nitrifying bacteria (with role in fixing the nitrogen) as a result of the fact that the soil nitrogen content is low. The improvement of soil quality is an important target; hence the soil scientist look for finding ways to improve the soil structure, to restore

Author to whom all correspondence should be addressed: e-mail: maria_harja06@yahoo.com

Ciocinta et al./Environmental Engineering and Management Journal 11 (2012), 2, 297-305

the organic material content, to enhance the soil microorganisms activity, to elucidate the mechanism of applied chemicals transformation, to establish the critical limits of pollution, to reduce the content of heavy metals ions and to diminish the risks for human and animal health (Diaz-Zorita, 2000). The amendment refers to any substance or additive that can improve the quality and the conditions (physical, chemical or biological) of the soil (Hickman and Whitney, 2006; Li et al., 2000; Reynolds et al., 2003; Trotti, 2006). The selection of the proper amendment depends on the properties that should be improved, degree of soil deterioration, soil composition, climate etc. The inorganic amendments are represented by natural or artificial minerals, such as: gypsum, lime, modified rocks, including sand, tile, perlite, ashes, zeolite, pyrite, dolomite and calcinated clay (Hill, 2005; Li et al., 2000; Reynolds et al., 2003). Among the inorganic materials that can be used for soil quality improvement, the fly ash and the fly ash based zeolites were chosen for the current study. Fly ash constitutes an important source of industrial wastes considering the very high volume that are produced. 600 million tones of ash result yearly worldwide, from which 75-80% represents the fly ash, fact that ranks it 5 as raw material source. (Ahmaruzzaman, 2010). Around 40 billion tons of ashes result yearly in Europe (Ecoba, 2005; Harja et al., 2012). The capitalization of ash depends on the chemical composition and its physical and technological properties. From chemical point of view, the fly ash can contain 60-65% silica, 25-30 % alumina, 6-15% magnetite, macro-nutrients such as P, K, Ca, Mg and micronutrients such as Zn, Fe, Cu, Mn, B, and Mo that are essential for plants growing (Brezeanu et al., 1990; Harja et al., 2009a, 2009b). Properties such as: specific gravity, permeability, bulk density, granulometric distribution, specific surface and porosity impose the usage of this type of waste (Harja et al., 2011). The ashes are used for different applications including geopolymers synthesis, synthesis of zeolites used for decontamination of waters and soils treatment; synthesis of adsorbents. They can be also utilized as filling material for roads, dams, excavations, mines; as stabilizer for some soils; as degreaser in tile etc. (Ahmaruzzaman, 2010; Barbuta et al., 2009, 2010a, 2010b; Harja et al., 2009a, 2009b, 2009c; Wang and Wu, 2006). The fly ash can be used in agriculture because it contains almost all macro and micro elements, excepting the organic carbon and nitrogen (Castaeda Muoz, 2006). At the same time, the fly ash can contain moderate contents of heavy metal ions, which affect groundwater and can be retained by plants (Kumar et al., 2001). The fly ash is an alternative for soils conditioning (Castaeda Muoz, 2006; Cline et al., 2000). The plants from soils treated with fly ash retained bigger quantity of Zn, Cu, Fe, Mn and Cd.

Also other modifications have been observed that refer to bulk density, hydraulic conductivity, and capacity of water retention. These modifications of soil characteristics were assigned to modification of distribution of micro and macro pore sizes (Kalra et al., 2000). The pH of treated soils has decreased and electric conductivity has increased, depending on the fly ash amount. Zeolites are the crystallized shape of alkaline aluminosilicate (Zeolite, 2006; Virta, 2002). They exhibit a stable tri-dimensional structure that contains one Al and 5 silica tetrahedrons, symmetrically arranged (Fansuri et al., 2008; Mumpton, 1999). As a result of the empty spaces within the structure, they have the ability to retain water. The negative charge inside the hole exchanges with a cation from the system. The zeolites are considered as intelligent fertilizer due to their capacity to exchange cations that allow to nutrients such as nitrogen, calcium, iron, magnesium, potassium and water to be available for plant nutrition and to be eliminated with a low rate (Zeolite, 2006). Zeolites improve the performances of fertilizers by increasing the resistance to washing, immobilization and gases emission (Ippolito et al., 2011). Zeolites are inert from chemical point of view, are not toxic for plants, animals, human or environment and adjust the balance of soil by immobilization of contaminants that are toxic for plants (Milosevic and Milosevic, 2009). In consequence, the use of zeolites: lead to increase of the ion exchange ability of soil that allows retention followed by controlled release of nutrients; reduce the consumption of fertilizers and water; cover the needed amount of potassium; increase the availability of phosphorus; adsorb toxic contaminants; act like buffers; decrease the effect of alkalinity; improve aeration of the soil; enhance the activity of microorganisms; influence the equilibrium of the alkaline metals; retain the humidity; is a cheap method for environmental applications. A possibility to capitalize the ash is to convert it into zeolites (Harja et al., 2010). The experimental researches have shown that the ash can react with KOH (Yoo and Jo, 2003). Three methods for conversion of ash into zeolite are reported in the literature. The first method, a conventional one, consists in direct hydrothermal conversion of a mixture of ash and alkaline solution. Only 50% of ashes can be converted in zeolite (Fansuri et al., 2008). The second method consists in mixing the ash with KOH or K2CO3 followed by fusion at high temperature (usually 550C), when ash conversion into a soluble silicate and potassium aluminates occurs, followed by dissolution in alkaline solution.

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Table 1. Experimental conditions Sample Z1 Z2 Z3 Z4 Z5 Z6 Z7 Z8 Z9 Z10 Z11 Z12 Z13 Z14 Materials 4g fly ash+ 8mL sol KOH 4g fly ash + 8mL sol KOH 4g fly ash + 12 mL KOH 4g fly ash + 12 mL KOH 10g fly ash + 20 mL KOH 10g fly ash +20 mL KOH 10g fly ash +10 mL KOH 10g fly ash + 20 mL KOH 10g fly ash + 30 mL KOH 10g fly ash + 40 mL KOH 10g fly ash + 10 g KOH 10g fly ash + 10 g KOH 5g fly ash + 10 g KOH 5g fly ash + 10 g KOH s/L ratios 1/2 1/2 1/3 1/3 1/2 1/2 1/1 1/2 1/3 1/4 1/2 1/2 1/3 1/3 Temperature 120C 120C 120C 120C 80C (stirred) 80C (stirred) 80C microwave 80C microwave 80C microwave 80C microwave 600C 600C 600C 600C Curing time 4 hour 8 hour 4 hour 8 hour 4 hour 8 hour 30 min 30 min 30 min 30 min 1 hour 2 hour 1 hour 2 hour

This method leads to an advanced conversion, the type of zeolite depending on the treatment conditions. Hollman et al. (1999) proposed a third method, that consists, in extraction of silicon from the ash as a first phase, followed by the addition of an aluminates solution, in fixed proportion, resulting in a very pure zeolite. Some studies recommend conversion of ash in microwaves oven, case when the conversion time is reduced to 30 minutes. For using this method, extensive researches are needed because not any type of ash can be modified. Although the direct method is considered unsatisfactory with respect to the purity of the resulted zeolite, it is adequate for the synthesis of agricultural zeolites due to its simplicity (synthesis in only one stage). The agricultural zeolites exhibit a role in controlling the release of the nutrients and may be used as amendments for soil. The zeolites obtained by alkaline activation are alumina-silicates type and include three classes of inorganic polymers, as function of the silica/alumina ratio: (SiOAlO) polysialates, SiO2/Al2O3=2; ( SiOAlOSiO),poly(sialate-siloxo) - SiO2/Al2O3 =4;(SiOAlOSiOSiO) poly(sialate-disiloxo) SiO2/Al2O3= 6 (Ramesh et al., 2010). The hydroxide concentration, activation temperature, solid/liquid ratio and pH significantly influence the formation and properties of zeolites. The variation limits of these parameters are sufficiently large: SiO2/Al2O3 ratio between 2 and 6; KOH concentration between 1 M and 5 M, activation temperature of 80-150C, activation time of 4 h to 48 h, solid/liquid ratio between 1/1 and 1/4 (Criado et al., 2007; Mishra et al., 2008; Ramesh et al., 2010). The objective of this study was to investigate the conversion of fly ash into zeolites. The specific aim was to analyze the zeolitic products. 2. Experimental The chemical and mineralogical characterization was performed as follows: Microanalysis of samples was determined by SEM/EDX with a QUANTA 3D - AL99/D8229;

Difractometer XPERT PRO MRD; FT-IR analysis with DIGILAB FTS 2000. Three methods were used for the hydrothermal modification of fly ash in the present paper: - in the first method, the synthesis was carried-out in an autoclave at a temperature of 120C, the treatment times being ranged between 4 h - 8 h. KOH 2 M solutions have been used for ensuring the K necessary for plants. - in the second method the modification of the ash at a temperature of 600C was achieved by fusion. The ash KOH mixture was thermally treated at 600C during 1-2 hours. - the third method (less reported in the literature) exhibits more ecological and economic benefits and consists in modifying the ash in a microwaves oven. In this case, the system was also s-L type, following the same parameters as in first method, but the treatment time decreases to 30 min. After synthesis, all samples were filtered, washed to remove the alkalinity (pH 6-7) and dried in the oven at 90C up to a constant mass. The working conditions are presented in Table 1. The zeolites were characterized with respect to: microstructure (electronic microscopy SEM), chemical and mineralogical composition (EDAX, X rays diffraction, FT-IR). 3. Results and discussion The synthesized zeolites were chemically analyzed and composition of Z4 zeolite is presented in Fig. 1 and Table 2. The analysis demonstrated that in the above mentioned zeolite, the main elements were the following: Si, O, Al, Ca, Fe, Na, K, N and small quantities of Ti and Mg. The quantity of carbon in ash depends on the combustion conditions, on the technology applied and the coal used. Potassium ions appear in the zeolite structure, as a result of the fact that the synthesis was performed with potassium hydroxide. The calcium content decreases compared to the raw material, evidencing the fact that potassium replaces calcium in the zeolite structure.

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Fig. 1. Chemical composition of zeolite

The elements are found as oxide form or combinations, fact confirmed by FTIR and XRD analyses. Also, all synthesized samples were found to contain the same elements, but in different amounts. EDAX analysis for ash and zeolite proved the absence of some heavy metal ions that have no role in the life cycle of living organisms as Hg, Cd, Pb.
Table 2. Composition of zeolite Z4, EDX Element C N O K Mg Al Si Na Ca Ti Fe Wt, % 14.69 6.92 24.24 04.75 0.76 8.66 32.58 01.40 2.13 0.74 3.14 At, % 30.15 9.08 31.31 3.80 0.58 9.31 12.82 0.66 0.98 0.28 1.03

The SEM images for the synthesized materials, at 50 m, respectively 20 m, are presented in Fig. 2 and Fig. 3. The results of FTIR analysis are presented in Fig. 4 and Fig 5. In the spectrum depicted in Fig. 4, the most relevant band is observed in the 950-1100 cm-1 range, corresponding to intense Si (Al)-O band. In accordance with the obtained data, the characteristics of IR vibration bands of the zeolite materials result as follows: 37003600 (s) cm-1stretching vibration (OH); 17001600 cm-1-bending vibration (HOH); 1200950 (s) cm-1-asymmetric stretching (SiOSi and AlOSi), 1100 cm-1 (sh)asymmetric stretching (SiOSi), 850 cm-1 (sh)-SiO

stretching, OH bending (SiOH); 795 cm-1 (m)symmetric stretching (SiOSi); 688 cm-1 (sh)symmetric stretching (SiOSi and AlOSi); 520 532 cm-1 (m)-double ring vibration and 424 cm-1 (s)bending (SiOSi and OSiO), where s-strong; wweak; m-medium and sh-shoulder (Harja et al. 2009). Analyzing the spectra for samples synthesized by direct method, it can be observed that few differences occur. The main band is moving from 1084 to 1078, which means that, for the same conditions of temperature and s/l ratio, the increase of treatment time from 4 hours to 8 hours does not bring major modifications in the structure of the synthesized material. Maintaining the treatment time of 8 hours, but increasing the solid/liquid ratio does not result in the appearance of new bands. Significant differences compared to the initial material were observed in the case of activation at high temperature (600C). From Fig. 5, one may observe that the most relevant band is improper in the direction of wavenumber, decreasing from 1075-1080 cm-1 to 995-1001 cm-1. In Fig. 6 are presented the XRD spectra for four synthesized zeolites. In this study, K-chabazite K2Al2SiO6 H2O and zeolite F linde KAlSiO41.5H2O were prepared from fly ash by a hydrothermal treatment with KOH. By varying the concentration of the KOH, the control over the type of zeolite formed was achieved. From Fig. 6 it can be observed that K chabazite was mainly obtained, alongside traces of F linde, in all cases. The conversion was lower or higher depending on the synthesis conditions.

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Fly ash unmodified

Zeolite Z2

Zeolite Z10 Fig. 2. Electronic microscopy for zeolite, at 50 m

Zeolite Z12

Zeolite Z1

Zeolite Z4

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Zeolite Z6

Zeolite Z9

Zeolite Z13 Zeolite Z14 Fig. 3. Electronic microscopy for zeolite, 20 m

Fig. 4. The FTIR spectra of zeolites

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Fig. 5. The FTIR spectra of zeolites

Z4

Z9

Z6 Fig. 6. The XRD spectra of zeolites

Z14

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4. Conclusions Based on the achieved experimental results, one may conclude that the type of fly ash studied in this work can be used to synthesize zeolitic materials that can be further used for improving the quality of soil. EDAX for ash and zeolite proved the absence of some heavy metal ions that are not essential for the life cycle of the living organisms: Hg, Cd, Pb. The XRD analysis confirms the presence of zeolite in synthesized materials. Depending of the working conditions and the used type of fly ash, K-chabazite and less quantity of F linde zeolites have been prepared by hydrothermal treatment of the fly ash with KOH. Compared with SEM for fly ash, in the case of zeolite one may see that the particles are modified. The conversion degrees are dependent on the contents of non-reactive phases and resistant aluminum silicate phases, such as mullite and quartz, as well as the grain size distribution. In the case of synthesized zeolites by classical method, the modifications are smaller than in the case of synthesis by diffusion, but comparable with the case of zeolite synthesized by thermal treatment with microwaves. Good results concerning the zeolite process can be obtained in the case of microwaves treatment; also the time of treatment significantly decreases.From SEM images it was observed that the most important modification was obtained in the case of zeolites synthesized by fusion and the less crystallized was the zeolite synthesized by the classical method without agitation. The occurrence of agitation, determined a significant modification of ash even when the treatment temperature decreased. Analyzing the obtained data, one may observe the destruction of the ash network and crystallization of the new phase, especially in the case of treatment by diffusion at ratios of 1/3 and 2 hours of treatment time. When synthesis by diffusion (Z13 and Z14) was performed a structure nearer to the zeolite ones was achieved by increasing the time of hydrothermal attack. It is obvious that the alkaline attack can convert fly ash into a beneficial product, which would prove effective in enhancing the soil quality. Further studies on the time of contact and hydroxide concentrations need to be performed, because these will determine the final conditions for capitalization of the material. Acknowledgments
This paper was realized with the support of POSDRU Postdoctoral School in Agriculture and Veterinary Medicine, ID 89/1.5/S62371, project funded by the European Social Found and Romanian Government.

References
Ahmaruzzaman M., (2010), A review on the utilization of fly ash, Progress in Energy and Combustion Science, 36, 327-363.

Ailinci C., Jitareanu G., Bucur D., Ailincai D., (2007), Influence of sewage sludge on maize yield and quality and soil chemical characteristics, Journal of Food, Agriculture & Environment, 5, 310-313. Ailinci C., Jitareanu G., Bucur D., Mercus A., (2011), Protecting the soil from erosion by cropping systems and fertilization in Moldavian Plateau, Journal of Food, Agriculture & Environment, 9, 570-574. Barbuta M., Taranu N., Harja M., (2009), Wastes used in obtaining polymer composite, Environmental Engineering and Management Journal, 8, 1145-1150. Barbuta M., Harja M., Babor D., (2010a), Concrete polymer with fly ash. Morphologic analysis based on scanning electron microscopic observations, Revista Romana de Materiale, 40, 337-345. Barbuta M., Harja M., Baran I., (2010b), Comparison of mechanical properties for polymer concrete with different types of filler, Journal of Material in Civil Engineering, 22, 696-701. Brezeanu M., Cristureanu E., Andruh M., (1990), Chimia metalelor, Ed. Tehnic i Pedagogic, Bucureti. Bucur D., Jitareanu G., Ailincai C., Tsadilas C., Ailincai Despina, Mercus A., (2007), Influence of soil erosion on water, soil, humus and nutrient losses in different crop systems in the Moldavian Plateau, Romania, Journal of Food, Agriculture & Environment, 5, 261264. Bucur D., Jitareanu G., Ailincai C., (2011), Effects of longterm soil and crop management on the yield and on the fertility of eroded soil, Journal of Food, Agriculture & Environment, 9, 207-209. Castaeda Muoz M., (2006), Industrial ecology approach to management of fly ash from fluized bed combustion: production of slow-release fertilizer and soil conditioner, PhD thesis, University Puerto Rico. Cline J.A., Bijl M., Torrenueva A., (2000), Coal fly ash as a soil conditioner for field crops in southern Ontario, Journal of Enviroment. Quality, 29, 1982-1989. Criado M., Fernandez-Jimenez A., Palomo A., (2007), Alkali activation of fly ash: Effect of the SiO2 /Na2O ratio. FTIR study, Microporous and Mesoporous Materials, 106, 180-191. Diaz-Zorita M., (2000), Effect of deep-tillage and nitrogen fertilization interactions on dryland corn (Zea mays L.) productivity, Soil and Tillage Research, 54, 11-19. Fansuri H., Pritchard D., Zang D., (2008), Manufacture of low grade zeolites from fly ash for fertilizer application, Research Report 91. Harja M., Barbuta M., Rusu L., (2009a), Obtaining and Characterization of Polymer Concrete with Fly Ash, Journal of Applied Science, 9, 88-91. Harja M., Barbuta M., Gavrilescu M., (2009b), Study of morphology for geopolymer materials obtained from fly ash, Environmental Engineering and Management Journal, 8, 1021-1027. Harja M., Barbuta M., Gavrilescu M., (2009c), Utilization of coal fly ash from power plants II. Geopolymer obtaining, Environmental Engineering and Management Journal, 8, 513-520. Harja M., Bucur D., Cimpeanu S.M., Ciocinta R.C., Gurita A.A., (2012). Conversion of ash on zeolites for soil application, International Journal of Food, Agriculture & Environment, 10, 10-16. Harja M., Barbuta M., Rusu L., Munteanu C., Buema G., Doniga E., (2011), Simultaneous removal of Astrazone Blue and lead onto low cost adsorbents based on power plant ash, Environmental Engineering and Management Journal, 10, 341-347.

304

Improving soil quality by adding modified ash

Hickman J.S., Whitney D.A., (2006), Soil Conditioners, North Central Regional Extension Publication 295, Kansas State University. Hill T., (2005), Plant Growth Media and fertilizer in the Nursery, On line at: http://depts.washington. edu/propplnt/Chapters/Soil%20media%20and%20Ferti lizers.htm. Hollman G.G., Steenbruggen G., Janssen-Jurkovicov M., (1999), A two-step process for the synthesis of zeolites from coal fly ash, Fuel, 78, 1225-1230. Ippolito J.A., Tarkalson D., Lehrsch G., (2011), Zeolite Soil Application Method Affects Inorganic Nitrogen, Moisture, and Corn Growth, Soil Science, 176, 136142. Jitreanu G., Ailincai C., Bucur D., (2007), Soil fertility management in North-East Romania, Journal of Food, Agriculture & Environment, 5, 349-353. Kalra N., Harit R.C., Sharma S.K., (2000), Effect of fly ash incorporation on soil properties of texturally variant soils, Bioresource Technology, 75, 91-93. Kumar V., Gautam G., Kiran A.Z., (2001). Fly Ash Use in Agricultura, Sigues & Concerns, On line at: http://www.tifac.org.in/news/flyagr1.htm Li D., Joo Y.K., Christians N.E., Minner D.D., (2000), Inorganic soil amendment effects on sand-based sports turf media, Crop Science, 40, 1121-1125. Milosevic T., Milosevic N., (2009), The effect of zeolite, organic and inorganic fertilizers on soil chemical properties, growth and biomass yield of apple trees, Pant Soil Environment, 55, 528535. Mishra A., Choudhary D., Jain N., Kumar M., Sharda N., Dutt D., (2008), Effect of concentration of alkaline liquid and curing time on strength and water absorption, Journal of Engineering and Applied Science, 3, 14-18.

Mumpton F.A., (1999), La roca magica: Uses of natural zeolites in agriculture and industry, Proceedings of the National Academi of Science, 96, 3463-3470. Ramesh K., Kumar Biswas A., Somasundaram J., Rao A.S., (2010), Nanoporous zeolites in farming: current status and issues ahead, Current Science, 99, 760-764. Reynolds W.D., Yang X.M., Drury C.F., Zhang T.Q., Tan C.S., (2003), Effects of selected conditioners and tillage on the physical quality of a clay loam soil, Canadian Journal of Soil Science, 83, 381-393. Rota Mining Co., Natural Zeolite as Soil Conditioner, July 18, 2006, On line at: http://www.zeoliteproducer. com/soilconditioner.html. Tatum D., Crouse K., (2006), Soil pH and Fertilizers, Mississippi State Univ. Extension Service, On line at: http://agrifor.ac.uk/browse/cabi63d96far3828012a3c27 4e28b8708e83.html Trotti J., (2006), Forum: Turning Dirt into Good Soil. Erosion Control, On line at: http://www.forester .net/ec_0003_forum.html. Virta R.L., Zeolites, (2002), U.S. Geological Survey Minerals Yearbook, July 2006, On line at: http://minerals.usgs.gov/minerals/pubs/commodity/zeol ites/zeolmyb02.pdf. Wang S., Wu H., (2006), Environmental-benign utilisation of fly ash as low-cost adsobents, Journal of Hazardous Materials, B136, 482-501. Yoo J.G., Jo Y.M., (2003), Utilization of coal fly ash as a slow-release granular medium for soil improvement, Journal of Air and Waste Management Association, 53, 77. Zeolite Soil Conditioner, (2006), On line at: http://www.industrialminerals.net/prod01.htm, http:// www. zeolite.ca/SoilConditionerAG.htm.

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