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ING Bulletins on
Regional Assessment of Reactive Nitrogen
Published By
INDIAN NITROGEN GROUP (ING)
SOCIETY FOR CONSERVATION OF NATURE (SCON)
In Association With
SOUTH ASIAN NITROGEN CENTRE (SANC)
INTERNATIONAL NITROGEN INITIATIVE (INI)
ii Varadachari and Goertz
All rights reserved. No part of this publication may be reproduced, utilised in any
form or by any means, electronic or mechanical, including photocopying, recording
or by any information storage and retrieval system without permisssion in writing
from the publishers.
ISBN: 81-85992-24-X
Suggested Citation:
Varadachari Chandrika and Goertz Harvey M (2010) Slow-release and Controlled-release
Nitrogen Fertilizers, In ING Bulletins on Regional Assessment of Reactive Nitrogen,
Bulletin No. 11, (Ed. Bijay Singh), SCON-ING, New Delhi, pp i-iv & 1-42.
1. Introduction 1
2. Condensation Polymers 2
2.1 Urea Formaldehydes 2
2.1.1 Overview 2
2.1.2 Chemistry 2
2.1.3 Synthesis Routes 4
2.1.3.1 Reaction Kinetics 4
2.1.3.2 U/F 4
2.1.3.3 Temperature 5
2.1.3.4 pH 5
2.1.3.5 Reaction time 6
2.1.4 Commercial processes 6
2.1.5 Properties 6
2.1.6 Molecular quantification 8
2.1.7 Product classification 8
2.1.8 Official definition of product classes 9
2.1.9 Mechanisms of release 10
2.1.10 Agronomic studies 10
2.2 Urea isobutyraldehydes 11
2.2.1 Overview 11
2.2.2 Chemistry 11
2.2.3 Commercial processes 11
2.2.4 Properties 12
2.2.5 Mechanisms of release 12
2.3 Urea crotonaldehydes 13
2.3.1 Overview 13
2.3.2 Chemistry 13
2.3.4 Commercial processes 13
2.3.5 Properties 14
2.3.6 Mechanisms of release 14
3. COATED FERTILIZERS 14
3.1 Sulphur coated (including sulphur/polymer coated) 15
3.1.1 Commercial processes 15
3.1.2 Mechanisms of release 15
3.1.3 Agronomic studies 16
3.2 Polymer coated 16
3.2.1 Overview 16
3.2.2 Processing methods 17
3.2.3 Mechanisms of Release 18
3.2.4 Advantages/Disadvantages 19
3.2.5 Agronomic Studies 19
3.3 Neem Coated 20
3.3.1 Overview 20
3.3.2 Commercial Processes 20
3.3.3 Agronomic Studies 20
3.4 Degradable Polymer Coated 21
3.5 Latex, Clay, Gypsum and Other Coatings 21
4. GEL BASED MATERIALS 22
4.1 Overview 22
4.2 Processes and Product Properties 22
4.3 Mechanisms of Release 23
4.4 Agronomic Studies 23
5. SUPERGRANULES AND COMPACTED MATERIALS 23
5.1 Overview 23
5.2 Agronomic Studies 24
6. ZEOLITE BASED MATERIALS AND OTHERS 25
7. STABILISED NITROGEN PRODUCTS 25
7.1 Nitrification Inhibitors 25
7.1.1 Overview 25
7.1.2 Commercial Materials 25
7.1.3 Agronomic Studies 26
7.2 Urease Inhibitors 26
7.2.1 Overview 26
7.2.2 Commercial Materials 27
7.2.3 Agronomic Studies 27
7.3 Natural Inhibitors 27
8. Commercial slow-release nitrogen fertilizers 28
9. Acknowledgement 28
Slow-Release and Controlled-Release
Nitrogen Fertilizers
Chandrika Varadachari1 and Harvey M. Goertz2
1 Raman Centre for Applied and Interdisciplinary Sciences, 16A Jheel Road, Kolkata
(Calcutta) 700075, India
2 Innovative Hort Solutions, LLC, 13261 Hinton Mill Rd., Marysville, Ohio 43040, USA
ABSTRACT
This bulletin reviews the status of research and development on slow-release
and controlled-release nitrogen fertilizers. The discussion encompasses
manufacturing processes, chemistry and mechanism, commercially available
materials and agronomic responses. Different groups of these fertilizers
have been broadly divided as (i) condensation polymers (including urea
formaldehydes, IBDU, CDU), (ii) coated fertilizers (sulphur/sulphur-polymer,
polymer, neem, degradable polymer, latex, clay and gypsum coated),
(iv) gel based materials, (v) supergranules and compacted materials, (vi) zeolite
based materials and (vii) stabilised nitrogen products (nitrification inhibitors,
urease inhibitors and natural inhibitors). A list of major manufacturers and
information on their products is also provided.
1. INTRODUCTION
Nitrogen, the most important fertilizer nutrient is probably the poorest in terms
of use-efficiency and the most serious of the pollutants. Run-off, leaching and
volatilization result in a massive wastage of resources. The root cause of the problems
associated with nitrogen fertilizers is their water solubility. Inorganic nitrogen
sources are not necessarily per se environmentally harmful but are effectively so,
because of their high water solubility. Reducing water solubility would eliminate
this problem and produce a fertilizer that is environmentally safe and also effective.
Conceptually, therefore, slow-release fertilizers provide the only effective solution
to the problems created by the ever increasing demand and use of water soluble
nitrogenous fertilizers. By substituting soluble compounds with sparingly soluble
compounds, it will be possible to greatly reduce fertilizer consumption, improve
fertilizer use-efficiency and prevent environmental damage.
The water solubility of nitrogenous compounds can be reduced by physical or
chemical methods. Physical methods depend on coating or encapsulation of water
soluble materials with outer layers of organic or inorganic materials. Encapsulated
materials are characterized by diffusion controlled release of nutrients through the
surface layer. Physical methods of control include sulphur, polymer and mixed
DMTU further reacts with monomethylol urea to form the four urea oligomer:
trimethylene tetraurea (TMTU). Again, a molecule of water is formed.
4 Varadachari and Goertz
This reaction sequence will continue until all the methylol ureas are consumed
(reacted). The higher polymers are: tetramethylene pentaurea (TMPU), pentamethylene
hexaurea (PMHU) and so on. Longer the polymer chain length, the lower the
solubility and the slower the release of nitrogen to the environment. The methylene
urea polymerization reactions can be more simply represented as:
U + UF UMU + H2O
UMU + UF UMUMU + H2O
UMUMU + UF UMUMUMU + H2O
UMUMUMU + UF UMUMUMUMU + H2O
UMUMUMUMU + UF UMUMUMUMUMU + H2O
polymer would have a U/F ratio approaching one (1), i.e., n urea molecules and
n-1 formaldehyde molecules. However, due to the random nature of the reaction,
high U/F ratio resins will generate some higher oligomers. Conversely, low U/F
ratio resins will produce some lower oligomers but the distribution will be towards
the higher chain length. U/F ratio can also be thought of as the average of the
polymer distribution. In most cases, unreacted (residual) urea will be present in the
final product. Again, this is because the random events of the reaction consume
all the monomethylol urea, before all the urea is consumed. Typically, low U/F
ratio products will have low amounts of residual urea; whereas products made
with higher U/F ratios will have higher amounts of unreacted (residual) urea.
2.1.3.3 Temperature
The temperature has a direct impact on the speed of the polymerization reaction.
Higher the temperature, quicker is the reaction. Temperature is a measure of
the kinetic energy in the system. At higher temperatures, the molecules have
higher kinetic energy and are moving around more rapidly. Since the reaction is
a random collision of molecules, higher temperatures also mean lower control
over the final polymer distribution. The speed of chemical reactions is typically
governed by the rate constant. This rate constant (k) is affected by temperature
and the dependence may be represented by the Arrhenius equation: k = Ae –E/RT
where the pre-exponential factor A is assumed to be independent of temperature,
R is the gas constant and T the temperature in degrees K. Generally speaking,
the rate of reaction will double with every 10oC. For example, the reaction at
100oC will proceed at twice the rate as the reaction at 90oC.
2.1.3.4 pH
The UF polymerization reaction proceeds under low pH conditions. Acid, used
to lower the pH, is the catalyst which initiates the reaction. Catalysts enable
reactions to occur much faster or at lower temperatures because of changes that
they induce in the reactants. Catalysts provide an alternative pathway of lower
activation energy for a reaction to proceed. Molecules that would not have had
the energy to react or that have such low energies that they probably would have
taken a long time to react are able to react in the presence of a catalyst. Thus,
more molecules that need to gain less energy to react will go through the chemical
reaction. This can be observed in the following energy profile diagram.
TN = CWSN + CWIN
The solid phase reaction involves feeding solid urea into a reactor at a
controlled rate. An acid is added to the urea in small amounts to act as a catalyst.
Liquid isobutyraldehyde is also metered on to the urea at a specified rate. Solid
IBDU is formed very rapidly. The reaction product is neutralized with a base to
neutralize the excess acid. Water is generated from the condensation reaction,
resulting in a wet solid. The wet IBDU is dried and screened. Oversize is crushed
and rescreened. Undersize is granulated to the desire size through a number of
granulation techniques, compaction being a common technique.
The liquid reaction method is similar, except that the isobutyraldehyde is
reacted with aqueous urea in the presence of an acid catalyst. The insoluble IBDU
precipitates out of solution and is filtered and washed prior to drying, screening
and granulation.
2.2.4 Properties
The IBDU is a white solid which can be granulated to various desired particle
sizes. Typical commercial sizes are: powder, Micro size (SGN ~100); Mid size
(SGN~150); Granular (SNG~230), and Horticulture grade (SGN~270). Fertilizer-
grade IBDU contains 31% N (theoretical N content is 32.18%), of which about
90% is water-insoluble.
2.2.5 Mechanisms of Release
Nitrogen from IBDU is released solely by hydrolysis, thus the release is dependent
on water and pH (acid conditions increases rate of release). The release mechanism
functions by gradual hydrolysis of the sparingly water insoluble IBDU to urea
which is transformed to ammonium ions and further to nitrate (by soil bacteria).
Conditions which affect the contact between water and the product also impact
the rate of release. A prime example of such a factor is the particle size of the
product. Smaller particles have greater surface area with which to contact water.
Consequently, smaller particles release faster than larger ones. Particle size is
one of the primary ways of controlling the rate of release (longevity) of IBDU.
Because microbes have little effect on the release of this compound (unlike UF),
N will be released even in winter. The physical standards that are used to describe
UF compounds (e.g. WIN) cannot be applied to IBDU. Instead, the rate of
dissolution is used.
The rate of N release is a function of soil moisture (hydrolysis) and the size
of the IBDU particle; the more moisture available and the finer the particle size,
the more rapid the rate of N release. Soil temperature and pH have a limited
effect on IBDU’s solubility and rate of N release.
The IBDU is used on turf grasses, in commercial nurseries, in landscaping
and in specialty agriculture. N is released by hydrolysis when soil moisture is
adequate. Breakdown is increased in acid soils (Hughes, 1976). Most of the
applications are in the form of blended fertilizers, with IBDU as a component.
Agronomic response and safety margin are good with turf while with greenhouse
crops, phytotoxicity has sometimes been observed.
Rodrigues et al. (2010) studied the effect of IBDU, a polymer-coated
fertilizer, and 3,4-dimethylpyrazole phosphate (DMPP) as nitrification inhibitor.
Slow-Release and Controlled-Release Nitrogen Fertilizers 13
Urea produced mean yields statistically higher than control in all crops and in
both field and pot experiments. No significant differences in yield were usually
found among fertilized treatments. Basacote, a commercial material, produced
yields often not significantly different from that of control. They concluded that
from the agronomic point of view, none of the slow-release N materials provided
advantages over urea to be advised for the studied agro-ecosystems, especially
considering their high cost.
2.3 Urea Crotonaldehydes
2.3.1 Overview
Crotonylidene diruea is the reaction product of urea and acetaldehyde. This also
represents some old chemistry. A commercial process was disclosed in a 1966
patent application by BASF. Chisso Corporation holds the trademark for CDU
urea-crotonaldehyde slow release nitrogen. CDU was manufactured in Japan from
1964 to 2007 by Chisso Corporation. After 2007, manufacturing was transferred
to the joint venture, Chisso Asahi Fertilizer. BASF Aktiengesellschaft formerly
manufactured CDU in Germany but ceased this production in the late 1980s.
BASF currently imports CDU from Japan.
2.3.2 Chemistry
Crotonylidene diruea (IBDU) is a condensation product prepared by the acid
catalyzed reaction of urea with acetaldehyde. The reaction yields the ring-structured
compound, CDU.
The reaction yields a single oligomer, unlike the urea formaldehyde reaction,
which produces a distribution of different polymer chain lengths. The total N
content of fertilizer-grade CDU is about 32%.
2.3.4 Commercial Processes
A process for the manufacture of CDU is disclosed in a 1966 patent publication
by BASF. An aqueous solution of urea is reacted with a molar excess acetaldehyde
(acetaldehyde/urea mole ratio between 1 and 1.5). An acid catalyst is added to
the reaction mixture such that the pH is less than 3. The reaction is staged at
elevated temperatures, below 100oC. After the reaction goes to completion, the
mixture is neutralized with a base. The CDU is separated from the mother liquor,
filtered and dried.
14 Varadachari and Goertz
2.3.5 Properties
The total N content of fertilizer-grade CDU is about 32%. Because its N is
released from the CDU through hydrolysis and microbial degradation in the soil,
CDU is normally formulated into granules which are designed to affect the water
contact (particle size) or the microbial populations. One example is Chisso Asahi’s
formulations marketed under the trade name UBER. These formulations combine
CDU with several different materials. A water repellent material (e.g., wax) is
added to control the dissolution rate of CDU into the soil solution. A phosphate
compound is added to control the microbial population.
2.3.6 Mechanisms of Release
Nitrogen is released from CDU through hydrolysis and microbial degradation in the
soil. When dissolved in water, it gradually decomposes to urea and crotonaldehyde.
Soil moisture and microbial activity in the soil affect the nitrogen release rate.
As with IBDU, particle size greatly affects the rate of N release, with the rate of
release decreasing dramatically as particle size increases. Temperature, moisture
and pH also influence the rate of N release. CDU degrades more rapidly in acidic
soils than in alkaline soils. Even in acidic soils, however, CDU degrades more
slowly than IBDU. The main use of CDU is on turf and in speciality agriculture.
It is typically formulated into granulated NPK fertilizers.
3. COATED FERTILIZERS
Coated fertilizers encompass an entirely different class of slow/controlled release
products. Unlike reaction products which rely upon chemical reactions to limit the
water solubility of the fertilizer, coated fertilizers rely upon a physical barrier, or
coating to prevent or control the rate of release of nutrient into the soil solution.
Typically, each individual fertilizer granule is encapsulated or wrapped with a
water insoluble or water impervious coating material. Water must, therefore,
penetrate the coating in order to solubilize the fertilizer core. Once solubilized,
the fertilizer solution inside the particle must be transported through the coating
before it can be released to the environment. The rate of nutrient release (rate
of water in/rate of fertilizer solution out) from coated products is affected by
the properties of the coating material (such a water permeability and fertilizer
permeability coefficients), the coating integrity (defects in the coating) and
coating thickness. When properly engineered, coated fertilizers have the potential
for controlling or metering the release of nutrients for very long periods of time
(up to 2 years) and with predetermined release profiles.
Some of the earliest work with coated fertilizers was conducted by the
Tennessee Valley Authority (TVA) with the development of sulphur coated
fertilizer. This work, dating back to the early 1960’s, centred around the concept
of encapsulating a fertilizer particle with sulphur. Sulphur was chosen because
of the high impermeability to water and because of its relatively low cost. This
work laid the foundation for a number of current day sulphur coated fertilizer
technologies. At about the same time frame, the Archer Daniels Midland company
was developing coated fertilizer technology, based upon polymer and resinous
coatings. This concept became the spring board to a large number of polymer
Slow-Release and Controlled-Release Nitrogen Fertilizers 15
initial release, to a linear release, among others. The quality of a polymer coated
fertilizer is measured by its repeatability in achieving a targeted nutrient release
pattern. A typical quality test for measuring the rate of nutrient release is to
place a small quantity of the coated product in a known quantity of water at a
set temperature. The water is sampled at predetermined time intervals to measure
the concentration of nutrient which has leached out of the coated fertilizer into
the water. The results are plotted against time to generate the nutrient release
profile at that particular test temperature. The rate of nutrient release from polymer
encapsulated fertilizer tends to be very temperature dependent. The rate of release
is accelerated at higher temperatures. Caution must be observed when trying to
extrapolate accelerated test results to actual field situation.
3.2.2 Processing Methods
All polymer encapsulated fertilizers are designed and built with three critical factors
in mind: selection of the fertilizer material, selection of the polymer coating and
selection of the application technique. Improper attention to any of these factors
can result in the formation of an inferior product. When all the three factors are
properly attended to, an excellent premium product can be manufactured.
1. Fertilizer selection: Numerous fertilizer products are available for coating. The
most common include urea, monoammonium phosphate (MAP), diammonium
phosphate (DAP), potassium chloride (MOP), ammonium nitrate and ammonium
sulphate; virtually any solid fertilizer can be coated. The key feature of the
fertilizer is that it must be granular. The smaller the granule, the greater the
amount of coating is required because of the increased surface area. The surface
characteristics of the granule are also very important. Irregular granules are
more difficult to coat uniformly and require larger amounts of coating than
smooth, round granules. The particle size distribution of the granules is also
very important. Products with high uniformity indexes (UI) and repeatable
particle size distributions will produce a consistently better final product than
those made with variable particle size distributions.
2. Polymer selection: A number of factors enter into the selection of the proper
polymer system. One of the most important is the permeability to water. This
is an inherent property of the polymer. Polymers with low water permeability
will provide better barriers than polymers with higher water permeability. The
water vapour transmission rate, the rate at which water moves through the
polymer coating is also a function of the coating thickness. The water vapour
transmission rate can be affected by imperfections in the coating. Sometimes,
imperfections are purposely introduced to provide channels for water movement
into and out of the particle. The viscosity or fluidity of the polymer system is
another important consideration. The viscosity affects the ability to uniformly
coat the fertilizer particles with an even coating thickness. If the viscosity
is too high, some particle will receive more polymer than others and they
will tend to agglomerate. Polymers are sometimes dissolved or diluted with
a solvent to reduce the viscosity. The solvent is subsequently evaporated and
recycled. Another consideration is the cure time of the polymer. This is the
amount of time needed for the polymer to cure to a non-tacky condition. A
18 Varadachari and Goertz
and has longevity of about 23 weeks. This product might be made with a thicker
coating or with a polymer having lower water permeability. Some manufacturers
utilize blends of different polymers or introduce impurities in the coating to create
channels to accelerate the water transport through the polymer film.
Christianson (1988) studied a reactive layer coated urea (RLCU) developed
by coating urea with a mixture of diisocyanate and polyol in the presence of a
catalyst. He showed that urea release tended to be in two stages (i) a constant
diffusive stage in which, it is postulated, urea was still dissolving within the
granule and diffusing to the soil at a constant rate and (ii) a slower logarithmic
stage where the rate of release decreased with time. Fujinuma et al. (2009) showed
that both soil temperature and soil moisture content controlled the cumulative N
release (CNR). The difference between model estimates and field measurements
of CNR indicated that the temperature model significantly underestimated CNR
by as much as 18% and this difference was reduced to 8% using the moisture-
temperature model. Therefore, a model parameterized by both soil temperature
and soil moisture would improve estimates of CNR from surface-applied CRF.
3.2.4 Advantages/Disadvantages
Polymer coated fertilizers represent the high end of the technology scale for
enhanced efficiency fertilizers. They can be designed for very long or short
longevities. They can also be designed to release in predetermined patterns and
they can control the release of multiple nutrients as well a single nutrient. The
disadvantages are usually associated with high cost. Also, the release patterns tend
to be highly temperature sensitive. As a result, the coatings need to be adjusted
for different climatic conditions. Finally, the products are limited by the fertilizer
which can be coated. This sometimes restricts the use in certain markets, for
instance, market requiring very small particles.
3.2.5 Agronomic Studies
Hummel (1989) evaluated four experimental resin-coated ureas (RCU) for
fertilization of turf grass. The most rapid response to fertilization as measured by
fresh weight yields and color ratings was produced by urea, followed by SCU,
RCU (with 70 days release rates), and RCU (with 100 days release rates). The
highest N recovery in the leaf tissue was obtained from oxamide, single-spring
application of SCU, and split applications of RCU-100 and RCU-70. Peacock
and DiPaola (1992) studied the response of Bermudagrass to RLC ureas and
concluded that best turf quality was for RLC carriers that combined slow and
intermediate release rate RLC ureas (12.5% or 10.8% coating + 7.2% coating)
with urea. Equivalent growth was noted for the urea together with 9.9% RLC and
sulfur coated urea. Use of slow release RLC N carriers as turf fertilizers showed
promise as a combination material with urea. Cahill et al., (2010) compared UAN
with four slow release fertilizer sources, viz., NutriSphere (Specialty Fertilizer
Products, Leawood, KS), Environmentally Smart Nitrogen Polymer Coated Urea
or ESN (Agrium Inc., Alberta, Canada), UCAN-23 (Yara, Tampa, FL) and UAN.
They concluded that the use of the alternative products did not regularly produce
more corn or wheat grain compared to UAN. Wheat straw yield was greater with
20 Varadachari and Goertz
NutriSphere, UCAN and UAN compared to ESN. Release time of NutriSphere and
UCAN was similar to UAN while ESN showed a slower release rates. However,
differences in release did not affect yields of spring planted corn, NutriSphere and
ESN increased corn stover yields in 3 of 6 site-years. Noellsch et al. (2009) studied
the effects of conventional and slow-release N fertilizer sources and landscape
position on corn (Zea mays L.) in a claypan soil. Anhydrous ammonia and PCU
treatments increased grain yield of 1470 to 1810 kg ha−1 over urea in the low-
lying position in 2005 and 2006. Based on the grain yield and different fertilizer
cost and crop prices, gross profit differences for use of PCU and preplant-applied
anhydrous ammonia compared with urea in the low-lying position could range
from $50 to $642 ha−1. In another study Smart Nitrogen (ESN) and Duration
Type 5 (D5) and preflood-applied urea showed that nitrogen recovery at panicle
differentiation averaged 30% for D5, 26% for ESN and 72% for urea and at
heading, averaged 47% for D5, 37% for ESN and 101% for urea (Golden et al.,
2009). Yield predictions for D5 were always lower than for urea at the same N
rates. Results suggested that the N release from D5 and ESN was too rapid for
rice cultivated in the direct-seeded, delayed-flood method. Wilson et al. (2009)
studied the effectiveness of a new type of PCU (Environmentally Smart Nitrogen,
Agrium) on potato. Overall, PCU and soluble N at equivalent N rates were found
to have similar total and grade A yields and net monetary returns. The optimal N
rate that resulted in maximum net returns was 251 and 236 kg N ha−1 as soluble
N and PCU, respectively. Overall, PCU may reduce or eliminate the need for split
applications of N on coarse-textured soils. Five different N sources were compared
with null N treatment to evaluate their performance for N-rich reference plot
establishment in corn (Yu et al., 2010). The sources included calcium ammonium
nitrate (CAN), urea ammonium nitrate (UAN), polymer-coated urea (PCU) and
environmentally smart nitrogen (ESN) and urea, broadcast or in-soil banded at
the rate of 225 kg N ha−1. All sources were observed to be equally effective to
establish N-rich reference plots.
3.3 Neem Coated
3.3.1 Overview
Azadirachta indica, the neem tree, which grows in India has nitrification retardation
properties as well as insect repellent and bacteriostatic properties. The oil obtained
from its fruits and the press cake from the production of neem oil are used for
the production of neem coated urea or NCU.
3.3.2 Commercial Processes
A technique for coating urea with neem cake was developed at IARI, New Delhi.
The neem cake is coated on to urea using a coal-tar kerosene mixture (Prasad et al.,
1999). Another technique of coating urea with neem oil micro-emulsion was
developed at IARI (Prasad et al., 1999; Suri et al., 2000). This has been adapted
by several companies in India and is sold as neem coated urea.
3.3.3 Agronomic Studies
Reddy and Prasad (1975) reported that percent inhibition of nitrification with
neem cake coated urea was 5% after 3 weeks. Other studies in India showed
Slow-Release and Controlled-Release Nitrogen Fertilizers 21
that coating urea with neem cake/oil/ bitterns could retard nitrification for 2-3
weeks (NAAS, 2006). Prasad et al. (2002) reported the superiority of NCU over
conventional urea for rice. Field trials by National Fertilizers Limited showed
a yield increase of 10.4 % in Haryana, 9.6 % in UP and 14 % in Punjab over
prilled urea. However, there are conflicting reports on the performance of NCU.
Bhatia et al. (1985) did not observe any significant advantage with wheat whereas
Chauhan (1999) and Tomar and Sharma (2000) observed yield benefits in rice-
wheat cropping systems with NCU. Trials conducted by Kribhco showed that neem
emulsion coating was superior to prilled urea, extends the shelf life of urea, helps
in sustaining nitorgen in the soil for a very long time resulting in better yields
for farmers and also acts as a pesticide. Reviews of the agronomic responses to
NCU are available in Prasad et al. (2005, 2007).
3.4 Degradable Polymer Coated
These are mostly in patent literature and describe biodegradable coatings containing
cellulose derivatives, lactic acid polymers, low molecular weight polyethylene, low
molecular weight wax and low molecular weight paraffin (Douglas and Golden,
1995; Gnatowiski et al., 1998). Haberle (2003) describes methods for producing a
biodegradable coating using dispersions containing polymers of urethane and urea
groups for surface treatment. Photodegradable polymers that undergo degradation
from the action of sunlight have also been developed for use as coatings. In many
cases, polymers are attacked photochemically and broken down to small pieces.
Further microbial degradation must then occur for true biodegradation to be achieved
(Kolybaba et al., 2003). Polyolefins polymers are found to be most susceptible
to photodegradation. Proposed approaches for further developing photodegradable
biopolymers include incorporating additives that accelerate photochemical reactions
(e.g. benzophenone), modifying the composition of the polymers to include more
UV absorbing groups (e.g. carbonyl) and synthesizing new polymers with light
sensitive groups (Andreopoulos et al., 1994).
3.5 Latex, Clay, Gypsum and Other Coatings
Different natural organic and inorganic materials have been developed for fertilizers
coatings. A lac coated urea (LCU) was developed by the Indian Lac Research
Institute, Ranchi. Studies by Singh et al. (1999) showed improved yields of
LCU over urea in rice-wheat cropping systems. Hassan et al., (1990) studied the
viability of an encapsulated urea-rubber matrix. Field trials and incubation studies
showed that it prevented the inhibition of seed germination, which is experienced
at high temperatures following high urea applications. Otey et al. (1984) described
a starch-blended urea with a N stabilizer. Depending upon the technique used,
the particles released 15-40% and 15-60% of the formulated urea in water within
1 hour. Nitrapyrin was slowly volatilized from moist particles but evaporation
from dry particles was negligible.
Vlnaty and Elizer (1991) describe a coating formed by the acidification of
preconditioned calcium metasilicate with citric acid which is then mixed with
cement. The calcium metasilicate was heated to 1300° C, then pelletized and cured
to form a silica gel matrix containing acicular calcium metasilicate and a cement
coating on the pellets. The Institute of Soil Science, Chinese Academy of Sciences
22 Varadachari and Goertz
soils saved up to 25% nitrogen with no reduction in yield of the rice crop. A
machine has been modified and now it is possible to deep-place N fertilizers
mechanically in just one pass of the machine (IFDC, 2010).
Placement of USG at 7–10 cm soil depth can be done by hand after or
during conventional line transplanting with one USG near the center of each of
four rice hills. The IFDC methods have been developed mainly for economically
disadvantaged small rice farmers of developing countries, who transplant rice at
random in rainfed areas. Various continuous operation-type applicators (prototypes)
have been developed in Philippines, India and China for mechanical deep placement
of USG in line-transplanted rice (Gupta, 2002). The non-continuous operation-type
can help to save up to 40% of the labour required for the hand placement method
(Savant and Stange, 1990). Since deep-placed USG-N is well protected from
various N loss mechanisms (except leaching) the placement sites in soils and the
spatial ammonium concentration gradients help to improve its plant availability.
The benefits are, viz., (1) uptake of N by rice plants (recovery) is significantly
increased, (2) relatively smaller amounts of USG-N as non-exchangeable ammonium
and/or immobilized organic N stay in soil and (3) eventually N losses (gaseous
and runoff) are markedly decreased. Thus, this practice is agronomically efficient
as well as environmentally safe.
5.2 Agronomic Studies
Several hundred field trials conducted by national and international institutions
in south and southeast Asia since 1975 have demonstrated that deep-placed USG
can result in urea savings of up to 65% with an average of 33% and can increase
grain yields up to 50% with an average of 15% to 20% over that with the same
amount of split-applied N as urea.
Roger et al. (1980) conducted field trials with supergranules and briquettes
of 1-3 g discrete particles placed 10 cm deep in the soil at a rate of one for
every 4 hills of rice. Experiments in 11 countries showed that deep placement of
urea supergranules and the use of a slow-release fertilizer increased rice yields
compared with conventional split application of urea. A two-year field study
was carried out to compare the efficiency of prilled urea and urea-supergranules
in the cultivation of a perennial aromatic grass, citronella in a sandy loam soil.
Application of 300 kg N ha–1 year–1 increased the herb and essential oil yields.
USG significantly increased the yields over prilled urea (Prakasa Rao et al., 1984).
It has been observed that depending upon soil and agroclimatic conditions, one
time application of deep placed USG produced on an average yield benefit of 15-
20% over that obtained by the same amount of N applied in split doses through
prilled urea (Meelu et al., 1983; Singh et al., 1990; Pandey et al., 1989; Prasad
et al., 1989). Deep placed USG, however, did not perform better than prilled
urea in coarse textures soils with high percolation rates as are commonly found
in Indian Punjab (Bijay-Singh and Katyal, 1987). In spite of distinct advantage
of USG in fine textured soils, it could not gain popularity with farmers due to
lack of suitable mechanical applicator.
Slow-Release and Controlled-Release Nitrogen Fertilizers 25
ammonia monooxygenase
NH3 + O2 + 2H+ ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ → NH OH + H O
2 2
hydroxylamine oxidoreductase
NH2OH + H2O ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ → NO – + 5H+
2
nitrite dehydrogenase
H+ + NO2– + H2O ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ → NO – + 3H+
3
Nitrification inhibitors are chemicals that slow down the process of nitrification,
i.e., the transformation of NH3 to NO2–. This is due to inhibition of the activities
of the Nitrosomonas group of bacteria that transform NH4+ to NO2–; the formation
of NO3– is thus, slowed down. Leaching as well as volatilization losses are reduced
because the nitrogen remains in the NH4+ form.
7.1.2 Commercial Materials
Two nitrification inhibitors such as Nitrapyrin (N-serve) and Dicyandiamide
(DCD) have been widely studied and successfully marketed. Nitrapyrin [2-chloro-
26 Varadachari and Goertz
soils which have high urease activity, volatilization loss of NH3 is high or urea
infiltration into the soil is poor.
7.2.2 Commercial Materials
Four main classes of urease inhibitors are: (i) reagents which interact with the
sulphydryl groups (sulphydryl reagents), (ii) hydroxamates, (iii) agricultural crop
protection chemicals and (iv) structural analogues of urea and related compounds
(Watson, 2005). However, few meet the requirements of being effective at low
concentrations, non-toxic, stable, inexpensive and compatible with urea (Trenkel,
1997). The most common urease inhibitor, NBTPT (N-[n-butyl] thiophosphoric
triamide), was initially developed by Freeport McMoRan and licensed to IMC-
Agrico. It was first introduced for the American corn market under the trade
name of Agrotain (Watson, 2005). Agrotain is primarily recommended for pre-
plant surface application of urea and urea-containing fertilizers but can be used
as pre-emergence, side dressing, top-dressing or other post-planting applications.
Agrotain has been shown to significantly reduce N leaching compared to urea in
a fine sandy soil (Prakash et al., 1999).
7.2.3 Agronomic Studies
Numerous field trials involving corn and solid urea plus NBTPT conducted in the
US showed that the average increase in yield to NBTPT addition in 316 replicated
nitrogen responsive sites was 0.89 t/ha (Watson, 2005). In contrast to solid urea,
UAN solutions treated with NBTPT resulted in an increase in corn yields of
0.56 t/ha, when averaged for 119 replicated sites (Trenkel, 1997). McKenzie et
al. (2010) evaluated PCU and NBTPT on winter wheat. When N fertilizer was
banded at seeding, grain yield was higher for PCU than NCU, but differences
were small (<100 kg ha−1, <5%) and likely not due to reduced N losses. Grain
protein concentration was unaffected by fertilizer type. When N fertilizer was
broadcast on the soil surface in the spring, grain yield and protein concentration
were comparable to urea, AN, and NTU (NBPT-treated urea) but reduced
for PCU due to excessive delay in N release. The negligible impact of polymer
coating or treatment with NBPT on urea efficacy reflects the low risk of urea N
loss in this region.
7.3 Natural Inhibitors
Subbarao et al. (2009) showed that certain plants release nitrification inhibitors
from their roots. Such biological nitrification inhibition (BNI) capacity appears
to be relatively widespread among tropical pasture plants, with Brachiaria spp.
having the highest capacity among the pasture grasses tested. The potential for high
BNI capacity also exists in wild wheat. A pasture grass, Brachiaria humidicola
(Rendle) Schweick, native to tropical Africa and grown extensively in tropical
South American grasslands, releases substantial amounts of BNIs from its roots,
ranging from 17 to 50 ATU per gram of root dry weight per day (23, 24). In a
review article, Subbarao et al. (2009) have discussed the potential for BNI.
An enzyme hydrolyzing slow release nitrogen fertilizer, methylene urea, was
purified from Rhizobium radiobacter. Based on the kinetic properties, substrate
28 Varadachari and Goertz
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Slow-Release and Controlled-Release Nitrogen Fertilizers 33
Cote N
Coating: Polymer
Substrates: Urea
Analysis: 14-14-14/ 15-7-15+Micro/10-48/
Longevity: 4 to 16 months
Markets: Arable crops
Chisso Asahi Fertilizer Corporation Ltd. (now JCAM Agri
Co. Ltd through merger with Mitsubishi Chemical Agri, Inc.)
LP Coat®, Meister®
Coating: Polyolefin resin
Substrates: Urea
Longevity: 20 to 270 days (25 C)
Size: 2-4 mm
Markets: Rice, Other Crops, Turf, Trees, Flowers, Export
Ecolong ®, Long ®, Hi-control®,Nutricote ®
Coating: Polyolefin resin
Substrates: N, P, K + micronutrients
Longevity: 20 to 270 days (25 C)
Size: 2-4 mm
Markets: Garden vegetables, landscape, export.
Central Glass Company
Analysis: 41-0-0
Markets: Paddy Rice
Nissan Agri Corporation
Zetto ®
Coating: Polymer
Substrates: Urea
Markets: Paddy Rice, Field Crops
Shandong Kingenta Ecological Engineering Co. Ltd.
Polymer Coated Fertilizers
Coating: Thermoplastic and Thermoset
Substrates: Urea, DAP, KNO3, NPK
Analysis: 42-0-0, 16-44-0, 12-0-43, 20-8-10, 14-14-14, 11-11-16.
Longevity: 3,6,9,12 months
Size: 1.5 to 4.75 m
Sumitomo Chemical Co. Ltd.
SR Coat®, Super SR Coat ®, Sumi-Coat®, Super Sumi-Coat®.
Coating: Polymer
Substrates: Urea, NPK
Analysis: 41-0-0
Longevity: 200-360 days
Markets: Rice, Vegetables, Fruit.
Taki Chemical Co. Ltd.
Taki-coat®, Magphos-coat®, Magphos-coat S®
Coating: Alkyd resin
Substrates: Urea, Magnesium Phosphate
Longevity: 40-140 days
Markets: Rice, Vegetables
Ube Agri-Materials, Ltd.
U-Coat®, AS-Coat®
Coating: Polymer
Substrates: Urea, Ammonium Sulfat, NPK
Longevity: 70, 100 days
Markets: Rice, Vegetables, Tea
2. NORTH AMERICA
2.1 Condensation Polymers
2.1.1 Urea formaldehydes
Agrium Advanced Technologies
Nutralene® Slow-Release Nitrogen
Chemistry: Methylene Ureas
Analysis: 40-0-0
Longevity: up to 16 weeks
Size: SGN 225, 150, 95
Markets: Professional Turf, Professional Horticulture
Ashland Hercules Water Technologies
Nitroform® Slow-Release Nitrogen
(produced under contract for Agrium Advanced Technologies)
Chemistry: Ureaform
Analysis: 38-0-0
Longevity: 2/3 of Nitrogen as WIN
Size: SGN 225, 150, Powder
Markets: Professional Turf, Professional Horticulture.
Slow-Release and Controlled-Release Nitrogen Fertilizers 37
Longevity: 12 to 16 weeks
Size: SGN 195, SGN 145
Markets: Professional Turf, Home and Garden,
Specialty Ag.
Morral Companies
NBN-30.
Chemistry: Urea, triazone
Analysis: 30-0-0, 50% slowly available N
Size: Clear liquid
Markets: Professional Turf
Scotts Miracle Gro Company
Turf Builder® (Granulated NPK); Lawn Pro® (Granulated NPK)
Chemistry: MDU/DMTU Compositions
Analysis: Variable analyses
Longevity: 6-8 weeks
Size: <10 mesh (US Sieves)
Markets: Home and Garden
3. EUROPE
3.1 Condensation Polymers
3.1.1 Urea formaldehydes
Sadepan Chimica S.r.l
Sazolene SC
Chemistry: Methylene ureas
Analysis: 28-0-0, 59%% slowly available
Longevity: 2-4 months
Size: Liquid
Markets: Professional Turf, Home and Garden, Professional Horticulture,
Specialty Ag.
Sazolene 39G Balanced
Chemistry: Methylene ureas
Analysis: 39-0-0, 91% slowly available
Slow-Release and Controlled-Release Nitrogen Fertilizers 41