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Slow-release and Controlled-release Nitrogen Fertilizers
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BULLETIN NO.: 11
ING Bulletins on
Regional Assessment of Reactive Nitrogen
Series Editor: Y.P. ABROL

Associate Editor: SUSMITA CHATTERJEE
Slow-release and Controlled-release

Nitrogen Fertilizers
CHANDRIKA VARADACHARI and HARVEY M. GOERTZ
EDITOR: BIJAY SINGH
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
SLOW-RELEASE AND CONTROLLED-RELEASE NITROGEN FERTILIZERS
First Published in 2010
© Society for Conservation of Nature
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.
For copies write to:

Professor Y.P. Abrol
President, Society for Conservation of Nature
G-4,CGIAR Block, NASC Complex,
Dev Prakash Shastri Marg New Delhi-110012
E-mail: ypabrol@gmail.com
Published and Printed by ING-SCON in collaboration with Angkor Publishers

Pvt. Ltd., B-66, Sector 6, Noida-201301. E-mail: angkor@rediffmail.com; Mobile:
9910161199
CONTENTS
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
2.2.4 Properties 12
2.3 Urea crotonaldehydes 13
2.3.1 Overview 13
2.3.2 Chemistry 13
2.3.5 Properties 14
3. COATED FERTILIZERS 14
3.1 Sulphur coated (including sulphur/polymer coated) 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
3.4 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
7.2 Urease Inhibitors 26
7.2.1 Overview 26
7.2.2 Commercial Materials 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
1.Corresponding Author’s E-mail: cv@rcais.res.in
Abbreviations : UF (urea-formaldehyde); IBDU (isobutylidene diurea); CDU (crotonylidene

diurea); UFP (urea formaldehyde polymer); UAN (urea ammonium nitrate); SCU
(sulphur coated urea); NCU (neem coated urea); PCU (polymer coated urea);
LCU (lac coated urea); USG (urea supergranules)
2 Varadachari and Goertz
sulphur-polymer encapsulated materials (Oertli, 1980; Hummel and Waddington, 1984;

Booze-Daniels and Schmidt, 1997) and resin coatings (thermoset and thermoplastic
resins) such as osmocote (Hulme and Buchheit, 2007). Chemical methods of control
include conversion of nitrogen to polymeric forms that have reduced water solubility.
Hydrolysis controlled release is characteristic of materials like urea formaldehydes,
isobutylidene diurea (IBDU) and crotonylidene diurea (CDU). Other types of slow-
release and controlled release formulations include gel forming materials, zeolite
based materials as also urease and nitrification inhibitors.
2. CONDENSATION POLYMERS
2.1 Urea Formaldehydes
2.1.1 Overview
Urea-formaldehyde reaction products represent one of the older Slow Release
Nitrogen (SRN) technologies. A disclosure of the reaction products of urea and
formaldehyde was made as early as 1924 in a German patent granted to Badische
Anilin und Sodafabrik (BASF, 1965). In 1948, United States Department of
Agriculture (USDA) reported that urea and formaldehyde could react to produce
a slow release fertilizer at urea to formaldehyde mole ratios (U/F ratio) greater
than one. Urea formaldehyde reaction products represented the first synthetically
produced form of slow release nitrogen and were commercialized in 1955 under
the trade names Uramite (DuPont) and Nitroform (Nitroform Corp).
2.1.2 Chemistry
Urea-formaldehyde (UF) fertilizers are prepared from the reaction of formaldehyde
with excess urea (U/F ratio > 1). The reaction proceeds in two steps, (1) methylol
urea resin formation and (2) methylene urea polymerization (Goertz, 1993a).
Step 1 — Methylol Urea Formation: Methylol ureas are necessary reaction
intermediates (precursors) to the formation of methylene urea polymers. These are
formed through an addition reaction between urea and formaldehyde under basic
(high pH) conditions. There are two types of methylol ureas, monomethylol urea
and dimethylol urea, both of which are soluble in water. The first formaldehyde
molecule attaches itself to urea to form monomethylol urea. If additional formaldehyde
is present, an additional formaldehyde molecule attaches itself to monomethylol
urea to form dimethylol urea. The reactions are reversible as shown below.
O O
base
H2C — C — NH2 + CH2O H2N — C — NH — CH2 — CH
urea formaldehyde monomethylol urea
The chemical equations can be more simply represented as:

U+F UF and F + UF FUF
Slow-Release and Controlled-Release Nitrogen Fertilizers 3
where: U = urea, F= formaldehyde, UF = monomethylol urea, FUF = dimethylol

urea.
As mentioned, the reactions are reversible. Therefore, a UF resin will contain

a mixture of all the aforementioned molecules. Excess formaldehyde will drive the
equilibrium to the right to form a predominance of dimethylol urea (FUF). Excess
urea will favour the formation of monomethylol urea (UF). UFC 85, a common
UF resin used for fertilizer manufacture, has a predominance of formaldehyde
over urea (F/U ratio = 4.8). It is essentially an equilibrium mixture of dimethylol
urea (FUF) and formaldehyde (F) in an aqueous solution. High pH conditions
(e.g.: pH>8.5) will keep these solutions stable for long periods of time.
Step 2 — Methylene Urea Polymerization: Methylene ureas are polymers
(oligomers) of varying chain length formed from the condensation reaction of
urea with methylol ureas (Goertz, 1993b). They have varying solubility in water.
The water solubility decreases as the chain length (degree of polymerization)
increases. This feature gives these compounds excellent utility as slow release
nitrogen fertilizer sources. For instance, urea has a solubility of about 100 g per
100 g of water at room temperature. By contrast, the two urea oligomer (MDU)
has a solubility of about 2.5 g per 100 g of water. The three urea oligomer
(DMTU) has a solubility of about 0.1 g per 100 g of water. The higher polymers
are essentially insoluble in cold water.
The methylene urea condensation reaction occurs, under acidic conditions, in a
step-wise fashion as shown below. First, urea (U) reacts with monomethylol urea
(UF) to form the two urea oligomer, methylene diurea (MDU). As it is formed,
a molecule of water is also formed.
Next, MDU reacts with another molecule of monomethylol urea to form

the three urea oligomer: dimethylene triurea (DMTU). As this occurs, another
molecule of water is liberated.
DMTU further reacts with monomethylol urea to form the four urea oligomer:
trimethylene tetraurea (TMTU). Again, a molecule of water is formed.
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
where: U = urea; M = methylene linkage; UF = monomethylol urea; UMU =

methylene diurea (MDU); UMUMU = dimethylene triurea (DMTU); UMUMUMU
= trimethylene tetraurea (TMTU); UMUMUMUMU = tetramethylene pentaurea
(TMPU); UMUMUMUMUMU = pentamethylene hexaurea (PMHU)
2.1.3 Synthesis Routes
2.1.3.1 Reaction Kinetics
In actual practice, the reaction of urea with formaldehyde produces a distribution
of polymers of varying chain length. The distribution is affected by the U/F mole
ratio as well as the reaction conditions such as temperature, pH and reaction
time (Alexander and Helm, 1990; Goertz 1993a). Under low pH conditions,
the polymerization reaction can be thought of as a sequence of random events.
Monomethylol urea seeks another molecule to attach to. If it finds a urea
molecule, it attaches to it to form MDU. If it happens to find an MDU molecule,
it attaches to it to form DMTU. If it finds a TMTU molecule, it attaches to it to
form TMPU and so on. The reaction proceeds until all the monomethylol urea
has been consumed. Because polymerization is a series of random events, the
speed of reaction affects the polymer distribution. Fast reactions tend to be less
controlled and produce longer chain polymers. Slower reactions tend to produce
shorter chain polymers.
2.1.3.2 U/F
The U/F ratio is the ratio of urea molecules to formaldehyde molecules in the
reaction mixture (resin). It determines the number of methylene linkages which
bind the methylene urea polymers together. Higher the U/F ratio, lower the amount
of methylene linkages and lower the degree of polymerization in the product.
Conversely, lower the U/F ratio, greater the amount of methylene linkages and
greater the degree of polymerization. In theory, MDU (methylene diurea) has a
U/F ratio of two – which means two urea molecules and one methylene linkage
(formaldehyde molecule). On the other hand, an infinitely long methylene urea
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.
Lower the pH (the more acid that

is used), quicker the reaction. The
quicker the reaction, control to prevent
the formation of long polymer chains
is lesser. Regulating the pH (amount
of acid) can be used as a means of
controlling the rate of reaction.
2.1.3.5 Reaction Time

Reaction time is a measure of reaction speed. Faster reaction suggests less control
over the random collisions of the reagents and intermediates. Such conditions
promote the formation of longer chain polymers. Slower reaction speed (slower
reaction time) affords better reaction control and lesser tendency to produce
long polymeric chains. Temperature and pH are the customary variables used to
control reaction time. Reactions can be quenched by rapid alteration of either pH
or temperature (raising the pH or lowering the temperature). In quenching the
reaction, it should be ensured that all the monomethylol ureas have been consumed.
Residual methylol urea will add to the phytotoxic potential of the fertilizer.
2.1.4 Commercial Processes
A number of processing methods have been employed to manufacture UF reaction
products. They can be categorized into two main types – dilute solution processes
and concentrated solution processes (Goertz, 1993a).
In the Dilute Solution Process (DSP), both steps of the reaction (Step 1-
Methylol urea formation and Step 2- Methylene urea polymerization) are carried
out completely in a water medium. Step 1 involves reacting urea and formaldehyde
in a water solution, which is held under basic conditions and temperatures to
produce methylol ureas. The methylol urea solutions are sometimes marketed
directly as end user products. The Step 1 solutions are also used as precursor to
the production of methylene urea polymers (Step 2). In Step 2, the solutions are
acid or heat catalyzed to initiate the polymerization of urea and methylol ureas
to produce a series of methylene urea oligomers. The liquid reaction is held at
prerequisite times, temperature and pH to generate the desired methylene urea
polymer distribution. The reaction mixture is then neutralized with a base to
quench the reaction. Methylene diruea (MDU) is soluble in water and is sold as
a component in UF solutions. The higher oligomers are relatively insoluble and
precipitate out of solutions. They are sold as liquid suspensions or alternatively,
filtered, dried and sold as solid products. They can be subsequently granulated
as granular solid products. In contrast, the Concentrated Solution process (CSP)
uses little or no water. Only enough water is added to the methylol urea formation
(Step 1) to permit the dissolution of the urea so that it can react with the formaldehyde
to form the methylol ureas. At this point, the condensation polymerization is initiated
by either heat or acid catalysis to form a wet semi-solid which is subsequently dried
and/or granulated to produce of solid fertilizer composition. The polymerization
reaction can also be conducted in molten urea. In this instance, granulation is
achieved through solidification of the molten solution or slurry.
2.1.5 Properties
Urea-formaldehyde fertilizers can be produced in various physical forms: clear
liquid, liquid suspensions, dry powders and granular solids. Chemically, these can
encompass a wide range of oligomer distributions. Each oligomer distribution has
its own characteristic nitrogen release pattern and associated longevity in the field.
Characterizing these oligomer distributions has been a challenge, as only the very
short ones are soluble in water.
When the first UF fertilizers were commercialized in the mid-1950’s, analytical

techniques were not developed to the extent as they are today. There was no
practical way to identify and quantify the individual oligomers (polymer chains)
in the methylene urea polymer distribution. Nevertheless, methods were needed
to characterize the slow release properties of the products. The answer was to
characterize products based upon water solubility at various temperatures. The theory
was that the higher polymers (longer chain) would be less soluble in water than
the shorter chains; and that this was directly related to the longevity of release.
As a result, a classification system was developed which separated the nitrogen
(N) content of each product into three fractions (AAPFCO, 2005).
Fraction I: That portion of total N which is soluble in cold water (20-25oC)
when 1 g of product is placed in 250 ml of cold water (20-25oC). Technically,
this is called the cold-water-soluble nitrogen (CWSN). This can contain unreacted
(residual) urea, MDU, DMTU and other soluble reaction products. Some of the
CWSN is immediately available agronomically, whereas some is released over
a period of weeks.
Fraction II: That portion of total N which is insoluble in cold water (20-25oC)
when 1 g of product is placed in 250 ml of cold water (20-25oC) but soluble in
hot water (100oC). This is called the hot-water-soluble nitrogen (HWSN). Fraction
II consists of medium -length polymers (DMTU, TMTU, TMPU) from which N
is released over a period of several months. Soil bacteria slowly decompose these
chains into shorter lengths until they become soluble and available to the plant.
Fraction III: That portion of total N which is insoluble in hot water (100oC).
This is called the hot-water-insoluble nitrogen (HWIN). Fraction III is composed
of the higher MU polymers (long chain lengths) typically PMHU and higher. The
microbial breakdown of these polymers (and consequently N availability) can
be very slow, possibly over a number of years. Under certain conditions (cool
environments), the agronomic efficacy of this fraction is questionable. Furthermore,
the HWIN analysis is much dependent upon the particle size of the product.
Products which are not properly crushed/screened, will give erroneous results.
The relationships between these terms are as follows:
TN = Fraction I + Fraction II + Fraction III
TN = CWSN + HWSN + HWIN
TN = CWSN + CWIN
CWIN = HWSN + HWIN

where TN= total nitrogen; CWSN= portion of nitrogen which is soluble in cold
water (20-25oC); CWIN= portion of nitrogen which is insoluble in cold water
(20-25oC); HWSN= portion of nitrogen which is insoluble in cold water (20-25oC)
but soluble in hot water (100oC); HWIN= portion of nitrogen which is insoluble
in hot water (100oC). Recognizing the limited utility of Fraction III (HWIN), the
industry adopted a term called Availability Index (AI) to further characterize the
agronomic utility of products (AAPFCO, 2005).
Availability Index (AI): Also referred to Nitrogen Availability Index (NAI),

this is the percent of the cold water insoluble nitrogen (CWIN) which is soluble
in hot water (HWSN). In other words, it is the efficient portion of the CWIN.
The mathematical expression for AI is: AI = 100 x (HWSN/CWIN) or AI= 100
x (CWIN-HWIN)/CWIN
where AI= Availability Index
An AI of 100 would mean all the CWIN is HWSN (or Fraction II). This
would be a much more efficient fertilizer than one with an AI of 0 (all the CWIN
is Fraction III or HWIN).
2.1.6 Molecular Quantification
As the industry evolved, it became clear that there should be better ways of
characterizing methylene urea products than measuring the fractions which were
agronomically inefficient. Techniques were developed using High Performance
Liquid Chromatography (HPLC) which not only identified but also quantified
some of the individual methylene urea polymers. With these techniques, it became
possible to isolate the shorter chain polymers (MDU, DMTU) and document their
slow release effectiveness in the field.
HPLC procedures consist of pumping a liquid containing the molecules to be
measured through a packed column. It works on the principle that each molecule
will travel through the column at its own rate (speed). For instance, smaller
molecules will normally travel through the column faster than larger molecules.
A detector at the discharge of the column measures when and how much of each
molecule is in the solution as it exits the column.
Thus, HPLC has become a standard method of measuring the water soluble
components of a methylene urea fertilizer. It can measure the amount of unreacted
urea, the water soluble MDU, DMTU and any other component that is water
soluble. Thus, it is possible to measure the potentially phytotoxic components (urea,
unreacted methylol ureas) of a fertilizer as well as the efficient slowly available
water soluble nitrogen (MDU, DMTU) in one analysis (AOAC, 2010).
2.1.7 Product Classification
The Association of American Plant Food Control Officials (AAPFCO) is the
official agency for classifying fertilizer products including slow release fertilizers
in the United States. They define slow or controlled release fertilizer as follows
(AAPFCO, 2005).
T-29. Slow or controlled release fertilizer: A fertilizer containing a plant nutrient
in a form which delays its availability for plant uptake and use after application,
or which extends its availability to the plant significantly longer than a reference
rapidly available nutrient fertilizer such as ammonium nitrate or urea, ammonium
phosphate or potassium chloride. Such delay of initial availability or extended time
of continued availability may occur by a variety of mechanisms. These include
controlled water solubility of the material (by semi-permeable coatings, occlusion,
or by inherent water insolubility of polymers, natural nitrogenous organics, protein
materials, or other chemical forms), by slow hydrolysis of water soluble low
molecular weight compounds, or by other unknown means. (AAPFCO, 2005)
Slow release urea-formaldehyde fertilizer products are often divided into

three classes:
1. Short Chain Polymer Products: Sometimes referred to a MDU/DMTU
Compositions (Example products: Scotts Turf Builder)
1. Intermediate Chain Polymer Products: Sometimes referred to a Methylene ureas
(Example products: Nutralene from Agrium Advanced Technologies)
2. Long Chain Polymer Products: Sometimes referred to a Ureaform or Urea-
formaldehyde products (Example products: Nitroform from Agrium Advanced
Technologies)
2.1.8 Official Definition of Product Classes
1. Short Chain Polymer Products: Sometimes referred to as MDU/DMTU
compositions.
(a) N-28. Urea-formaldehyde products (water soluble) are reaction products
of urea and formaldehyde which contain at least thirty percent (30%)
nitrogen, largely in water soluble form. Some slowly available nitrogen
products are also present. Stable aqueous solutions may be prepared
from these materials. The reaction products shall contain a maximum
of fifty-five percent (55%) free urea, with the remainder of the urea
being chemically combined as methylolureas, methylolurea ethers and/
or methylenediurea (MDU) and dimethylentriurea (DMTU) (AOAC,
2010).
(b) N-29. Methylenediurea (MDU) is a water soluble condensation product
resulting from the reaction of one molecule of formaldehyde with two
molecules of urea, with the elimination of one molecule of water. It has
a minimum total nitrogen content of forty-two (42%) and is a source
of slowly available nitrogen (AOAC, 2010).
(c) N-30. Dimethylenetriurea (DMTU) is a water soluble condensation
product resulting from the reaction of two molecules of formaldehyde
with three molecules of urea, with the elimination of two molecules of
water and having a minimum total nitrogen content of forty-one (41%).
It is a source of slowly available nitrogen (AOAC, 2010).
2. Intermediate Chain Polymer Products: Sometimes referred to a Methylene
Ureas.
No official definition.
3. Long Chain Polymer Products: Sometimes referred to a Ureaform or Urea-
formaldehyde products.
(a) N-25. Ureaform fertilizer materials (sparingly soluble) are reaction
products of urea and formaldehyde which contain at least thirty five
percent (35%) nitrogen, largely in insoluble but slowly available form.
The water insoluble content shall be at least sixty percent (60%) of the
total nitrogen. The water insoluble nitrogen in these products shall have
an activity index of not less than forty percent (40%) when determined
by the appropriate AOAC International method. (AOAC, 1984)
(b) N-25. Urea-formaldehyde products (sparingly soluble) are reaction

products of urea and formaldehyde which contain less than thirty-five
(35%) percent nitrogen, largely in insoluble but slowly available form.
They shall have the percentage of total nitrogen as part of the product
name; for example, 20% N Urea-formaldehyde. The water insoluble
nitrogen shall be at least sixty percent (60%) of the total nitrogen. The
activity index of the water insoluble nitrogen shall be either (i) not less
than forty percent (40%) by the AOAC International method for urea-
formaldehyde products or (ii) not less than fifty percent (50%) by the
AOAC International alkaline permanganate method or eighty percent
(80%) by the neutral permanganate method (AOAC, 2005).
2.1.9 Mechanisms of Release
The UF fertilizers become assimilated into plants through a multi-step process.
As most UF oligomers are either sparingly soluble or insoluble in water, the first
step in assimilation involves getting the materials into the soil solution. Microbial
attack of the carbon in the methylene linkages is the generally accepted mechanism
(Christianson et al., 1988). As the methylene linkages are broken, the polymer
chain length is shortened and, eventually, molecular urea is liberated from the
polymer chain (Corke and Robinson, 1966). The rate at which this occurs is
dependent upon the original polymer chain length and by the intensity of the
microbial population. Thus, factors that promote a healthy microbial activity,
such as higher soil temperature, moisture, organic matter, soil aeration all tend
to accelerate the N release from UF fertilizers. Step 2 in the process occurs once
urea has been liberated from the polymer and is in the soil solution. The enzyme,
urease, catalyzes the hydrolysis of urea to the ammonium ion. Ammonium ion
can be taken up directly into the plant or (more likely) converted to the nitrite
ion, through the action of nitrosonomas bacteria and then to nitrate ion by
nitrobacter bacteria. Depending on the temperature and the health of the microbial
environment, Fraction 1 from UF fertilizers can release over a 2-4 week period.
Fraction 2 releases gradually over a 1-3 month period, and Fraction 3 releases
for four to six months or more.
Jhans and Kaltwasser (2000) studied microbial breakdown of UF products
and observed that N was released as ammonia and urea, and the formaldehyde
released was immediately oxidized via formate to carbon dioxide. A strain of the
gram-negative bacterium Ralstonia paucula completely degraded methylenediurea
and dimethylenetriurea to urea, ammonia, formaldehyde, and carbon dioxide.
Fungal degradation of methyleneureas may occur via the formation of organic
acids, thus leading to a nonenzymatic degradation of methyleneureas, which are
unstable under acidic conditions.
2.1.10 Agronomic Studies
Cahill et al. (2007) studied the effect of UFP (urea formaldehyde polymer) and
UAN (urea ammonium nitrate) on winter wheat and maize and concluded that
grain yield with UAN was similar to or better than UFP. Since UFP release
was limited to a time scale of days, it did not significantly improve yield. They
proposed that UFP may only be economical if priced similar to UAN. Power (1979)
compared the effects of S-coated urea and ureaformaldehyde with ammonium

nitrate on production of mixed native prairie vegetation. He observed dry matter
production from all rates of N application was greatest for ammonium nitrate and
least for ureaformaldehyde, with intermediate production for the S-coated ureas.
Fertilizer N recovery in harvested forage followed this same order. In general,
mixed prairie grasses used N from urea-containing fertilizers less efficiently than
that from ammonium nitrate. Hollingsworth et al. (2005) studied the effect of
the N sources, urea or methylene urea, on ultradwarf Bermudagrass cultivars. It
was concluded that turf colour and quality were often improved by application
of soluble N while thatch depth was unaffected by N source.
2.2 Urea Isobutyraldehydes
2.2.1 Overview
Isobutylidene diurea is a white, nitrogenous slow release fertilizer and is the
reaction product of urea and isobutyraldehyde. The chemistry is quite old,
dating back to a patent publication in 1964 by Mitsubishi Chemical Industries.
Subsequent patents were obtained by BASF and Hoechst Celanese. Mitsubishi
Chemical registered the tradename IBDU, which has become synonymous with
the product. Lebanon Seabord Corporation is the current holder of the tradename
IBDU in the United States.
2.2.2 Chemistry
Isobutylidene diruea (IBDU) is a condensation product prepared by a simple
reaction of isobutyraldehyde (a liquid) with urea. Unlike the urea formaldehyde
reaction, which produces a distribution of different polymer chain lengths, the
reaction of isobutyraldehyde and urea produces a single oligomer. It has the
following structural formula:
The reaction proceeds in two steps. In Step 1, urea reacts is isobutyraldehyde

to form the intermediate, iso-butrylol urea (IBU). The IBU subsequently reacts
with an additional urea molecule to form isobutylidene diruea (IBDU).
The IBDU is manufactured by the condensation reaction of urea and isobutyraldehyde
(Goertz, 1993a). A number of processing methods have been employed. They can
be categorized into solid phase and liquid phase reactions.
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.
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.
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%.
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.
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.
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
coated fertilizer products currently in the market. At present, coating materials

include synthetic organic polymers such as alkyd resins and polyurethane-like
materials, natural organics like latex, peat or neem cake and inorganics like
sulphur, clay, phosphates, oxides or gypsum.
3.1 Sulphur Coated (including sulphur/polymer coated)
Sulphur-coated urea (SCU) was developed at the TVA in 1961. It is prepared by
spraying molten sulphur over granular urea to yield a product containing between
31 to 38% N. A wax sealant is then sprayed to seal cracks in the coating and
thereby reduce leakage and microbial degradation of the S coating (Oertli, 1980;
Shaviv, 2000). This is followed by a layer of a conditioner such as attapulgite or
talc. The wax sealant may be replaced by an organic polymer layer to produce
a polymer-coated SCU called PSCU or PSCF. One example of a polymer
coating over SCU is produced by first coating an isocyanate-reactive component
that includes a polyether (polyol) onto fertilizer particles and then applying an
isocyanate component. Polymer-cum-sulphur-based coatings of different fertilizers
and SCU form the majority of coated products now in practice. This is mainly
due to their extensive use in non-agricultural markets, such as turfs, landscaping
and horticulture.
Currently, manufactured products contain between 30% to 42% N and 6% to 30%
S plus various sealants and conditioners (Trenkel, 1997). Release of nutrients is
controlled by physical breakdown of coatings, microbial decomposition of the
sulphur and hydrolytic cleavage of S-S linkages. Jarrell and Boersma (1980)
suggested an Arrhenius-type expression for the model pertaining to the effect of
temperature on nitrogen release from sulphur-coated urea (SCU). Immediate release
of fertilizer which is due to damaged coatings is termed catastrophic release whereas
perfectly coated granules are considered locked off (Goertz, 1993b). As the water
penetrates though the coating, a part of the solid core dissolves and this induces
internal pressure leading to catastrophic release wherein the entire content of the
granule is released instantaneously. However, if the membrane resists the internal
pressure, the fertilizer simply diffuses out across the coating. This is termed the
diffusion mechanism. The failure mechanism is considered typical in sulphur or
other inorganic coatings. Diffusion release has been observed with polymer-coated
fertilizers such as with polyurethane, alkyd type resins and polyolefins (Raban
and Shaviv, 1995; Shaviv, 1996; Shaviv 2005). With PSCU, diffusion of water
through the polymer coat improves its nutrient release rate. PSCUs also possess
abrasion resistance and do not leave waxy residues on application equipment. It
has been noted that PSCU has an initial burst of more than 20% of its content and
a tailing of more than 30% (Shaviv, 2000). Du et al. (2008) applied generalized
regression neural network (GRNN) to predict nitrate release profiles from polymer
coated fertilizers. They concluded that the thickness of coating membrane was the
most important parameter in controlling nitrate release, followed by temperature,
granule radius and saturated concentration of nitrate.

Guertal (2000) studied the effect of slow-release preplant SCU, preplant PCU and
fertigated ammonium nitrate on ball pepper yields. She concluded that nitrogen
source rarely affected the partitioning of harvested peppers into grade groups. There
were few consistent differences in pepper yield or quality due to N source. Given
cost considerations of drip application and N sources, slow-release N materials
may be a viable option for small-scale growers not using drip application systems.
Snyder and Gascho (1976) examined nitrogen release from sulfur-coated urea and
K release from S-coated KCl. They observed that variations in N and K release
were comparatively small. Release was rapid during the first 6 months, averaging
70–80% of that applied, but was much slower thereafter. Mead et al. (1975)
studied the performance of sulfur-coated urea with seedlings of Pinus radiata. After
slash burning on a strongly weathered clay soil, slow-release nitrogen fertilizers,
including three formulations of S-coated urea, proved more effective than urea. In
India too, S-coated urea has outperformed ordinary urea for rice in experiments
conducted by Bijay-Singh and Katyal (1987). On a more fertile pumice soil, on
both slash burnt and unburnt sites, no response to N fertilizers was detected. In
these two disturbed areas, S-coated urea showed no advantage over conventional
soluble NH4-N fertilizers. Hummel and Waddington (1981) evaluated several N
sources for maintenance fertilization of Kentucky bluegrass (Poa pratensis L.)
turf. Treatments included isobutylidene diurea (IBDU), sulfur-coated ureas (SCU),
ureaformaldehyde (UF), activated sewage sludges, Organiform, soluble N sources
and combinations of slow-release and soluble N. Sulfur-coated urea produced a more
uniform growth and had higher N recovery than IBDU which was characterized
by a delayed response following fertilization. Particle-size effects with CIL SCU
were slight; however, N release was quicker from fine IBDU than coarse IBDU.
Slow-release characteristics were also observed for ureaform, Organiform and
sludges, but turf quality was generally poor with these treatments. Substituting
soluble N for a portion of the SCU N gave inferior turfgrass response as compared
to SCU applied alone. Recovery of N in the clippings was greatest for soluble N
sources and SCU treatments (48 to 52%) while lowest values (15 to 29%) were
associated with ureaform, Organiform and sludges.
3.2 Polymer Coated
3.2.1 Overview
The concept of encapsulating a soluble fertilizer granule with multiple layers of
polymer film to slow or control the availability of nutrients was disclosed in a US
patent issued in 1965 to Hansen and assigned to Archer Daniels Midland (Hansen,
1965). Although, the preferred embodiment of this patent involved coatings derived
from copolymers of dicyclopentadiene and glyceryl esters of unsaturated fatty
acids, a plethora of alternative coatings were suggested. Today, fertilizer coatings
are derived from numerous coating materials, ranging from the ADM copolymers,
to polyolefins, to polyurethanes, to epoxies to alkyds and more.
Targeted release patterns can vary in longevity from several weeks to several
years. The pattern of release within these time intervals can take on a number
of desired shapes, ranging from a delayed release (S shaped curve), to a high
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
final consideration in choosing a polymer is the elasticity or brittleness of the

polymer. This factor affects the durability of the coating to withstand handling
(Goertz, 1993b).
3. Polymer application: Once a quality fertilizer substrate and an acceptable
polymer system have been identified, the remaining task is to apply the polymer
to the fertilizer in a uniform, consistent method. Polymers can be applied
as resins, as reactive monomers, as latexes or as solutions. In all cases, the
key is to apply a uniform film that cures without sticking or agglomerating
to adjacent fertilizer particles. Resins are typically mixtures of prepolymers,
which are reacted by the addition of a catalyst or auto oxidized with air. Unlike
resins, reactive monomers are added as two or more separate flow streams and
reacted with a catalyst. Latexes are water or solvent emulsions of a reacted,
film forming polymer. The latex is applied to the surface of the fertilizer
and the film congeals around the particle as the water/solvent is evaporated.
Similarly polymer solutions are solutions of a film forming polymer dissolved
in a solvent. As the solvent is evaporated, the polymer congeals to form a
tight film around the fertilizer particle.
A number of different processes have been developed for producing polymer
coated fertilizers. These use a number of different types of equipment and
application techniques. The basic goal of all these processes is the same; namely
to apply the polymer uniformly over all the fertilizer particles in a way which
prevents agglomeration of particles and degradation of the coating. The processes
involve a solid metering system for the fertilizer, a liquid metering system for the
polymer, and a coater for the application of the liquid polymer to the surface of
the fertilizer. Some processes require a pre-heater to bring the fertilizer up to a
target temperature prior to coating. Other processes require a cooler to cool the
coated product and a conditioner to apply parting agents (e.g., clays) or sealer coats
(e.g., waxes) to the surface of the polymer coated fertilizer. The processes can be
either batch or continuous. Batch processes are usually relatively low production
rate units but give very good uniformity of coated product. Continuous units are
better suited to high production volumes but can compromise the uniformity of
the product.
Release from all polymer coated fertilizers is by variations of the same fundamental
mechanism. Water must find its way through the coating to the fertilizer particle.
The water solubilizes the fertilizer inside the encapsulated granule and finally
the fertilizer solution makes it way through the coating into the environment.
The design of the coating (coating material and thickness) and temperature
dictate the rate and the pattern at which the fertilizer releases from the particle.
The example below illustrates the range of different release patterns which can
be achieved by manipulating the coating. For example, product A releases rather
quickly and has longevity (80% release) of about 13 weeks. This product could be
engineered by picking a polymer coating with relatively high water permeability
or by using a relatively thin coating. By contrast, the product B is slow to start
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.
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
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.
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.
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
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
developed urea coated with calcium magnesium phosphate. Beijing Institute of

Landscape Gardening and Beijing Chemical Industry Research Institute developed
resorcinol-formaldehyde resin-coated compound fertilizer in 1985; China Petroleum
and Chemical Cooperation along with China National Hybrid Rice R&D Center
developed a hybrid-rice-specific slow release fertilizer (Yan et al., 2008).
Wu and Liu (2008) described a new type of chitosan-coated NPK compound
fertilizer with controlled-release and water-retention, which possessed the three-
layer structure. Its core was granular water soluble NPK fertilizers, the inner
coating was chitosan and the outer coating was superabsorbent (polyacrylic acid-
co-acrylamide) polymer.
Ko et al. (1996) developed a mathematical model describing the controlled
release of urea from rosin-coated urea granules which has been developed on the
basis of the experimental results. Two classes of release pattern were observed
from single-pellet release experiments, viz., (1) immediate and relatively rapid
release through a few holes or many microscopic pores originally present in the
coating and (2) little or no release for an extended period of time followed by a
sudden, rapid release through the holes formed in the coating.
4. GEL BASED MATERIALS
4.1 Overview
Gel based fertilizers work on the principle of absorption of soluble fertilizers
within a matrix of polymer gel. They are generally based on polyacrylic acid and
its derivates. Fertilizers of this type are perceived to have an additional function
as water absorbent.
4.2 Processes and Product Properties
Liang and Liu (2006) described a coated N fertilizer with slow release and water
retention properties prepared by cross-linked poly(acrylic acid)/organo-attapulgite
(outer coating), urea-formaldehyde (inner coating) and urea granule (core). The
water absorbency of this fertilizer was 80 times of its own with a N content of
28.3%. The product had a high initial swelling rate and excellent water retention
capacity. Carboxyl methyl starch, acrylic acid, ammonia, urea and DAP were also
used for synthesis of a slow-release NP compound fertilizer (Guo et al., 2005).
The product contained 22.6% N and 7.2% P2O5. Its water absorbency was about
85 times of its own weight.
A superabsorbent, slow release N fertilizer was prepared by inverse suspension
polymerization of partially neutralized acrylic acid using N,N′-methylene
bisacrylamide as a crosslinker and ammonium persulfate as an initiator in the
presence of urea (Liu et al., 2007). The N content under optimal conditions was
22.7%, and the water absorbencies were about 965 g g−1 in distilled water and
185 g g−1 in tap water. Biodegradable superabsorbent matrixes for slow-release
fertilizers were also prepared by using crosslinked acrylic acid and water-soluble
granular phosphorus fertilizer KH2PO4. Hydrogel structure and swelling capacity
was observed to be affected by concentration of crosslinker and initiator, as well
as by the amount of KH2PO4 (Tyliszczak et al., 2008).
4.3 Mechanisms of Release

Shavit et al. (2003) studied the role of vapour and fluid flows in the wetting
process of controlled release fertilizers (CRF) consisting of urea or KNO3 mixed
with polyacrylamide (PAM). Vapor adsorption isotherms were obtained for typical
fertilizer–PAM mixtures. They observed that wetting front motion was affected by
transport and adsorption of vapour and release rates were different when wetting
was governed by vapour flow or by liquid flow. The release pattern from a multi-
region device was consistent with the wetting pattern, demonstrating the possibility
to tailor the release according to periods of peak demand (Shaviv et al., 2003).
4.4 Agronomic Studies
Mikkelsen et al. (1993) studied the addition of gel-forming, hydrophilic polymers
to N fertilizer solutions. Nitrogen leaching losses were reduced from 0 to
45% during the first four weeks due to polymer addition, compared with urea
ammonium nitrate (UAN) alone. The addition of various guar derived polymers
to UAN also reduced leaching losses by 26% to 7% during the first four weeks
following fertilizer application with the addition of polymer. When UAN was
applied with some polymers, growth of fescue was increased by 40% and N
accumulation increased by 50% as compared to UAN alone. It was concluded
that under highly leached conditions, N leaching loss may be temporarily reduced
and plant recovery of N increased through use of some gel-forming, hydrophilic
polymers (Mikkelsen et al., 1993).
Talaat et al. (2008) developed a hydrogel blend containing 65-70% starch,
28-33% urea and 2% of other ingredients (zinc, potassium and phosphorus). The
grain yield for wheat showed 116% increase using hydrogel blend as compared
with the normal fertilizing treatments. Preliminary cost estimates conducted for a
small scale industrial production facility (10 ton/day) was about 770 US $/ton. They
concluded that economics of the production could be significantly improved with
the use of cheap substrates like waste food grains and other polysaccharides.
5. SUPERGRANULES AND COMPACTED MATERIALS
5.1 Overview
In 1975, IFDC (International Fertilizer Development Center, Muscle Shoals,
Alabama) proposed the use of supergranules of urea (USG) with deep placement
of fertilizer N in transplanted rice. Urea supergranules are large, particles of urea
with weights varying from 1 to 2 g per particle. USG from melt granulation
processes are nearly spherical with smooth surfaces, while briquetting produces
pillow-shapes with broken edges. The USG technology has been promoted by
IRRI (International Rice Research Institute, Manila) in collaboration with the
IFDC-executed Agro-based Industries and Technology Development Project (ATDP)
in Bangladesh. A urea briquette machine has been developed for production of
briquettes for rice farmers. Farmers bring fertilizer to a place to make into the
granules. The equipment makes round free flowing USG, is mounted on wheels
with tractor and uses tractor power so that the tractor can be used as source of
energy for making USG. In Bangladesh, the cost of urea briquettes is about 10
% higher than that of prilled urea. USG when placed at 10 cm depth, in puddled
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.
6. ZEOLITE BASED MATERIALS AND OTHERS

Eberl (2002) described the production of slow-release fertilizers using zeolites.
Zeolites are heated to 400°C to drive out pore water which is then replaced by
molten urea. The product contains about 17% N. The sequestering action of zeolite
reduces leaching and slows down nitrification. Zeolite based fertilizers have been
studied by NASA as a means to sustain plant growth in space environments.
These are currently being sold under the brand name Zeoponix for use in golf
courses, sports playing fields and for greenhouse horticultural use as a proven
combination fertilizer and soil amendment. Perrin et al. (1998) suggested that
ammonium-loaded clinoptilolite may reduce N leaching from sandy soils while
sustaining plant productivity. Bansiwal et al. (2006) studied the feasibility of
using surfactant-modified zeolite (SMZ) as a carrier for fertilizer and for slow
release of P. Zeolite surface was modified by using hexadecyl trimethylammonium
bromide, a cationic surfactant, to increase its capacity to retain phosphate. It was
observed that the P loading on SMZ increased by a factor of 4.9 as compared to
the unmodified zeolite; P supply from fertilizer-loaded SMZ was available even
after 1080 h of continuous percolation whereas P from KH2PO4 was exhausted
within 264 h.
7. STABILISED NITROGEN PRODUCTS
7.1 Nitrification Inhibitors
7.1.1 Overview
Nitrification process in soils may be autotrophic or heterotrophic. Autotrophic
nitrification which is dominant in soils, is carried out by chemolithotrophic bacteria
such as nitrosomonas. It occurs in several steps starting with the oxidation of NH3
to hydroxylamine and then to NO2– by bacteria. Subsequently, NO2– oxidizing
bacteria (such as nitrobacter) oxidise nitrite to nitrate.
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-
6 (trichloromethyl) pyridine] is manufactured by Dow Chemical Company and

marketed as N-Serve. It may be used with any N fertilizer including anhydrous
ammonia, urea, urea-ammonium nitrate solutions, ammonium nitrate, ammonium
sulphate and animal manures (Frye, 2005). N-Serve has a very selective effect
on Nitrosomonas bacteria; however, it has some bactericidal effect, i.e. the
Nitrosomonas bacteria are not only inhibited in their activity for a certain period
of time but also a part of the population is killed. Other nitrification inhibitors
include thiourea, terrazole like 5-ethoxy-3-trichloromethyl 1,2,4-thiadiazole, pyridines
such as 4,6-dichloro-2-trichloromethylpyridine, ethylene urea, etc (Malzer, 1979;
McCarty, 1999; Subbarao et al., 2006). DCD has only a bacteriostatic effect on
the Nitrosomonas bacteria, i.e. the bacteria are not killed but only depressed or
inhibited in their activities for a certain period of time. Even several applications
only led to a depressive effect on Nitrosomonas bacteria.
The potential benefit from application of nitrification inhibitors depends on a
number of factors, such as soil type, climate, cultural practices and N management
program. Highest yield responses occur with excessively drained or poorly drained
soils because of N losses from leaching and denitrification, respectively. A study
in Indiana with fall-applied anhydrous ammonia showed that N-Serve application
increased corn yields by 300% with a very poorly drained silty clay soil and 1%
with a well-drained sandy loam soil (Nelson and Huber, 2001).
Only a few nitrification inhibitors, N-serve, DCD (dicyandiamide) and DMPP
(3,4-dimethyl pyrazole phosphate) have been thoroughly evaluated under field
conditions (Guthrie and Bomke, 1980; Weiske et al., 2001; Zerulla et al., 2001;
Di and Cameron, 2002; Subbarao et al., 2006). However, these synthetic chemical
inhibitors have not been widely adopted by production agriculture as they are often
not cost-effective. In addition, there are concerns over their lack of consistent
performance across diverse agro-climatic and soil environments (McCall and
Swann, 1978; Gomes and Loynachan, 1984; Subbarao et al., 2006).
7.2 Urease Inhibitors
7.2.1 Overview
When urea fertilizers are applied to the soil, an enzyme called urease begins
their conversion to ammonia gas. If this conversion takes place below the soil
surface, the ammonia is converted to NH4+ and then bound to soil particles. If
the conversion takes place on the soil surface, ammonia gas can escape back into
the atmosphere by volatilization. Volatilization losses depend on the environmental
conditions at the time of application. Soil temperature, soil moisture, amount of
surface residue, soil pH, length of time between application and the first rain
or irrigation are factors that determine the total amount of N that could be lost
via volatilization. Volatilization losses can be substantially reduced if a urease
inhibitor is used with the fertilizer. Urease inhibitors reduce the activity of the
urease enzyme for up to 14 days. As long as it rains during this 14-day period,
the urea will be moved into the soil where it can be converted to NH4+ without
the risk of volatilization. Urease inhibitors are, therefore, most beneficial on
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).
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
selectivity, and inhibition characteristics, the novel enzyme was characterized as an

intracellular enzyme complex with urease activity (Koivunen et al., 2003, 2004).
8. COMMERCIAL SLOW-RELEASE NITROGEN FERTILIZERS
US, Canada, Japan and Europe are the largest producers and consumers of slow-
release fertilizers with about 66% being consumed in US and Canada. Whereas in
North America, the major fraction being consumed is in non-agricultural markets
such as turfs but in Japan, consumption is mainly in agriculture (Shaviv, 2005;
Landels, 2010). Urea-formaldehyde condensation products represent more than
half of the total consumption of slow and controlled-release fertilizers in the
United States whereas in Western Europe, IBDU-formulations comprise the largest
group (Trenkel, 1997). Selected list of slow-release fertilizers available globally
are presented in Appendix 1.
ACKNOWLEDGEMENT
The first author is grateful to the Department of Science & Technology, Government
of India for support.
References
AAPFCO. 2005. Official Publication No. 58, Association of Amercan Plant Food Control
Officials Inc., West Lafayette, Indiana.
Alexander A, Helm HU. 1990. Ureaform as a slow release fertiliser: A review. Z Pflanzenernaehr
Bodenkd. 153: 249–255.
Andreopoulos AG. 1994. Degradable plastics: A smart approach to various applications.
J. Elastom Plast. 24: 308–326.
AOAC International. 2010. In Official Methods of Analysis, ed., W Horwitz, G Latimer, 18th
Edition, Revision 3; AOAC International: Maryland: USA.
Bansiwal AK, Rayalu SS, Labhasetwar NK, Juwarkar AA, Devotta S. 2006. Surfactant-modified
zeolite as a slow release fertilizer for phosphorus. J. Agric. Food Chem. 54: 4773–4779.
BASF. 1965. Die Landwirtschaftliche Versuchsstation Limburgerhof 1914–1964. 50 Jahre
landwirtschaftliche Forschung in der BASF (The Agricultural Research Station, Limburgerhof,
1914–1964. 50 Years of Agricultural Research in BASF). BASF. Aktiengesellschaft:
Limburgerhof, Germany.
Bhatia KB, Kumar V, Dahiya SS. 1985. Effect of methods of urea application with farmyard manure
and neem cake on wheat yield and nitrogen uptake. Indian J. Agron. 30: 150–153.
Bijay-Singh, Katyal JC. 1987. Relative efficacy of some new urea-based nitrogen fertilizers for
growing wetland rice on a permeable alluvial soil. J. Agril. Sci., Camb. 109: 27–31.
Booze-Daniels JN, Schmidt RE. 1997. The Use of Slow Release Nitrogen Fertilizers on the
Roadside, A Literature Review, Blacksburg, VA: Virginia Tech.
Cahill S, Osmond D, Weisz R, Heiniger R. 2010. Evaluation of alternative nitrogen fertilizers
for corn and winter wheat production. Agron. J. 102: 1226–1236.
Cahill S, Osmond D, Crozier C, Israel D, Weisz R. 2007. Winter wheat and maize response
to urea ammonium nitrate and a new urea formaldehyde polymer fertilizer. Agron. J. 99:
1645–1653.
Chauhan RPS. 1999. Efficiency of coated urea materials in rice-wheat system under partially
reclaimed sodic soils. Indian J. Agric. Science 69: 311–316.
Christianson CB. 1988. Factors affecting N release of urea from reactive layer coated urea.
Nutr. Cycl. Agroecosys. 16: 273–284.
Christianson CB, Carter MF, Holt L. 1988. Mineralization and nitrification of ureaform fertilizers.
Fertilizer Res. 17:85–95.
Corke J, Robinson JB. 1966. Microbial decomposition of various fractions of urea formaldehyde.
Nature 221:1202–1203.
Di HJ, Cameron KC. 2002. The use of a nitrification inhibitor, dicyandiamide (DCD) to decrease
nitrate leaching and nitrous oxide emissions in a simulated grazed and irrigated grassland.
Soil Use Manage. 18: 395–403.
Douglas W, Golden DC. 1995. US Patent No 5433766.
Du C, Tang D, Zhou J, Wang H, Shaviv A. 2008. Prediction of nitrate release from polymer-
coated fertilizers using an artificial neural network model. Biosyst. Eng. 99: 478 – 486.
Eberl DD. 2002. Controlled release fertilizers using zeolites. US Geological Survey, 19 August
2002, Fact Sheet http://www.usgs.gov/tech-transfer/factsheets/94-066b.html 02 December,
2002.
Frye W. 2005. Nitrification inhibition for nitrogen efficiency and environment protection. IFA
International Workshop on Enhanced-Efficiency Fertilizers. Frankfurt, Germany, 28–30
June 2005.
Fujinuma R, Balster NJ, Norman JM. 2009. An improved model of nitrogen release for surface-
applied controlled-release fertilizer. Soil Sci. Soc. Am. J. 73: 2043–2050.
Gnatowski M, Koutsandreas A, Foster T, Fookes D. 1998. United States Patent 5763518.
Goertz HM. 1993a. Controlled release technology. In Kirk-Othmer Encyclopedia of Chemical
Technology, Fourth Edition, Vol.7, pp. 251–274, John Wiley, NJ.
Goertz HM. 1993b. Technology developments in coated fertilizers. Presented at: Dahlia Greidinger
Memorial International Workshop on Controlled/Slow Release Fertilizers, Technion – Israel
Institute of Technology, Haifa, Israel.
Golden BR, Slaton NA, Norman RJ, Wilson CE, DeLong RE. 2009. Evaluation of polymer-coated
urea for direct-seeded, delayed-flood rice production. Soil Sci. Soc. Am. J. 73: 375–383
Gomes SL, Loynachan TE. 1984. Nitrification of anhydrous ammonia related to nitrapyrin and
time-temperature interactions. Agron. J. 76: 9–12.
Guertal EA. 2000. Preplant slow-release nitrogen fertilizers produce similar Bell pepper yields
as split applications of soluble fertilizer. Agron. J. 92: 388–393
Gupta RK. 2002. Rice-wheat Consortium for Indo-Gangetic Plains. http://www.rwc.cgiar.org/
rwc/text_det.asp?id=t1033.
Guthrie TT, Bomke AA. 1980. Nitrification inhibition by NServe and ATC in soils with varying
texture. Soil Sci. Soc. Am. J. 44: 314–320.
Guo M, Liu M, Hu Z, Zhan F, Wu L. 2005. Preparation and properties of a slow release NP
compound fertilizer with superabsorbent and moisture preservation. J. Appl. Polymer Sci.
96: 2132–2138.
Haberle K . 2003. US patent Publication No. US 2003/0040435.
Hansen LI. 1965. U.S. Patent No. 3,223,518.
Hassan ZA, Young SD, Hepburn C, Arizal, R. 1990. An evaluation of urea-rubber matrices as
slow-release fertilizers. Fertilizer Res. 22: 63–70.
Hollingsworth BS, Guertal EA, WalkerRH. Cultural management and nitrogen source effects
on ultradwarf Bermudagrass cultivars, Crop Sci. 45: 486–493.
Hughes TD. 1976. Nitrogen release from isobutylidene diurea: Soil pH and fertilizer particle
size effects. Agron. J. 68: 103–106.
Hulme F, Buchheit C. 2007. The Value in Osmocote® Controlled Release Technology. The
Scotts Exchange Tech Shares. URL: http://www.scottsprohort.com.
Hummel NW Jr. 1989. Resin-coated urea evaluation for turfgrass fertilization. Agron. J. 81:
290–294.
Hummel NW, Waddington DV. 1981. Evaluation of slow-release nitrogen sources on Baron
Kentucky bluegrass1. Soil Sci. Soc. Am. J. 45: 966–970.
IFDC. 2010. http://www.ifdc.org/Expertise/Fertilizer/Fertilizer_Deep_Placement_(UDP)
Jahns T, Kaltwasser H. 2000. Mechanism of microbial degradation of slow-release fertilizers
J..Polym. Environ. 8: 11–16.
Jarrell WM, Boersma L. 1980 Release of urea by granules of sulfur coated urea. Soil Sci. Soc.
Am. J. 44: 418–422.
Ko SB, Cho YS, Rhee HK. 1996. Controlled release of urea from resin-coated fertilizer particles.
Ind. Eng. Chem. Res. 35: 250–257.
Koivunen ME, Morisseau C, Newman JW, Horwath WR, Hammock BD. 2003. Purification
and characterization of a methylene urea-hydrolyzing enzyme from Rhizobium radiobacter
(Agrobacterium tumefaciens). Soil Biol. Biochem. 35: 1433–1442.
Koivunen ME, Morisseau C, Newman JW, Horwath WR, Hammock BD. 2004. Isolation of
a strain of Agrobacterium tumefaciens (Rhizobium radiobacter) utilizing methylene urea
(ureaformaldehyde) as nitrogen source. Can. J. Microbiol. 50: 167–174.
Kolybaba M, Tabil LG, Panigrahi S, Crerar WJ, T. Powell T, Wang B. 2003. Biodegradable
Polymers: Past, Present, and Future, ASAE Meeting Presentation RRV03-0007 CSAE/ASAE
Annual Intersectional Meeting North Dakota, USA October 3–4, 2003.
Landels, SP. 2010. Enhanced-Efficiency Fertilizers: World Market Overview. Presented at: IFA-New
Ag International Conference on Enhaced Efficiency Fertilizers (March 23–34), Miami, FL.
Liang R, Liu M. 2006. Preparation and properties of coated nitrogen fertilizer with slow release
and water retention. Ind. Eng. Chem. Res. 45: 8610 –8616.
Liu M, Liang R, Zhan F, Liu, Z, Niu A. 2007. Preparation of superabsorbent slow release
nitrogen fertilizer by inverse suspension polymerization Polymer Int. 56: 729–737.
Malzer GL. 1979. Progress with nitrification inhibitors. Down to Earth 35: 1–3.
McCall PJ, Swann RL.1978. Nitrapyrin volatility from soil. Down to Earth 34: 21–27.
McCarty GW. 1999. Modes of action of nitrification inhibitors. Biol. Fertil. Soils 29: 1–9.
McKenzie RH, Middleton AB, Pfiffner PG, Bremer E. 2010. Evaluation of polymer-coated urea
and urease inhibitor for winter wheat in Southern Alberta. Agron. J. 102: 1210–1216.
Mead DJ, Ballard R, Mackenzie M. 1975. Trials with sulfur-coated urea and other nitrogenous
fertilizers on Pinus radiata in New Zealand. Soil Sci. Soc. Am. J. 39: 978–980.
Meelu OP, Rekhi RS, Brar JS, Katyal JC. 1983. Comparative efficiency of different modified
urea materials in rice. In: Proceedings of the Fertiliser Association of India – Northern
Region Seminar on Fertilizer Use Efficiency. pp. 47–59. The Fertiliser Association of India,
New Delhi, India.
Mikkelsen RL, Behel AD, Williams HM. 1993. Addition of gel-forming hydrophilic polymers
to nitrogen fertilizer solutions. Nutr. Cycl. Agroecos. 36: 55–61.
NAAS. 2006. Low and declining crop response to fertilizers. Policy Paper 35. National Academy
of Agricultural Sciences, New Delhi pp3.
Nelson DW, Huber D. 2001. Nitrification Inhibitors for Corn Production. Iowa State University
Extension NCH55.
Noellsch AJ, Motavalli PP, Nelson KA, Kitchen NR. 2009. Corn Response to conventional and
slow-release nitrogen fertilizers across a claypan landscape. Agron. J. 101: 607–614.
Oertli JJ. 1980. Controlled-release fertilizers. Fert. Res. 1: 103–123.
Otey FH, Trimnell D, Westhoff RP, Shasha BS. 1984. Starch matrix for controlled release of
urea fertilizer. J. Agric. Food Chem. 32: 1095–1098.
Pandey PC, Bisht PS, Gautam RC and Pyare Lal. 1989. Evaluation of modified urea forms for
increasing N use efficiency in irrigated transplanted rice. In: Soil Fertility and Fertilizer Use.
(V. Kumar, G.C. Shrotriya and S.V. Kaore Eds.), volume 3, pp. 114–126. Indian Farmers
Fertilizer Cooperative, New Delhi, India.
Peacock CH, DiPaola JM. 1992. Bermudagrass response to reactive layer coated fertilizers.
Agron. J. 84: 946–950.
Perrin TS, Drost DT, Boettinger JL, Norton JM. 1998. Ammonium-loaded clinoptilolite: A
slow-release nitrogen fertilizer for sweet corn. J. Plant Nutr. 21: 515–530.
Power JF. 1979. Use of slow-release N fertilizers on native mixed Prairie. Agron. J. 71: 446–
449.
Prakash O, Alva AK, Paramasivam S. 1999. Use of urease inhibitor N-(n-butyl) thiophosphoric
triamide decreased nitrogen leaching from urea in a fine sandy soil. Water, Air Soil Poll.
116: 587–595.
Prakasa Rao EVS, Singh M, Narayana MR, Chandrasekhara G. 1984. Relative efficiency of
prilled urea and urea-supergranules in Java citronella (Cymbopogon winterianus Jowitt)
Nutr. Cycl. Agroecos. 5: 435–437.
Prasad R. 2005. Research on nitrification inhibitors and slow-release nitrogen fertilizers in

India: A review P. Natl. A. Sci. India B LXXV: 149–157.
Prasad R. 2007. Nitrogen in Indian Agriculture. In, Agricultural Nitrogen Use and Its
Environmental Implications Ed., Y. P. Abrol, N. Raghuram, MS Sachdev pp 29–54, IK
International Publishing, New Delhi,
Prasad R, Sharma SN, Singh S, Shivay YS. 2002. Neem coating of urea for the environment
and agriculture. Fert. News 47: 63–67.
Prasad R, Sharma SN, Singh S, Prasad M. 1989. Relative efficiency of prilled urea and urea
supergranules for rice. In: Soil Fertility and Fertilizer Use. (V. Kumar, G.C. Shrotriya and S.V.
Kaore Eds.), volume 3, pp. 38–46. Indian Farmers Fertilizer Cooperative, New Delhi, India.
Prasad R, Singh S, Saxena,VS, Devakumar C. 1999. Coating of prilled urea with neem oil for
efficient nitrogen use. Naturwissenschaften 86: 529–538.
Raban S, Shaviv A. 1995. Controlled release characteristics of coated urea fertilisers. In:
Proceedings of 22nd Int. Symposium on controlled release of bio-active materials. 105–106.
CRS, Inc, Seattle.
Reddy RNS, Prasad R. 1975. Studies on the mineralization of urea, coated urea, and nitrification
inhibitor treated urea in soil. Eur. J. Soil Sci. 26: 304–312.
Rodrigues MA, Santosa H, Ruivoa S, Margarida Arrobasa M. 2010. Slow-release N fertilisers
are not an alternative to urea for fertilisation of autumn-grown tall cabbage. Eur. J. Agron.
32: 137–143.
Roger PA, Kulasooriya SA, Tirol AC, Craswell ET. 1980. Deep placement: A method of
nitrogen fertilizer application compatible with algal nitrogen fixation in wetland rice soils.
Plant Soil 57: 137–142.
Savant NK, Stange PJ. 1990. Deep placement of urea supergranules in transplanted rice:
Principles and practices. Nutr. Cycl. Agroecos. 25: 1–83.
Shavit U, Reiss M, Shaviv A. 2003. Wetting mechanisms of gel-based controlled-release
fertilizers. J. Control. Release 88: 71–83.
Shaviv A. 1996. Plant response and environmental aspects as affected by rate and pattern of
nitrogen release from controlled release N fertilisers. In Progress in Nitrogen Cycling Studies
ed., Van Clempt et al., p. 285–291. Kluwer Academ. Netherlands.
Shaviv A. 2000. Advances in controlled release of fertilizers. Advances Agron. 71: 1–49.
Shaviv A. 2005. Controlled release fertilizers. In IFA International Workshop on Enhanced-
Efficiency Fertilizers. Frankfurt, Germany.
Shaviv A, Raban S, Zaidel E. 2003. Modeling controlled nutrient release from a population
of polymer coated fertilizers: Statistically based model for diffusion release Environ Sci.
Technol. 37: 2257–2261.
Singh MK, Verma, UN, Pal SK, Thakur R. 1999. Efficiency of slow-release N-fertilizers from
rice and their residual effect on wheat. Indian J. Agron. 44: 216–218.
Singh MP, Singh RP, Singh VP, Verma SC 1990. Effect of modified urea materials on the
performance of rice under varying nitrogen levels. Indian J. Agron. 35: 384–390.
Snyder GH, Gascho GJ. 1976. Sulfur-coated fertilizers for sugarcane: II. Release Characteristics
of sulfur-coated urea and KCl. Soil Sci. Soc. Am. J. 40: 122–126.
Subbarao GV, Ito O, Sahrawat KL, Berry WL, K. Nakahara K, et al. 2006. Scope and strategies
for regulation of nitrification in agricultural systems—challenges and opportunities. Crit.
Rev. Plant Sci. 25: 303–335.
Subbarao GV, Kishii M, Nakahara K, Ishikawa T, Ban T, et al. 2009. Review: Biological
nitrification inhibition (BNI)—Is there potential for genetic interventions in the Triticeae?
Breeding Sci. 59: 529–545.
Suri IK, Mathews S, Saxena VS. 2000. Coating of prilled urea with neem in trial at KRIBHCO’s
Hajira Plant. Fert. News 45: 71–72.
Talaat HA, Sorour MH, Aboulnour AG, Shaalan HF, Enas M et al. 2008. Development of a
multi-component fertilizing hydrogel with relevant techno-economic indicators, American-
Eurasian. J. Agric. & Environ. Sci. 3: 764–770.
Tomar SS, Sharma JP. 2000. Assesment of N-regulatory efficiency of some non-edible oilseed
cakes and synthetic regulation on urea in rice-wheat cropping system. J Indian Soc. Soil
Sci. 48: 840–842.
Trenkel ME, 1997. Controlled-Release and Stabilized Fertilizers in Agriculture. International
Fertilizer Industry Association, Paris.
Tyliszczak BJ, Polaczek J, Pielichowski K. 2008. Preparation and Properties of Biodegradable
Slow-Release PAA Superabsorbent Matrixes for Phosphorus Fertilizers.
Macromolecular Symposia 279: 236 – 242. Special Issue: Polymers at Frontiers of Science
and Technology.
Vlnaty J., Elizer MC. 1991. US Patent No 5030267.
Watson C. 2005. Urease inhibitors. IFA International Workshop on Enhanced-Efficiency
Fertilizers. Frankfurt, Germany.
Weiske A, Benckiser G, Ottow JCG. 2001. Effect of new nitrification inhibitor DMPP in
comparison to DCD on nitrous oxide (N2O) emissions and methane (CH4) oxidation during
3 years of repeated applications in field experiments. Nutr. Cycl. Agroecosys. 60: 57–64
Wilson ML, Rosen CJ, Moncrief JF. 2009. Potato response to a polymer-coated urea on an
irrigated, coarse-textured soil. Agron. J. 101: 897–905.
Wu L, Liu M. 2008. Preparation and properties of chitosan-coated NPK compound fertilizer
with controlled-release and water-retention. Carbohyd. Polym. 72: 240–247.
Yan X, Jin JY, He P, Liang MZ. 2008. Recent advances on the technologies to increase fertilizer
use efficiency. Ag. Sci. China 7: 469–479.
Yu H, Tremblay N, Wang Z, Bélec C, Yang G, Grant C. 2010. Evaluation of nitrogen sources
and application methods for nitrogen-rich reference plot establishment in corn. Agron. J.
102: 23–30.
Zerulla W, Barth T, Dressel J, Erhardt K, von Locquenghien KH, et al. 2001. 3,4-Dimethylpyrazole
phosphate (DMPP)—a new nitrification inhibitor for agriculture and horticulture. Biol.
Fert. Soils 34: 79–84.
Appendix 1: Selected list of slow-release fertilizers available globally

1. ASIA: MAINLY FROM JAPAN, ISRAEL, INDIA AND CHINA
1.1 Coated Fertilizers
1.1.1 Inorganic coated

Henan Golden Hope
Luxecote
Coating: Inorganics
Substrates: Urea
Longevity: 4 to 16 months (21 C)
Markets: Nurseries & ornamentals.
1.1.2 Sulphur coated (including sulphur/polymer coated)

Hanfeng Slow-Release Fertilizer (Shanxi) Co
SCU
Coating: Sulphur/microcrystalline wax
Substrates: Urea, NPK
Analysis: 32-0- t 38-0-0
Markets: Nurseries & ornamentals
Mitsui Toatsu Fertilizers, Inc.
S-Coat®
Coating: Sulfur and Wax
Longevity: 50-140 days
Markets: Paddy Rice, Vegetables, Fruits, Turf
Nissan Agri Corporation
Mild Chiyoda ®
Coating: Sulfur
Substrates: NPK
Markets: Paddy Rice, Field Crops
Shandong Kingenta Ecological Engineering Co. Ltd.
Coating: Sulfur and Sulfur/Poly
1.1.3 Polymer coated

Haifa
Multicote
Coating: Polymer
Substrates: N, P, K
Analysis: 14-14-14/ 15-7-15+Micro/10-48/
Multicote Agri
Coating: Polymer
Substrates: N, P, K
Longevity: 2 to 2 months
Markets: Agriculture & horticulture.
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
Coating: Vegetable oil polyurethane resin

Substrates: N, P, K
Analysis: 20-15-13/ 18-14-15/ 15-15-15
Longevity: 25 to 130 days
Markets: Agricultural crop, rice
Co-op Chemical Co., Ltd.
(Acquired by Shin-Etsu Chemical Co., Ltd. )
Co-op Coat®
Coating: Alkyd Resin
Substrates: Urea, NK, K, NPK
Markets: Vegetables.
Hangfeng Evergreen Inc.
Hancote®
Coating: Resin
Substrates: NPK, U
Markets: Nursery, greenhouse,.
Katakura Chikkarin Co. Ltd.
SigmaCoat®
Coating: Alkyd Resin
Substrates: Urea, N
Markets: Paddy Rice, Vegetables.
Mitsubishi Chemical Agri Inc.
(now JCAM Agri Co. Ltd through merger Chisso Asahi
Fertilizer Corporation, Ltd.)
M-Coat ® L, M-Coat® SH, M-Coat® Complex
Coating: Polymer
Substrates: Urea
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
Analysis: 41-0-0
Markets: Rice, Vegetables, Fruit.
Taki Chemical Co. Ltd.
Taki-coat®, Magphos-coat®, Magphos-coat S®
Coating: Alkyd resin
Substrates: Urea, Magnesium Phosphate
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
1.1.4 Neem coated

National Fertilizers Limited (NFL), Shriram Fertilizers &
Chemicals, Indo-Gulf Fertilizers, Chambal Fertilizers
Coating: Neem cake/ neem oil
Substrates: Urea
Markets: Rice
1.2 Condensation Polymers

1.2.1 Urea formaldyhydes
Haifa
HiGreen
Chemistry: Methylene urea + solubles
Analysis: 13-0-17/ 22-5-10/6-26-10 (all with MgO)
Longevity: up to 4 months
Hangfeng Evergreen Inc.

UF/MU
Chemistry: Ureaform, Methylene Ureas
Analysis: 38-0-0,, 40-0-0
Longevity: 16 weeks to 12 months
Markets: Nursery, greenhouse, turf
Mitsui Toatsu Fertilizers, Inc.
Super-Kasei®
Chemistry: Ureaform
Analysis: 38-0-0
Markets: Rice, Other Field Crops, Turf
Sumitomo Chemical Company, Ltd.
Sumikaform®
Chemistry: Ureaform
Analysis: 38-0-0
Markets: Rice, Vegetables, Fruit, Trees.
1.2.2 Urea isobutyraldehydes

Mitsubishi Chemical Agri Inc. (see above)
IBDU®.
Chemistry: Isobutyraldehyde diurea
Analysis: 31-0-0
Markets: Rice, vegetables, fruits, turf
1.2.3 Urea crotonaldehydes
Chisso Asahi Fertilizer Corporation Ltd. (see above)
Green Phoska®, Chisso Phoska®, Hyper-CDU®, UBER®
Chemistry: Crotonylidene diruea
Markets: Vegetables, Trees, Nurseries,
Greenhouse, Professional Turf, Export
2. NORTH AMERICA
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.
bluAgro™ Slow-Release Nitrogen

(produced under contract for Agrium Advanced Technologies)
Chemistry: Ureaform
Analysis: 38-0-0
Longevity: 70% of Nitrogen as WIN
Size: SGN 225, 150, Powder
Markets: Professional Turf, Professional Horticulture.
Georgia Pacific Resins Inc
(subsidiary of Koch Industries Inc)
Nitamin® 30L
Chemistry: Methylene Ureas, triazone
Analysis: 30-0-0, 60% slowly available
Size: Liquid
Markets: Professional Turf, Specialty Ag
Nitamin Nfusion®
Chemistry: Methylene Ureas, triazone
Size: Liquid
Growth Products, Ltd
Nitro-30SRN®
Chemistry: MDU/DMTU
Size: Liquid
Helena Chemical Company
CoRoN®
Chemistry: MDU/methylene ureas
Size: Liquid
Markets: Foliar Specialty Ag
Kugler Company
KQXRN™
Chemistry: MDU/methylene ureas
Longevity: 8-10 weeks
Size: Liquid
Lebanon Seabord Corporation
Meth-Ex® 40
Chemistry: Methylene ureas
Longevity: up to 16 weeks
Size: SGN 195, SGN 145
Markets: Professional Turf, Home Garden, Specialty Ag
Meth-Ex® 40 Composites
Analysis: Variable homogenous granulated products containing
methylene ureas
Longevity: 12 to 16 weeks
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
Size: <10 mesh (US Sieves)
Markets: Home and Garden
2.2 COATED FERTILIZERS

XCU™
Coating: Sulfur, Polyurethane
Substrates: Urea
Analysis: 38-0-0 to 43-0-0
Longevity: 8 to 12 weeks (@80F)
Size: SGN 250, 200, 150
Markets: Professional Turf, Professional Horticulture,
Home and Garden.
Poly-S®
Coating: Sulfur, Polymer
Substrates: Urea, SOP, NPK’s
Analysis: 35-0-0 to 40-0-0; 0-0-40; 10-10-10
Longevity: 8 to 20 weeks (@75F)
Size: SGN 260, 220, 150
Markets: Professional Turf, Professional Horticulture, Home and Garden,
Specialty Ag
Turf Care Supply Corp.
TCS GrowStar™ Poly Plus ®
(exclusive to Lesco, Division of John Deere Landscapes)
Coating: Sulfur, Polymer
Substrates: Urea, DAP, SOP
Analysis: 39-0-0, 35-0-0, 32-0-0, 0-0-39, 0-0-38.
Longevity: Not disclosed
Size: SGN 240, 150, 100

DURATION CR®
Coating: Polyurethane Family
Substrates: Urea
Analysis: 43-0-0 to 44-0-0
Longevity: 45, 75, 120 and 180 days (@73F)
Size: SGN 250, 195, 150
Specialty Ag.
ESN® (Environmentally Smart Nitrogen)
Substrates: Urea
Analysis: 44-0-0
Longevity: 40-90 days (@73F)
Size: SGN 270
Markets: Agriculture, Specialty Ag.
POLYON®
Substrates: Urea, MAP, SOP, K-Mag, NPK’s Iron Sulfate.
Analysis: Varied
Longevity: 1-2 months to 12-14 months at 80F
Size: SGN 310, 300, 250, 220, 210, 200, 150, 90.
Specialty Ag.
Florikan ESA
Florikote® (Staged Nutrient Release)
Substrates: NPK’s, Urea, MAP, DAP, Ammonium Sulfate; SOP; Muriate
of Potash; Potassium Nitrate; Sul-po-Mag; Iron sulfate, Iron chelate,
Mg sulfate.
Analysis: Variable
Longevity: 2 months to 12 months (@77 F)
Size: SGN 225-250 (Ag & Horticulture); SGN 90-200 (Turf)
Markets: Professional Horticulture, Professional Turf, Specialty Ag
KMB Technologies, LLC
XRT
Coating: Epoxy
Substrates: Urea
Analysis: 44-0-0
Longevity: up to 3 months (@21C)
Size: SGN 240
Surfcote (Sustained Uniform Release Fertilizer)
Coating: Epoxy
Substrates: Urea, SOP
Analysis: 44-0-0, 0-0-48
Longevity: up to 3 months (@21C)
Size: SGN 150

Osmocote® Classic
Coating: Copolymer of dicyclopentadiene and glycerol esters of fatty
acids
Substrates: NPK’s, SOP
Analysis: Variable
Longevity: 3-4; 5-6; 8-9; 12-14; 14-16 months (@21C)
Markets: Professional Horticulture, Home and Garden, Specialty Ag
Osmocote® Pro
acids
Substrates: NPK’s
Analysis: Variable
Longevity: 3-4; 5-6; 8-9; 12-14months (@21C)
Size: SGN 275
Markets: Professional Horticulture,
Osmocote® Plus (Pattern Release: Lo Start, Standard, Hi Start)
acids
Substrates: NPK’s
Analysis: Variable
Longevity: 3-4; 5-6; 8-9; 12-14 months (@21C)
Size: SGN 275,
Markets: Professional Horticulture
X-Calibur Plant Health Company, LLC
Plantacote®
Coating: Polyurethane
Substrates: NPK’s, NPK plus micronutrients
Analysis: Variable
Longevity: 2, 4, 6, 8, 12, 16 months (@21C)
Size: SGN 275
Markets: Professional Horticulture, Professional Turf
3. EUROPE
3.1.1 Urea formaldehydes
Sadepan Chimica S.r.l
Sazolene SC
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

Size: Big (3-4mm); Standard (2-3mm); Micro (0.5-1.5mm); Powder
Specialty Ag.
Sazolene 39G Longer
Size: Big (3-4mm); Standard (2-3mm); Micro (0.5-1.5mm); Powder
Specialty Ag.
Sierraform GT® (Granulated NPK’s)
Chemistry: Methylene urea
Osmoform® (Granulated NPK’s)
Chemistry: Methylene urea
Longevity: 8-10 weeks; 12-14 weeks
3.1.2 Urea isobutryaldehydes

BASF AG
Isodur
Chemistry: Isobutylidene diurea
Analysis: 31-0-0
Longevity: variable based on moisture, particle size
Size: Granulated into NPK fertilizers by Compo GmbH & Co KG
Specialty Ag.
3.2 Coated Fertilizers

Aglukon Spezialdunger GmbH & Co KG
Plantacote®
Coating: Polyurethane
Substrates: NPK’s, NPK plus micronutrients
Analysis: Variable
Longevity: 2, 4, 6, 8, 12, 16 months (@21C)
Size: SGN 275
Markets: Professional Horticulture, Professional Turf
Compo GmbH & Co. KG
Basacote®
Coating: Not disclosed

Substrates: NPK’s
Analysis: Variable
Longevity: 3-4, 5-6, 8-9, 10-12 months @ 21 C
Size: 2.5-3.5mm
Markets: Professional Turf & Horticulture, Specialty Ag.
Osmocote® Pro; Ficote®
acids
Substrates: NPK’s
Analysis: Variable
Longevity: 3-4; 5-6; 8-9; 12-14 months (@21C)
Markets: Professional Horticulture, Specialty Ag
Osmocote® Exact (Pattern Release: Lo Start, Standard, Hi Start)
acids
Substrates: NPK plus minor elements
Analysis: Variable
Longevity: 3-4; 5-6; 8-9; 12-14months (@21C)
Size: SGN 275
Osmocote® Exact Protect (Delayed Release)
acids
Substrates: NPK plus minor elements
Analysis: Variable
Longevity: 12-14 months (@21C)
Size: SGN 275
Slow-Release and Controlled-Release Nitrogen Fertilizers A
ING Bulletins on Regional Assessment of Reactive Nitrogen (2010)

1. Nitrogen Management in Rice-Wheat Cropping Systems of Asia and its Environmental
and Health Implications
Rajendra Prasad, Himanshu Pathak and J.K. Ladha Editor: Bijay Singh
2. Nitrogen Losses, N-Use Efficiency and N-Management in Rice and Rice-based Cropping System
T.K. Adhya, Arvind K. Shukla and D. Panda Editor: Bijay Singh
3. Reactive Nitrogen Emissions from Crop and Livestock Farming in India
Viney P. Aneja, William H. Schlesinger, Jan Willem Erisman, Mukesh Sharma,
Sailesh N. Behera and William Battye Editor: Himanshu Pathak
4. Atmospheric Deposition of Reactive Nitrogen over Continental Sites and Oceanic
Regions of India: A Review
R. Rengarajan, B. Srinivas and M.M. Sarin Editor: Himanshu Pathak
5. Nitrogen and Sustainabilty Issues of Waste Management in Urban Ecosystems
H.N. Chanakya and H.C. Sharatchandra Editor: N Raghuram
6. Role of Soil Nitrogen in Efficient Management of Fertilizer Nitrogen in India
D.K. Benbi and Bijay Singh Editor: Himanshu Pathak
7. Management of Solid Wastes in Agricultural Systems
for Nitrogen Conservation in India
Reena Singh, Alok Adholeya and Deepak Pant Editor: N. Raghuram
8. Harnessing the Nitrogen Fixing Potential of Cyanobacteria in Integrated Nutrient Management
Strategies for Sustainable Agriculture
Dolly Wattal Dhar, Radha Prasanna and K. Swarnalakshmi Editor: N. Raghuram
9. Nitrogen Use in Agriculture in Arid and Semiarid Regions–Indian Perspective
K.L. Sharma, M. Maheswari, B. Venkateswarlu and Y.P. Abrol Editor: Bijay Singh
10. Nitrogen in the North Indian Ocean
M. Dileep Kumar Editor: N. Raghuram
11. Slow-Release and Controlled-Release Nitrogen Fertilizers
Chandrika Varadachari and Harvey M. Goertz Editor: Bijay Singh
12. Nutrient Dynamics under Shifting Agricultural (Jhum) Landscape in North-East India
and Linked Sustainability Issues
P.S. Ramakrishnan Editor: Bijay Singh
13. Nitrification: Is it a Strategic Point of Intervention to Limit Nitrogen Losses from Agricultural Systems?
G.V. Subbarao, K.L. Sahrawat, K. Nakahara, M. Kishii, I.M. Rao, C.T. Hash, T.S. George,
W. Berry, J.C. Lata and O. Ito Editor: N. Raghuram
14. Green Manure Approaches to Crop Production and Sustainable Agriculture
Yadvinder Singh, Bijay Singh and H.S. Thind Editor: N. Raghuram
15. Contribution of Energy Sector to Nitrogen Emissions
S.K. Goyal and C.V. Chalapati Rao Editor: Himanshu Pathak
16. N-Dynamics in the Coastal Regions of India
T.K. Adhya, S. Adhikari, M. Muralidhar and S. Ayyappan Editor: Himanshu Pathak
17. Hydrogen from Biomass
Parag A. Deshpande, M.S. Hegde and Giridhar Madras Editor: Bijay Singh
18. Physiological Approaches for Improving Nitrogen use Efficiency
Altaf Ahmad, Lata, Vanita Jain and YP Abrol Editor: N. Raghuram
19. Greenhouse Gas Emission and Mitigation in Indian Agriculture – A Review
H. Pathak, A. Bhatia, N. Jain and P.K. Aggarwal Editor: Bijay Singh
20. Pathophysiology of Nitrate Toxicity in Human and its Mitigation Measures
Sunil Gupta, R.C. Gupta, A.B. Gupta, E.V.S. Prakasa Rao, K. Puttanna and
Aditi Singhvi Editor: N. Raghuram
COMPREHENSIVE STATUS REPORT (2010)

REACTIVE NITROGEN: GOOD, BAD AND UGLY – V. Balasubramanian
Other Publications from the Society for Conservation of Nature

1. Policy Options for Efficient Nitrogen Use
Eds. Y.P. Abrol. and B.N. Johri
Angkor ✆ 9910161199
2. Agricultural Nitrogen Use and Its Environmental Implications

Eds. Y.P. Abrol, N. Raghuram and M.S. Sachdev
3. Reactive Nitrogen in Agriculture, Industry and Environment in India
Bijay Singh, M.K. Tiwari and Y.P. Abrol
4. Reactive Nitrogen in Agriculture, Industry and Environment in India
Y.P. Abrol, N. Raghuram and H.N. Chanakya
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Slow-release and Controlled-release Nitrogen Fertilizers

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Slow-release and Controlled-release

EDITOR: BIJAY SINGH

SLOW-RELEASE AND CONTROLLED-RELEASE NITROGEN FERTILIZERS

First Published in 2010

© Society for Conservation of Nature

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Published and Printed by ING-SCON in collaboration with Angkor Publishers

1.Corresponding Author’s E-mail: cv@rcais.res.in

Abbreviations : UF (urea-formaldehyde); IBDU (isobutylidene diurea); CDU (crotonylidene

sulphur-polymer encapsulated materials (Oertli, 1980; Hummel and Waddington, 1984;

The chemical equations can be more simply represented as:

where: U = urea, F= formaldehyde, UF = monomethylol urea, FUF = dimethylol

As mentioned, the reactions are reversible. Therefore, a UF resin will contain

Next, MDU reacts with another molecule of monomethylol urea to form

where: U = urea; M = methylene linkage; UF = monomethylol urea; UMU =

Lower the pH (the more acid that

2.1.3.5 Reaction Time

When the first UF fertilizers were commercialized in the mid-1950’s, analytical

TN = CWSN + HWSN + HWIN

CWIN = HWSN + HWIN

Availability Index (AI): Also referred to Nitrogen Availability Index (NAI),

Slow release urea-formaldehyde fertilizer products are often divided into

(b) N-25. Urea-formaldehyde products (sparingly soluble) are reaction

compared the effects of S-coated urea and ureaformaldehyde with ammonium

The reaction proceeds in two steps. In Step 1, urea reacts is isobutyraldehyde

coated fertilizer products currently in the market. At present, coating materials

3.1.3 Agronomic Studies

final consideration in choosing a polymer is the elasticity or brittleness of the

developed urea coated with calcium magnesium phosphate. Beijing Institute of

4.3 Mechanisms of Release

6. ZEOLITE BASED MATERIALS AND OTHERS

6 (trichloromethyl) pyridine] is manufactured by Dow Chemical Company and

selectivity, and inhibition characteristics, the novel enzyme was characterized as an

Prasad R. 2005. Research on nitrification inhibitors and slow-release nitrogen fertilizers in

Appendix 1: Selected list of slow-release fertilizers available globally

1.1.1 Inorganic coated

1.1.2 Sulphur coated (including sulphur/polymer coated)

1.1.3 Polymer coated

Coating: Vegetable oil polyurethane resin

1.1.4 Neem coated

1.2 Condensation Polymers

Hangfeng Evergreen Inc.

1.2.2 Urea isobutyraldehydes

bluAgro™ Slow-Release Nitrogen

2.2 COATED FERTILIZERS

2.2.2 Polymer coated

Scotts Miracle Gro Company

Longevity: 4-6 months

3.1.2 Urea isobutryaldehydes

3.2 Coated Fertilizers

Coating: Not disclosed

ING Bulletins on Regional Assessment of Reactive Nitrogen (2010)

COMPREHENSIVE STATUS REPORT (2010)

Other Publications from the Society for Conservation of Nature

2. Agricultural Nitrogen Use and Its Environmental Implications

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