Agricultural Reviews, 37 (2) 2016 : 101-108 AGRICULTURAL RESEARCH COMMUNICATION CENTRE

Print ISSN:0253-1496 / Online ISSN:0976-0539 www.arccjournals.com

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 age- M2nO . Al2O3 . xSiO2 . yH2O
old 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
Tetrahedral AlO4-5 and SiO4-4 bound by oxygen
(1928) reports. In this context farming with natural zeolites atoms to form tectosilicates called Zeolites and
have assumed great significance. Vertisoils contain lot of used for catalysts
Zeolites 77.2–81.0 mg per kg (Pal, 2003) Japanese farmers
M represents any alkali or alkaline earth cation, n the valence
have used zeolite rock for years to control the moisture
of the cation, x varies between 2 and 10, and y varies between
content and offensive odour of animal wastes and to increase
2 and 7 , with structural cations comprising Si, Al and Fe3+,
the pH of acidic volcanic soils (Bernardi et al., 2014.)
and exchangeable cations K, Na and Ca (Sheppard and
Structure of Zeolite: Zeolites are composed of pores and Mumpton,1981); (Hemingway and Robie,1984).
corner sharing aluminosilicate (AlO4 and SiO4) tetrahedrons, Origin, nature and properties: Identification of zeolites
joined into three dimensional frameworks. The pore structure as a mineral goes back to 1756, when a Swedish mineralogist,
is characterized by cages approximately 12Å in diameter, Alex Fredrik Cronstedt, collected some crystals from a
which are interlinked through channels about 8Å in diameter, copper mine in Sweden. Zeolites mean ‘boiling stones’ in
composed of rings of 12 linked tetrahedrons (Kaduk and Greek, because of their ability to froth when heated to about
Faber, 1995). The pores are interconnected and form long 200°C. Thereafter, zeolites were considered as a mineral
wide channels of varying sizes depending on the mineral. found in volcanic rocks for a period of 200 years. Their
These channels allow the easy movement of the resident ions commercial production and use started in the 1960s (Polat
and molecules into and out of the structure. Zeolites have et al., 2004).Different combinations of SiO44 – and Al(OH)36
large vacant spaces or cages within and resemble honeycomb –
tetrahedral lead to the formation of a three-dimensional
or cage like structures. The presence of aluminium results in framework with pores and voids of molecular dimension.
a negative charge, which is balanced by positively charged Shape, dimensions and linkage of zeolite pores and voids
cations. The general empirical formula, which represents a are the key characteristics of zeolite materials. The pores
zeolite chemical structure, is shown below: 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.
102 AGRICULTURAL REVIEWS
molecules. The structure of each zeolite mineral is complex, on New Minerals and Mineral Names had recommended
but they all have large open ‘channels’ in the crystal structure nomenclature for zeolite minerals (Coombs et al., 1997).
that provide a large void space for the adsorption and The report suggested that zeolite species are not to be
exchange of cations. The internal surface area of these distinguished solely on the Si : Al ratio, except for heulandite
channels is reported to reach as much as several hundred (Si : Al < 4.0) and clinoptilolite (Si : Al e” 4.0). Dehydration,
square metres per gram of zeolite, making zeolite an partial hydration and over hydration are not sufficient
extremely effective ion exchanger. Cations can be changed grounds for the recognition of separate species of
by ion exchange and water can be removed reversibly by zeolites.Later, Flanigen (2001) has classified zeolites based
application of heat. The mineral has a three-dimensional on pore diameter. (i) Small-pore zeolites (8 rings) with free
crystal lattice, with loosely bound cations, capable of pore diameter 0.3–0.45 nm. (ii) Medium-pore zeolites (10
hydrating and dehydrating without altering the crystal rings) with free pore diameter 0.45–0.6 nm. (iii) Large-pore
structure. Other useful chemical and physical properties zeolites (12 rings) with free pore diameter 0.6–0.8 nm. (iv)
include: high void volume (~ 50%), low density (2.1–2.2 g/ Extra largepore zeolites (14 rings) with free pore diameter
cm3), excellent molecular sieve properties and high cation 0.8–1.0 nm.
exchange capacity (CEC) of 150–250 cmol/kg (Bhattachayya Why we use zeolite in agriculture : Utilization of zeolites
et al., 2015), cation selectivity, specifically for cations like in agriculture is possible because of their special cation
ammonium, potassium, cesium, etc. (Auerback et al., 2003) exchange properties, molecular sieving and dsorption (Glisic
The kinetics of ion-exchange process in zeolites and Milosevic, 2008; Hecl and Toth, 2009). It is believed
has been extensively studied. Two processes have been that because zeolites have the ability to lose and gain water
identified, viz. particle diffusion and film diffusion. Diffusion reversibly, without the change of crystal structure, they could
within the zeolite (particle diffusion) and diffusion transport be used as fertilizers, stabilizers and chelators. As an
through the liquid film surrounding the particle (film example, a study has shown that zeolites enable both
diffusion) have been assumed to be the most important steps inorganic and organic fertilizers to slowly release their
in the ion-exchange process. The preference of a zeolite for nutrients (Perez-Caballero et al., 2008). However, there is
a particular cation in a multicomponent system depends on dearth of information on the right amount of zeolites to be
various factors, viz. Si/Al ratio of the zeolite, the used with for instance inorganic and organic fertilizers.
exchangeable cation of the starting zeolite (co-ions), the
Uses: Zeolites are useful in agriculture because of their large
hydration ratio of the co-ion and the in-going ions as well as
the temperature and three-dimensional framework of zeolite. porosity, their high cation exchange capacity and their
Therefore, these features should be analysed for a better selectivity for ammonium and potassium cations. They can
understanding of the multi-component ion exchange be used both as carriers of nutrients and as a medium to free
mechanism. nutrients. The main use of zeolites in agriculture is, however,
for nitrogen capture, storage and slow release. It has been
Classification: More than 50 different species of this shown that zeolites, with their specific selectivity for
mineral group have been identified (Tsitsishvili et al., 1992).
ammonium (NH4+), can take up this specific cation from
Zeolites have been classified on the basis of their
either farmyard manure, composts or ammonium-bearing
morphological characteristics, crystal structure, chemical
fertilizers, thereby reducing losses of nitrogen to the
composition, effective pore diameter and natural occurrence.
environment (Kocakusak et al., 2001).
Zeolites are classified on the basis of silica : alumina ratio
as follows: (i) Low Si : Al ratio, between 1 and 1.5 – zeolite Ammonium-charged zeolites have also been tested
A; (ii) Intermediate Si : Al ratio, between 2 and 5 – zeolite successfully for their ability to increase the solubilization of
Y; (iii) High Si : Al ratio from 10 to several thousands – phosphate minerals (Lai and Eberl 1986; Chesworth et al.,
erionite, mordenite. In 1997, the Subcommittee on zeolites 1987), leading to improved phosphorus uptake and yields
of the International Mineralogical Association, Commission for sudangrass (Barbarick et al., 1990). Eberl and Lai (1992)
TABLE 1: Physical characteristics of some naturally occurring zeolites (Dogan, 2003)
Zeolite Porosity(%) Heat stability Ion exchange capacity Specific gravity Bulk density
(meq/g) (g/cm3) (g/cm3)
Analcine 18 High 4.54 2.24-2.29 1.85
Chabezite 47 High 3.84 2.05-2.10 1.45
Clinoptilolite 34 High 2.16 2.15-2.25 1.15
Erionite 35 High 3.12 2.02-2.08 1.51
Heulandite 39 Low 2.91 2.18-2.20 1.69
Mordenite 28 High 4.29 2.12-2.15 1.70
Philipsite 31 moderate 3.31 2.15-2.20 1.58

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 Volume 37 Issue 2 (2016) 103
developed urea-impregnated zeolite chips, which can be used clinoptilolite (Ramesh et al., 2015b) is most commonly used
as slow release nitrogen fertilizers. In Cuba, zeolites have in agriculture. As they play an important role in modifying
also been successfully used as potting media in horticulture the physics, chemistry and biology of soils. (Pal et al., 2013)
(‘zeoponics’), where nutrient-charged zeolites together with reported that at Iran application of zeolite along with plant
other mineral phases provide the plants with substrate and residues in soil have shown even positive effects on
nutrients for growth. But the performance of natural zeolites improving carbon pools and increasing carbon sequestration
must be assessed critically. (Aminiyan and Akhgar, 2014) and ammonia diffused in
There are about 50 different species of zeolites, each wastewater too (Markou et al., 2014)
having a different chemical composition and structure. While Organic manure handling and management : Zeolites
most zeolites are beneficial in improving animal and plant could be used as an effective additive to control the odour
growth, there are cases where zeolites do not perform (Sharadeqah and Al-Dwairi, 2010), as they could adsorb the
effectively. For example, it has been demonstrated that volatile substances (Rodriguez et al., 1994) like acetic acid,
certain zeolites with sodium as the main exchangeable cation butanoic acid, isovaleric acid,indole, skatole (Cai et al.,
can actually decrease rather than increase plant growth and 2007) and enhances effectiveness of the manure (Leggo,
yield (Barbarick and Pirela, 1984). Also, the zeolite erionite 2000). Surface application of zeolite has potential for
can be harmful to health when inhaled by animals and humans mitigating farmyard manure NH3 losses thereby reducing
(Suzuki and Kohyama, 1988). This demonstrates the losses of nitrogen to the environment, but specific zeolite
importance of good mineralogical and chemical properties influenced its effectiveness (Waldrip et al., 2014).
characterization of zeolites and an intelligent selection of Nitrifying bacteria could not use the manure- ammonia in
zeolites to suit their application. the zeolite due to small pore size (Mumpton, 1999). Ramesh
Zeolites improves the efficiency of nutrient use by and Islam (2012) have found reduced loss of ammonium
increasing the availability of P from phosphate rock, the from zeolite mixed with cow manure at Ohio, USA. Mature
utilization of N-NH4+ and N-NO3- and reduced losses by compost with good agronomic properties was produced by
leaching of exchangeable cations, especially K+ (Leggo co-composting chicken slurry and paddy husk using zeolite
2000; and Pickering et al. 2002). Zeolites also improves and urea as additives by Latifah et al. (2015).
the efficiency of water use by increasing the soil water Nitrogen management: Although nitrogen is regarded as
holding capacity and its availability to plants (Xiubin and kingpin in agriculture and widely used in all crops and
Zhanbin 2001; Bernardi et al. 2008). While literature shows cropping system, its use efficiency is just 30-40% only.
that zeolites are useful for increasing nutrient use efficiency Natural zeolites have been used in partial liquidation of fast
in a range of crops, little information exists on the use of and liquid wastes from animal production in agriculture and
stilbite, in agricultural systems especially on acid soils. The can be utilized for removing unpleasant smell in stables
objective of this report was to characterize and test the (Ramesh et al., 2010a).A reduction in soil urease activity
application of Brazilian zeolitic sedimentary rock as a slow with zeolite was also noticed by Ramesh et al. (2010 b,c).
release fertilizer and soil conditioner. Urea impregnated zeolite chips have also been developed
Applications : Zeolites are important materials with broad elsewhere. Kavoosi (2007) found increased nitrogen-use
applications in refineries as catalysts, sorption and separation efficiency in rice owing to application of zeolites and ensured
processes, and also in agriculture and environmental good retention of soil-exchangeable cations, available P and
engineering. Some significant uses of zeolites are discussed NO3 within the soil in maize at Malaysia (Rabai et al., 2013).
here,but their importance is growing day-by-day. Today, There is possibility of surfactant- modified zeolite as a good
synthetic zeolites are mainly being used widely in petroleum sorbent for nitrate (Li, 2003), besides retaining large
refining and chemical process industries as selective quantities of ammonium ion, interfere with the process of
adsorbents, catalysts and ion exchangers. However, the nitrification (Perrin et al., 1998). Zeolites with fertilizers in
importance of zeolites has been realized in a greater extent Cocoa enhanced fruiting (Sanchez-Mora et al., 2013),
in the agriculture sector. Most of the initial research on the reduced nitrate and ammonium leaching (Moradzadeh et al.,
use of zeolites in agriculture took place in the 1960s in Japan. 2014) and so Clinoptilolite with 75 % fertilizers to maize
A brief review of the literature points out that Japanese was equally good to that of 100 % fertilizers alone at
farmers have used zeolite rocks over the years to control Malaysia (Aainaa et al., 2015).
moisture content and increase the pH of acidic volcanic soils. Phosphorus management : Zeolite rock phosphate (Allen
Ion exchange properties of zeolites can be utilized in et al., 1993) combination acted as an exchange fertilizer,
agriculture because of their large porosity and high cation with Ca2+ exchanging onto the zeolite in response to plant
exchange capacity. They can be used both as carriers of uptake of nutrient cations (NH4+ or K+ ), enhancing the
nutrients and as a medium to free nutrients.(Ramesh et al., dissolution of rock phosphate (Pickering et al., 2002).
2010a, 2011; Ramesh, 2013). Among the natural zeolites, Ammonium-charged zeolites have shown their ability to

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104 AGRICULTURAL REVIEWS
increase the solubilization of phosphate minerals (Hua et increases available water to the plants by 50% (Voroney and
al., 2006) or animal bone ash (Lancellotti et al., 2014) and Van Straaten 1988).
promoted the rock- phosphate dissolution in all soil types Remediation of contaminated soil : The application of
(Mihajloviae et al., 2014) and reduced fixation in soils zeolites to soil contaminated with heavy metals or
(Shokouhi et al., 2015). radionuclides can be effective in lowering their input. This
Slow release of nutrient : The main use of zeolite is nitrogen area of research is promising and needs extensive studies
capture, storage release, as they adsorb molecules at (Ramesh et al., 2010a).
relatively low pressure (Kamarudin et al., 2003) and is As soil amendment : Zeolites consist of cage-like polyhedral
considered as nano-enhanced green application (Lavicoli et units with a high cation-exchange capacity and internal pores
al., 2014). The is new possibility, which is the addittion of in crystal lattices that result in high water adsorption and
zeolite to the organic substrate (Leggo, 2000). Zeolite as nutrient retention (Zelazny and Calhoun, 1977). Zeolite does
coating material has shown the potential to increase water not break down over time, but remains in the soil to improve
absorption and water retention of NPK fertilizers and to nutrient retention. Therefore, its addition to the soil may
retard N,P and K release from the fertilizers in a sandy soil significantly reduce water and fertilizer costs by retaining
in Indonesia (Sulakhudin and Sunarminto, 2011). Zeolite beneficial nutrients in the root zone. The porous structure of
applied with urea reduced the ammonia volatilization by 8%. natural zeolite helps keep the soil aerated and moist as well
Concentrated zeolite used a sand-soil amendment also as active for a long time. Natural zeolites have been reported
increased at least 10 % of soil –water retention and 15 % of to be used extensively in Japan as amendments for sandy
available water capacity (Bernardi et al., 2013). soils, and small tonnages have been exported to Taiwan for
Slow release of herbicides : The most hydrophobic solids this purpose. Zeolitic amendment is an effective way to
such as zeolite ‘ZSM 5’ were found to adsorb atrazine better improve soil condition in an arid and semiarid environment
when organics were present (Bottero et al., 1994) in the (Yasuda,1998). Zeolites have been tested for use as a soil
compartmentalized intracrystalline void space of zeolites amendment on various crops, including vegetables and in
(Corma and Garcia, 2004). This was brought a considerable greenhouses in Russia, field crops in Japan, as constituents
attention on soil clay minerals for slow-release formulation of golf course greens and tees in order to improve drainage
of herbicides. Zeolite (ZSM-5) was found to accommodate and aeration, to improve compaction resistance, and reduce
herbicide paraquat in the microstructure with restricted leaching of pesticides and fertilizers from the soil. Zeolites
mobility (Walcarius and Mouchotte, 2004).This was increase the water-retention capacity of the soils (Notario
followed by surface modification of paraquat by Zhang et del Pino, 1994). The higher the average ionic potential of
al., (2006). Humic acid zeolites were also found to be the extra- framework cations, the larger the hydration
sorbents for phenylurea herbicides (Capasso et al., 2007). capacity of the clinoptilolite. This trend may be attributed
Clinoptilolitic tuff was considered as a suitable material for to the small size as well as the efficient water–cation packing
removing atrazine from soil (Salvestrine et al., 2010) and of high field strength cations in the zeolite structure (Yang
water (Jamil et al., 2011) too. Later an enhanced activity of et al., 2001).
zeolite- loaded catalysts on herbicide isoproturon was found Wastewater treatment : Zeolites may be used for removing
to be synergistic effect of increased visible light absorption ammonia from wastewater. Clinoptilolite is effective for
and the high porous nature of zeolite facilitating the selective removal of NH4 + cations from wastewater. Zeolites
adsorption of recalcitrant molecules (Reddy et al., 2012). are an appropriate material for removing heavy metal ions
This was followed by Bakhiary et al. (2013) with 2,4-D from wastewater because of their relatively low price coupled
herbicide showed gradual temporal release pattern and kept with the harmless nature of their exchangeable ions (Barros
the active ingredient in the upper 5 cm soil layer (Shirvani et al., 2003). Since most zeolites are beneficial for plant
et al., 2014). growth, it has been demonstrated that certain zeolites with
Improving soil physical properties: Zeolites have been sodium as the main exchangeable cation can actually
reported to improve the soil physical properties. They may decrease plant growth and yield. Also, the zeolite erionite is
hold water more than half of their weight due to high porosity reported to be harmful to health. Therefore, proper selection
of the crystalline structure. Water molecules in the pores of appropriate zeolites to suit their application is important.
could easily be evaporated or reabsorbed without damage A few important applications of zeolites have been discussed
to such structures. Zeolites assure a permanent water above, but the possibilities of their usage are much broader.
reservoir. Providing prolonged moisture dry periods helps Future research: The following issues have been identified
plants to withstand dry spell; they also promote a rapid for further research in soil and plant management: (1)
rewetting and improve the lateral spread of water into the To characterize the Bronsted and Lewis acid centres in
root zone during irrigation. This results in saving water zeolites. (Bronsted acid sites are assigned to bridging
needed for irrigation. Amendment of sand with zeolite hydroxyl groups, whereas Lewis acid sites are essentially

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 Volume 37 Issue 2 (2016) 105
electronacceptor centres and they can be cations or different current public concern about the adverse effects of chemical
aluminium species located in defect centres; the latter are fertilizers on the agro-ecosystem. Ion-exchange properties
the so-called true Lewis acid sites). (2) To characterize the of zeolites are recognized as important for plant nutrition
available zeolite deposits in each country. (3) To probe due to their high cation-exchange capacity and porosity. Both
whether zeolite amendment will reduce the potential for ion-exchange and porosity are relevant to agronomy and soil
nitrate leaching in agriculture. (4) To develop methodologies science. The specific structure and diversity of the zeolites
for organo-zeolitic manure/fertilizers. (5) To characterize the vary as also their application. They can be used either as
nutrient release pattern from organo-zeolites.(6) To probe carriers of nutrients and/or a medium to free the nutrients.
the physical stability of zeolites in a variety of soil Several applications have been identified in zeolite research
environments. (7) To probe the long-term impact of zeolites and attempts are being made worldwide. Considerable
on soil flora and fauna. (8) To develop zeolitic herbicides to research has been carried out globally to exploit the potential
minimize herbicidal residues. (9) To carry out field testing of zeolites in the perpetual maintenance of soil productivity.
of zeolites on soil and plant systems. The current growing awareness of the phenomenon and
CONCLUSION availability of inexpensive natural zeolites has aroused
There is an increasing interest in the utilization of considerable commercial interest. Also, a number of issues
nanoporous zeolites in farming over the years because of have been identified for future research.

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