Agricultural Reviews, 37 (2) 2016 : 101-108

AGRICULTURAL RESEARCH COMMUNICATION CENTRE

Print ISSN:0253-1496 / Online ISSN:0976-0539

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Zeolite and its potential uses in agriculture : A critical review C. Sangeetha* and P. Baskar1 Department of Agronomy, Tamil Nadu Agricultural University, Coimbatore – 641 003, India. Received: 10-09-2015 Accepted: 25-02-2016

DOI:10.18805/ar.v0iof.9627

ABSTRACT In many parts of the world food security is being affected due to declining quality and/or quantity of the soil resource base and climate change. In this context, farming with zeolites has drawn attention. Zeolites are natural aluminosilicates present in rocks different part of the world. Use of zeolite has gained a momentum in the recent past owing to multitude of benefits accured from them. Zeolites are useful in agriculture because of their large porosity, cation exchange capacity and selectivity for ammonium and potassium cations. They can be used both as carriers of nutrients and as a medium to free nutrients. Although considerable research has been advanced, further research needs to carried out for their efficient utilization in farming. Key words: Agriculture, Odour, Slow release nutrient, Waste water treatment, Zeolite. Farming with natural rocks and minerals is an ageold practice for food production since stone ages.The intensive production practices concomitant with imbalanced fertilizer management practices has led to declining quality and/or quantity of the soil resource base and climate change. To feed the growing population, soil degradation is the key issue which needs urgent attention. World soils are less fertile which is evident from Royal Commission of Agriculture (1928) reports. In this context farming with natural zeolites have assumed great significance. Vertisoils contain lot of Zeolites 77.2–81.0 mg per kg (Pal, 2003) Japanese farmers have used zeolite rock for years to control the moisture content and offensive odour of animal wastes and to increase the pH of acidic volcanic soils (Bernardi et al., 2014.) Structure of Zeolite: Zeolites are composed of pores and corner sharing aluminosilicate (AlO4 and SiO4) tetrahedrons, joined into three dimensional frameworks. The pore structure is characterized by cages approximately 12Å in diameter, which are interlinked through channels about 8Å in diameter, composed of rings of 12 linked tetrahedrons (Kaduk and Faber, 1995). The pores are interconnected and form long wide channels of varying sizes depending on the mineral. These channels allow the easy movement of the resident ions and molecules into and out of the structure. Zeolites have large vacant spaces or cages within and resemble honeycomb or cage like structures. The presence of aluminium results in a negative charge, which is balanced by positively charged cations. The general empirical formula, which represents a zeolite chemical structure, is shown below:

M2nO . Al2O3 . xSiO2 . yH2O

Tetrahedral AlO4-5 and SiO4-4 bound by oxygen atoms to form tectosilicates called Zeolites and used for catalysts

M represents any alkali or alkaline earth cation, n the valence of the cation, x varies between 2 and 10, and y varies between 2 and 7 , with structural cations comprising Si, Al and Fe3+, and exchangeable cations K, Na and Ca (Sheppard and Mumpton,1981); (Hemingway and Robie,1984). Origin, nature and properties: Identification of zeolites as a mineral goes back to 1756, when a Swedish mineralogist, Alex Fredrik Cronstedt, collected some crystals from a copper mine in Sweden. Zeolites mean ‘boiling stones’ in Greek, because of their ability to froth when heated to about 200°C. Thereafter, zeolites were considered as a mineral found in volcanic rocks for a period of 200 years. Their commercial production and use started in the 1960s (Polat et al., 2004).Different combinations of SiO44 – and Al(OH)36 – tetrahedral lead to the formation of a three-dimensional framework with pores and voids of molecular dimension. Shape, dimensions and linkage of zeolite pores and voids are the key characteristics of zeolite materials. The pores and interconnected voids are occupied by cations and water

*Corresponding author’s e-mail: [email protected]. 1Kumaraguru Institute of Agriculture, Sakthinagar, Erode –638 315 Tamilnadu.

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molecules. The structure of each zeolite mineral is complex, but they all have large open ‘channels’ in the crystal structure that provide a large void space for the adsorption and exchange of cations. The internal surface area of these channels is reported to reach as much as several hundred square metres per gram of zeolite, making zeolite an extremely effective ion exchanger. Cations can be changed by ion exchange and water can be removed reversibly by application of heat. The mineral has a three-dimensional crystal lattice, with loosely bound cations, capable of hydrating and dehydrating without altering the crystal structure. Other useful chemical and physical properties include: high void volume (~ 50%), low density (2.1–2.2 g/ cm3), excellent molecular sieve properties and high cation exchange capacity (CEC) of 150–250 cmol/kg (Bhattachayya et al., 2015), cation selectivity, specifically for cations like ammonium, potassium, cesium, etc. (Auerback et al., 2003) The kinetics of ion-exchange process in zeolites has been extensively studied. Two processes have been identified, viz. particle diffusion and film diffusion. Diffusion within the zeolite (particle diffusion) and diffusion transport through the liquid film surrounding the particle (film diffusion) have been assumed to be the most important steps in the ion-exchange process. The preference of a zeolite for a particular cation in a multicomponent system depends on various factors, viz. Si/Al ratio of the zeolite, the exchangeable cation of the starting zeolite (co-ions), the hydration ratio of the co-ion and the in-going ions as well as the temperature and three-dimensional framework of zeolite. Therefore, these features should be analysed for a better understanding of the multi-component ion exchange mechanism. Classification: More than 50 different species of this mineral group have been identified (Tsitsishvili et al., 1992). Zeolites have been classified on the basis of their morphological characteristics, crystal structure, chemical composition, effective pore diameter and natural occurrence. Zeolites are classified on the basis of silica : alumina ratio as follows: (i) Low Si : Al ratio, between 1 and 1.5 – zeolite A; (ii) Intermediate Si : Al ratio, between 2 and 5 – zeolite Y; (iii) High Si : Al ratio from 10 to several thousands – erionite, mordenite. In 1997, the Subcommittee on zeolites of the International Mineralogical Association, Commission

on New Minerals and Mineral Names had recommended nomenclature for zeolite minerals (Coombs et al., 1997). The report suggested that zeolite species are not to be distinguished solely on the Si : Al ratio, except for heulandite (Si : Al < 4.0) and clinoptilolite (Si : Al e” 4.0). Dehydration, partial hydration and over hydration are not sufficient grounds for the recognition of separate species of zeolites.Later, Flanigen (2001) has classified zeolites based on pore diameter. (i) Small-pore zeolites (8 rings) with free pore diameter 0.3–0.45 nm. (ii) Medium-pore zeolites (10 rings) with free pore diameter 0.45–0.6 nm. (iii) Large-pore zeolites (12 rings) with free pore diameter 0.6–0.8 nm. (iv) Extra largepore zeolites (14 rings) with free pore diameter 0.8–1.0 nm. Why we use zeolite in agriculture : Utilization of zeolites in agriculture is possible because of their special cation exchange properties, molecular sieving and dsorption (Glisic and Milosevic, 2008; Hecl and Toth, 2009). It is believed that because zeolites have the ability to lose and gain water reversibly, without the change of crystal structure, they could be used as fertilizers, stabilizers and chelators. As an example, a study has shown that zeolites enable both inorganic and organic fertilizers to slowly release their nutrients (Perez-Caballero et al., 2008). However, there is dearth of information on the right amount of zeolites to be used with for instance inorganic and organic fertilizers. Uses: Zeolites are useful in agriculture because of their large porosity, their high cation exchange capacity and their selectivity for ammonium and potassium cations. They can be used both as carriers of nutrients and as a medium to free nutrients. The main use of zeolites in agriculture is, however, for nitrogen capture, storage and slow release. It has been shown that zeolites, with their specific selectivity for ammonium (NH4+), can take up this specific cation from either farmyard manure, composts or ammonium-bearing fertilizers, thereby reducing losses of nitrogen to the environment (Kocakusak et al., 2001). Ammonium-charged zeolites have also been tested successfully for their ability to increase the solubilization of phosphate minerals (Lai and Eberl 1986; Chesworth et al., 1987), leading to improved phosphorus uptake and yields for sudangrass (Barbarick et al., 1990). Eberl and Lai (1992)

TABLE 1: Physical characteristics of some naturally occurring zeolites (Dogan, 2003) Zeolite Analcine Chabezite Clinoptilolite Erionite Heulandite Mordenite Philipsite

Porosity(%)

Heat stability

Ion exchange capacity (meq/g)

Specific gravity (g/cm3)

Bulk density (g/cm3)

18 47 34 35 39 28 31

High High High High Low High moderate

4.54 3.84 2.16 3.12 2.91 4.29 3.31

2.24-2.29 2.05-2.10 2.15-2.25 2.02-2.08 2.18-2.20 2.12-2.15 2.15-2.20

1.85 1.45 1.15 1.51 1.69 1.70 1.58

Volume 37 Issue 2 (2016) developed urea-impregnated zeolite chips, which can be used as slow release nitrogen fertilizers. In Cuba, zeolites have also been successfully used as potting media in horticulture (‘zeoponics’), where nutrient-charged zeolites together with other mineral phases provide the plants with substrate and nutrients for growth. But the performance of natural zeolites must be assessed critically. There are about 50 different species of zeolites, each having a different chemical composition and structure. While most zeolites are beneficial in improving animal and plant growth, there are cases where zeolites do not perform effectively. For example, it has been demonstrated that certain zeolites with sodium as the main exchangeable cation can actually decrease rather than increase plant growth and yield (Barbarick and Pirela, 1984). Also, the zeolite erionite can be harmful to health when inhaled by animals and humans (Suzuki and Kohyama, 1988). This demonstrates the importance of good mineralogical and chemical characterization of zeolites and an intelligent selection of zeolites to suit their application. Zeolites improves the efficiency of nutrient use by increasing the availability of P from phosphate rock, the utilization of N-NH4+ and N-NO3- and reduced losses by leaching of exchangeable cations, especially K+ (Leggo 2000; and Pickering et al. 2002). Zeolites also improves the efficiency of water use by increasing the soil water holding capacity and its availability to plants (Xiubin and Zhanbin 2001; Bernardi et al. 2008). While literature shows that zeolites are useful for increasing nutrient use efficiency in a range of crops, little information exists on the use of stilbite, in agricultural systems especially on acid soils. The objective of this report was to characterize and test the application of Brazilian zeolitic sedimentary rock as a slow release fertilizer and soil conditioner. Applications : Zeolites are important materials with broad applications in refineries as catalysts, sorption and separation processes, and also in agriculture and environmental engineering. Some significant uses of zeolites are discussed here,but their importance is growing day-by-day. Today, synthetic zeolites are mainly being used widely in petroleum refining and chemical process industries as selective adsorbents, catalysts and ion exchangers. However, the importance of zeolites has been realized in a greater extent in the agriculture sector. Most of the initial research on the use of zeolites in agriculture took place in the 1960s in Japan. A brief review of the literature points out that Japanese farmers have used zeolite rocks over the years to control moisture content and increase the pH of acidic volcanic soils. Ion exchange properties of zeolites can be utilized in agriculture because of their large porosity and high cation exchange capacity. They can be used both as carriers of nutrients and as a medium to free nutrients.(Ramesh et al., 2010a, 2011; Ramesh, 2013). Among the natural zeolites,

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clinoptilolite (Ramesh et al., 2015b) is most commonly used in agriculture. As they play an important role in modifying the physics, chemistry and biology of soils. (Pal et al., 2013) reported that at Iran application of zeolite along with plant residues in soil have shown even positive effects on improving carbon pools and increasing carbon sequestration (Aminiyan and Akhgar, 2014) and ammonia diffused in wastewater too (Markou et al., 2014) Organic manure handling and management : Zeolites could be used as an effective additive to control the odour (Sharadeqah and Al-Dwairi, 2010), as they could adsorb the volatile substances (Rodriguez et al., 1994) like acetic acid, butanoic acid, isovaleric acid,indole, skatole (Cai et al., 2007) and enhances effectiveness of the manure (Leggo, 2000). Surface application of zeolite has potential for mitigating farmyard manure NH3 losses thereby reducing losses of nitrogen to the environment, but specific zeolite properties influenced its effectiveness (Waldrip et al., 2014). Nitrifying bacteria could not use the manure- ammonia in the zeolite due to small pore size (Mumpton, 1999). Ramesh and Islam (2012) have found reduced loss of ammonium from zeolite mixed with cow manure at Ohio, USA. Mature compost with good agronomic properties was produced by co-composting chicken slurry and paddy husk using zeolite and urea as additives by Latifah et al. (2015). Nitrogen management: Although nitrogen is regarded as kingpin in agriculture and widely used in all crops and cropping system, its use efficiency is just 30-40% only. Natural zeolites have been used in partial liquidation of fast and liquid wastes from animal production in agriculture and can be utilized for removing unpleasant smell in stables (Ramesh et al., 2010a).A reduction in soil urease activity with zeolite was also noticed by Ramesh et al. (2010 b,c). Urea impregnated zeolite chips have also been developed elsewhere. Kavoosi (2007) found increased nitrogen-use efficiency in rice owing to application of zeolites and ensured good retention of soil-exchangeable cations, available P and NO3 within the soil in maize at Malaysia (Rabai et al., 2013). There is possibility of surfactant- modified zeolite as a good sorbent for nitrate (Li, 2003), besides retaining large quantities of ammonium ion, interfere with the process of nitrification (Perrin et al., 1998). Zeolites with fertilizers in Cocoa enhanced fruiting (Sanchez-Mora et al., 2013), reduced nitrate and ammonium leaching (Moradzadeh et al., 2014) and so Clinoptilolite with 75 % fertilizers to maize was equally good to that of 100 % fertilizers alone at Malaysia (Aainaa et al., 2015). Phosphorus management : Zeolite rock phosphate (Allen et al., 1993) combination acted as an exchange fertilizer, with Ca2+ exchanging onto the zeolite in response to plant uptake of nutrient cations (NH4+ or K+ ), enhancing the dissolution of rock phosphate (Pickering et al., 2002). Ammonium-charged zeolites have shown their ability to

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increase the solubilization of phosphate minerals (Hua et al., 2006) or animal bone ash (Lancellotti et al., 2014) and promoted the rock- phosphate dissolution in all soil types (Mihajloviae et al., 2014) and reduced fixation in soils (Shokouhi et al., 2015). Slow release of nutrient : The main use of zeolite is nitrogen capture, storage release, as they adsorb molecules at relatively low pressure (Kamarudin et al., 2003) and is considered as nano-enhanced green application (Lavicoli et al., 2014). The is new possibility, which is the addittion of zeolite to the organic substrate (Leggo, 2000). Zeolite as coating material has shown the potential to increase water absorption and water retention of NPK fertilizers and to retard N,P and K release from the fertilizers in a sandy soil in Indonesia (Sulakhudin and Sunarminto, 2011). Zeolite applied with urea reduced the ammonia volatilization by 8%. Concentrated zeolite used a sand-soil amendment also increased at least 10 % of soil –water retention and 15 % of available water capacity (Bernardi et al., 2013). Slow release of herbicides : The most hydrophobic solids such as zeolite ‘ZSM 5’ were found to adsorb atrazine better when organics were present (Bottero et al., 1994) in the compartmentalized intracrystalline void space of zeolites (Corma and Garcia, 2004). This was brought a considerable attention on soil clay minerals for slow-release formulation of herbicides. Zeolite (ZSM-5) was found to accommodate herbicide paraquat in the microstructure with restricted mobility (Walcarius and Mouchotte, 2004).This was followed by surface modification of paraquat by Zhang et al., (2006). Humic acid zeolites were also found to be sorbents for phenylurea herbicides (Capasso et al., 2007). Clinoptilolitic tuff was considered as a suitable material for removing atrazine from soil (Salvestrine et al., 2010) and water (Jamil et al., 2011) too. Later an enhanced activity of zeolite- loaded catalysts on herbicide isoproturon was found to be synergistic effect of increased visible light absorption and the high porous nature of zeolite facilitating the adsorption of recalcitrant molecules (Reddy et al., 2012). This was followed by Bakhiary et al. (2013) with 2,4-D herbicide showed gradual temporal release pattern and kept the active ingredient in the upper 5 cm soil layer (Shirvani et al., 2014). Improving soil physical properties: Zeolites have been reported to improve the soil physical properties. They may hold water more than half of their weight due to high porosity of the crystalline structure. Water molecules in the pores could easily be evaporated or reabsorbed without damage to such structures. Zeolites assure a permanent water reservoir. Providing prolonged moisture dry periods helps plants to withstand dry spell; they also promote a rapid rewetting and improve the lateral spread of water into the root zone during irrigation. This results in saving water needed for irrigation. Amendment of sand with zeolite

increases available water to the plants by 50% (Voroney and Van Straaten 1988). Remediation of contaminated soil : The application of zeolites to soil contaminated with heavy metals or radionuclides can be effective in lowering their input. This area of research is promising and needs extensive studies (Ramesh et al., 2010a). As soil amendment : Zeolites consist of cage-like polyhedral units with a high cation-exchange capacity and internal pores in crystal lattices that result in high water adsorption and nutrient retention (Zelazny and Calhoun, 1977). Zeolite does not break down over time, but remains in the soil to improve nutrient retention. Therefore, its addition to the soil may significantly reduce water and fertilizer costs by retaining beneficial nutrients in the root zone. The porous structure of natural zeolite helps keep the soil aerated and moist as well as active for a long time. Natural zeolites have been reported to be used extensively in Japan as amendments for sandy soils, and small tonnages have been exported to Taiwan for this purpose. Zeolitic amendment is an effective way to improve soil condition in an arid and semiarid environment (Yasuda,1998). Zeolites have been tested for use as a soil amendment on various crops, including vegetables and in greenhouses in Russia, field crops in Japan, as constituents of golf course greens and tees in order to improve drainage and aeration, to improve compaction resistance, and reduce leaching of pesticides and fertilizers from the soil. Zeolites increase the water-retention capacity of the soils (Notario del Pino, 1994). The higher the average ionic potential of the extra- framework cations, the larger the hydration capacity of the clinoptilolite. This trend may be attributed to the small size as well as the efficient water–cation packing of high field strength cations in the zeolite structure (Yang et al., 2001). Wastewater treatment : Zeolites may be used for removing ammonia from wastewater. Clinoptilolite is effective for selective removal of NH4 + cations from wastewater. Zeolites are an appropriate material for removing heavy metal ions from wastewater because of their relatively low price coupled with the harmless nature of their exchangeable ions (Barros et al., 2003). Since most zeolites are beneficial for plant growth, it has been demonstrated that certain zeolites with sodium as the main exchangeable cation can actually decrease plant growth and yield. Also, the zeolite erionite is reported to be harmful to health. Therefore, proper selection of appropriate zeolites to suit their application is important. A few important applications of zeolites have been discussed above, but the possibilities of their usage are much broader. Future research: The following issues have been identified for further research in soil and plant management: (1) To characterize the Bronsted and Lewis acid centres in zeolites. (Bronsted acid sites are assigned to bridging hydroxyl groups, whereas Lewis acid sites are essentially

Volume 37 Issue 2 (2016) electronacceptor centres and they can be cations or different aluminium species located in defect centres; the latter are the so-called true Lewis acid sites). (2) To characterize the available zeolite deposits in each country. (3) To probe whether zeolite amendment will reduce the potential for nitrate leaching in agriculture. (4) To develop methodologies for organo-zeolitic manure/fertilizers. (5) To characterize the nutrient release pattern from organo-zeolites.(6) To probe the physical stability of zeolites in a variety of soil environments. (7) To probe the long-term impact of zeolites on soil flora and fauna. (8) To develop zeolitic herbicides to minimize herbicidal residues. (9) To carry out field testing of zeolites on soil and plant systems. CONCLUSION There is an increasing interest in the utilization of nanoporous zeolites in farming over the years because of

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current public concern about the adverse effects of chemical fertilizers on the agro-ecosystem. Ion-exchange properties of zeolites are recognized as important for plant nutrition due to their high cation-exchange capacity and porosity. Both ion-exchange and porosity are relevant to agronomy and soil science. The specific structure and diversity of the zeolites vary as also their application. They can be used either as carriers of nutrients and/or a medium to free the nutrients. Several applications have been identified in zeolite research and attempts are being made worldwide. Considerable research has been carried out globally to exploit the potential of zeolites in the perpetual maintenance of soil productivity. The current growing awareness of the phenomenon and availability of inexpensive natural zeolites has aroused considerable commercial interest. Also, a number of issues have been identified for future research.

REFERENCES Aainaa, H.N., Ahmed, O.H., Kasim, S., and Ab.Majid, N.M. (2015). Reducing Egypt rock phosphate use in zea mays cultivation on an acid soil using clinoptilotic zeolite. Sustainable Agricultural Research 4: 56. Allen, E.R., Hossner, L.R., Ming, D.W. and Henninger, D,L. (1993).Solubility and cation exchange in phosphate rock and satutrated clinoptilotic mixtures. Soil Science Society of America Journal 57:1368-1374. Aminiyan, M. and Akhgar, A. (2014). The effect of zeolite and plant residues on soil microbial characteristics-incubation study. Agricultural Advances 3: 6-12. Auerback, S.M., Carrado, K.M. and Dutta, P.K. (2003). Handbook of Zeolite Science and Technology. Marcel Dekker, Inc., New York. Bakhtiary, S., Shirvani, M. and Shariatmadari, H. (2013). Adsorption desorption behavior of 2,4-D on NCP-modified bentonite and zeolite: Implications for slow release herbicide formulations. Chemosphere 90: 699-705. Barbarick, K.A. and Pirela, H.J.(1984). Agronomic and horticultural uses of zeolite. In: Pond WG, Mumpton FA, editors. Zeo-agriculture: Use of Natural Zeolites in Agriculture and Aquaculture. Boulder, CO, USA: Westview Press, pp. 93–104. Barbarick, K.A., Lai, T.M, and Eberl, D.D. (1990). Exchange fertilizer (phosphate rock plus ammonium-zeolite) effects on sorghum-sudangrass. Soil Science Society of America Journal 54: 911-916. Barros, M. A. S. D., Zola, A. S., Arroyo, P. A., Sousa-Aguiar, E. F. and Tavares, C. R. G. (2003). Binary ion exchange of metal ions in Y and X zeolites. Brazilian Journal of Chemical Engineering 20: 413–421. Bernardi, A.C.C., Oliveria, P.P.A., Barros, F. (2013). Brazilian sedimentary zeolite use in agriculture. Microporous and Mesoporous Materials 17: 16-21 Bernardi, A.C.C., Polidoro, J.C., Piereira, E.I. and Oliveria, C.R.D. (2014). The use of clay minerals to improve nitrogen fertilizer efficiency (In) 16th World congress of CIEC Technological Innovation For a Sustainable Tropical Agriculture, October 20-24, Brazil. Bernardi, A.C.C., Werneck, C.G., Haim, P.G., Rezende, N.G.A.M., Paiva, P.R.P., Monte, M.B.M. (2008). Crescimento enutrição mineral do porta-enxerto limoeiro ‘Cravo’ cultivado em substrato com zeólita enriquecida com NPK. Revista Brasileira de Fruticultura 30: 794-800. Bhattacharyya, T., Chandran, P., Ray, S. K., Pal, D. K., Mandal, C. and Mandal, D. K. (2015). Distribution of zeolitic soils in India. Current Science 109: 1305-1313 Bottero, J.Y., Khatib, K., Thomas, F., Jucker, K., Bersillon, J.L. and Mallevialle, J. (1994). Adsorption of atrazine onto zeolites and organoclays, in presence of background organics. Water Research 28: 483-490. Cai, L., Koziel, J.A., Liang,Y., Nguyen, A.T. and Xin, H. (2007). Evaluation of zeolite for control of odorants emission from simulated poultry manure storage. Journal of Environmental Quality 36: 184-193. Capasso, S., Coppola, E., Lovino, P., Salvestrini, S. and Colella, C. (2007). Uptake of phenylurea herbicides by humic acid-zeolite tuff aggregate. Studies in Surface Science and Catalysis 170: 2122-2127. Chesworth, W., Van straiten, P., Smith, P and Sadura, S. (1987). Solubility of apatite in clay aeolite-bearing system: application to agriculture. Applied clay science 2 : 291-297.

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