Soil Science Notes

Department Soil Science and Agricultural Chemistry
University of Agricultural Sciences, GKVK, Bangalore
1. Degree : B.Sc.(Agri.)/ B.Sc.(AgMaCo)
2. Class : III B.Sc.(Agri.)
3. Semester : I Sem
4. Course No : SAC 301
5. Course Title : Manures, Fertilisers and Agro-chemicals
6. Credit hours: : 1+1
7. Prepared by : Dr.T.H.Hanumantharaju
Associate Professor
Department Soil Science and Agricultural Chemistry
University of Agricultural Sciences, GKVK, Bangalore
University of Agricultural Sciences, Bangalore
Dept. of Soil Science & Agril. Chemistry, College of Agriculture, GKVK, Bangalore
SAC 301, Manures, Fertilizers and Agro-Chemicals, (1+1)

I Semester, 2012-13
(From 11-06-2012 to 13-10-2012, Pra. Exam: 16-10-2012 to 22-10-2012)
Class and Section Course Teachers

III B.Sc. (Agri.) - A Sec : Dr. T. H. Hanumantharaju, Associate Professor
III B.Sc. (Agri.) - B Sec : Dr. V.R.Ramakrishna Parama, Professor
III B.Sc. (Ag. Ma. Co) : Dr. C. A. Srinivasamurthy, Professor and Head
Theory
Manures – types of manures; Bulky organic manures - FYM, Composts - raw materials – methods
of composting, vermi-composting; Green manures – types and composition; concentrated organic
manures- Oil cakes, types and composition; sewage and sludge – types and composition.
Fertilizers – classifications, manufacturing processes, properties of major nitrogenous, phosphatic,
potassic and complex fertilizers; their fate and reactions in soil; Fertilizer use efficiency – time and
methods of application; soil amendments; Fertilizer Control Order. Agrochemicals – classification,
chemistry of mode of action of agrochemicals; Botanical insecticides, Synthetic organic
insecticides, major classes, properties and uses of some of insecticides, herbicides, fungicides,
acaricides and rodenticides; compatibility of fertilizers with pesticides, Insecticides Act.
Practical
Determination of nitrogen, phosphorus and potassium in manures/ composts; Qualitative tests for
fertilizers; Determination of ammoniacal and nitrate nitrogen; water soluble phosphorus;
potassium, calcium, sulphur and zinc contents of fertilizers. Adulteration in fertilizer.
Determination of active ingredients in insecticides (lindane/ parathion/ carbofuron), herbicides
(glyposate/ butachlor/ atrazine) and fungicides (carbendazim/ captan/ copper oxy chloride).
References
1. Cremlyn, R. J., 1991, Agrochemicals – Preparation and Mode of action, Wiley, New York.
2. Das, P.C, 2008, Manures and Fertilizers, 3rd Edition, Kalyani publishers, New Delhi.
3. Gupta, P. K., 2004, A Hand Book of Soil, Fertiliser and Manure. Agrobios (India), Jodhpur
4. Handa, S. K., 2004, Principles of Pesticide Chemistry, Agribios (India), Jodhpur, Rajasthan
5. Ranjan Kumar Basak, 2004, Fertilizers - A Text Book, Kalyani publishers, New Delhi
6. Sreeramulu, U. S., 1979, Chemistry of Insecticides and Fungicides, Oxford & IBH Pub. Co., New Delhi.
7. Sreeramulu, U.S., 1985, Methods of Pesticides Analysis, Oxford & IBH Pub. Co., New Delhi.
8. Tandon H.L.S., 1993, Methods of Analysis of Soils, Plants, Waters and Fertilizers. FDCO, New Delhi.
9. Yawalkar,K.S., Agarwal, J.P. and Bokde, S, 1997, Manure and Fertilizers. Agri-Horti. Pub. House, Nagpur.
Scheme of Evaluation Max. Marks

1. Midterm Exam : 20
2. Practical Exam : 15
3. Practical record and Assignment : 10
4. Attendance : 05
5. Final (External) exam : 50
Total : 100
Lecture schedule of SAC 301, Manures, Fertilizers and Agro-Chemicals, (1+1)
Lectures Topics
01 Manures - types of manures, Bulky organic manures - FYM, factors influencing
manure composition
02 -03 Composts - raw materials, principles of composting, factors affecting composting,
methods of composting, vermi-composting
04 Sewage and sludge - types, composition and use
Night soil- composition and Poudrette system
05 Green manures - types, advantages and disadvantages, composition, characteristics of
green manuring crops
06 Concentrated organic manures- Oil cakes, types and composition; blood meal, bone
meal, meat meal, fish manure, horn and hoof meal
07-08 Fertilizers - classifications, materials used for preparation of fertilisers, manufacturing
processes (ammonium sulphate, urea), properties of major nitrogenous fertilizers
(ammonium sulphate, ammonium nitrate, ammonium sulphate nitrate, calcium
ammonium nitrate, urea) and their fate and reactions in soil
09-10 Manufacturing processes, properties of major phosphatic fertilizers (super phosphate,
rock phosphate, diammonium phosphate, ammonium poly phosphate) and their fate
and reactions in soil
11 Manufacturing processes, properties of major potassic fertilizers (muriate of potash
and sulphate of potash) and their fate and reactions in soil
12 Fertiliser mixtures- types- mixed fertilisers and complex fertilizers- advantages and
disadvantages, materials used; Fertilizer use efficiency – time and methods of
application
13 Soil amendments- types of amendments like liming materials, gypsum and soil
conditioners; Fertilizer Control Order
14 Agrochemicals – classification based on target organisms, chemical nature, LD50;
Botanical insecticides - nicotine, rotenone, pyrethroids, azadhiractin
15 Insecticides – Classification of insecticides based on mode of penetration, mode of
action and chemical nature. Major classes, properties and uses of insecticides –
organo-chlorines, organo-phosphates and carbamates
16 Herbicides - Classification of herbicides based on time of application, mode of action
and chemical nature. Major classes, properties and uses of herbicides
17 Fungicides - Classification of fungicides based on time of application, mode of action
and chemical nature. Major classes, properties and uses of fungicides
18 Major classes, properties and uses of acaricides, rodenticides and nematicides,
Compatibility of fertilizers with pesticides, Insecticides Act
Copy to Professor and Head, Dept. of Soil Science & Agril. Chem., GKVK, Bangalore
Copy to Dean (Agri.), College of Agriculture, GKVK, Bangalore
Copy to Coordinator, External Exam Cell, College of Agriculture, GKVK, Bangalore
UNIVERSITY OF AGRICULTURAL SCIENCES,
Bangalore
PRACTICAL MANUAL
SAC 301 (1+1), Manures, Fertilisers and Agro-chemicals
I Semester, 2012-13
Course teachers
Dr.T.H.Hanumantharaju
Dr.V.R.Ramakrishna Parama
Dr.C.A.Srinivasamurthy
Name :
ID No. :
Class :
Batch :
Dept. of Soil Science and Agricultural Chemistry

College of Agriculture, GKVK,
University of Agricultural Sciences, Bangalore
2012
Dept. of Soil Science and Agricultural Chemistry
College of Agriculture, GKVK, Bangalore – 560 065
CERTIFICATE
This is to certify that Mr./ Ms _____________________________bearing

I.D. No. __________ has satisfactorily completed the experiments in the course
SAC 301 (1+1), Manures, Fertilisers and Agrochemicals prescribed by the
UAS, Bengalure for the B. Sc. (Agri.)/ B. Sc. (Ag.Ma.Co.), Dept. of Soil Science
and Agricultural Chemistry, College of Agriculture, GKVK, Bengaluru during
the I semester 2009 – 2010.
His/ Her attendance and performance in the practical classes were found
to be ___________________ and has scored _____________ marks.
Date Signature of the Teacher

SAC 301 (1+1), Manures, Fertilizers and Agrochemicals
Particulars of Experiments
CONTENTS
Sl. Page Remarks

Date Experiment
No. No.
1 Study of manures and fertilizers 1
2 Determination of nitrogen in organic manures 15
3 Determination of phosphorus in organic manures 17
4 Determination of potassium in organic manures 19
5 Study of principles of fertilizer sampling 21
6 Study of qualitative test for fertilizers 23
7 Study of identification of adulterants in fertilizers 27
8 Determination of ammonium, nitrate and total nitrogen in 31
nitrogenous fertilizers
9 Determination of amide nitrogen in nitrogenous fertilizers 34
10 Determination of phosphorus in phosphatic fertilizers 36
11 Determination of potassium in potassic fertilizers 40
12 Determination of calcium in fertilizers/ amendments 42
13 Determination of sulphur in fertilizers/ amendments 43
14 Determination of zinc in fertilizers 45
15 Study of agrochemicals 46
16 Determination of active ingredients in BHC 57
17 Determination of active ingredients in copper fungicides 59
18 Determination of active ingredients in 2,4 D 61
Ex. No. 1 Date:
Study of manures and fertilisers
The word manure is originated from French “Mano-euvrer” which refers

to ‘work with soil’ that is why the word tillage and manure which synonyms as it
is clear by the statement of Jethro Jull (1700 BC) ‘Tillage is manure’. The word
manure is originated from Latin ‘manuren’ meaning cultivating the land.
Manures/ Organic manures

Manures are relatively bulky organic materials added to soils to supply
plant nutrients, which are added mainly to improve the physical condition of the
soil. Thus, supply practically all the elements of fertility, which a crop requires,
though not in adequate proportions. The plant food elements contained in
manure are released in an available form after it is applied to the soil.
Classification of manures and fertilizers

I. Organic manures
The organic manures are classified mainly based on the nutrient content
and organic matter content present in them.
i) Bulky organic manures
The term bulky organic manure generally includes those materials of
natural origin, organic in nature having greater volume per unit content of
nutrients and being used to increase the nutrient status of the soils as well as
organic matter content of soils. The nutrient contents of bulky organic manure
are less in terms of N, P and K and relatively higher amounts of organic matter.
Ex: Farmyard manure, compost, sewage sludge and green manure.
ii) Concentrated organic manures

The nutrient contents of concentrated organic manure are higher in terms
of N, P and K and relatively lower amounts of organic matter. The concentrated
organic manures are classified based on the origin of the materials.
A) Plant /vegetation: Derived from plants based products from the industries.
Ex. Oil-cakes, pressmud
Edible oil cakes: Mustard oil cake, groundnut cake, sesame cake, linseed cake,
coconut cake, sunflower cake etc
Non edible oil cakes: Castor cake, neem cake, mahuva cake, karanj cake etc.
B) Animals: Derived from excreta and wastes of birds, animals and fishes.
Ex. Gauno, blood meal, meat meal, fish meal, bone meal and horn and hoof meal
Prepared by Dr. T. H. Hanumantharaju, Associate Professor, Dept. of Soil Science & Agril. Chemistry, UAS, GKVK, Bangalore
-1-
Organic manures
1) Farm yard manure (FYM): Farm yard manure refers to the refuse from
farm animals, mainly sheep, cattle and poultry. It consists of decomposed or
partly decomposed mixture of dung, urine and the litter. It is a mixture of
vegetative refuse from the farm and it mostly consist of the nutrient elements
required by the plant. The FYM contains on an average 0.50 % N, 0.25 % P2O5
and 0.50 % K2O, on dry-weight basis.
2) Compost: Compost is an organic manure prepared from plant residues and

animal waste products. The process of making compost is known as composting.
It is a biological process in which aerobic and anaerobic micro-organisms
decompose organic matter and lower the C:N ratio of the refuse. Compost is a
dark coloured powdered material derived from decomposition of plant refuses by
the microbes in the presence of little amount of soluble nitrogen. Composts are
of two types and they differ in nature and composition.
(i) Rural/ village compost: Rural compost is prepared from farm waste
products, e.g. straws, crop stubbles, crop residues such as sugarcane trash,
groundnut husks and leaves, cotton stalks, etc, weeds, waste folder, urine soaked
earth and litter from cowshed. Rural compost contains 0.4-0.8 % N, 0.3-0.6 %
P2O5 and 0.7-1.0 % K2O.
(ii) Urban or city or town compost: Urban compost is prepared from town
waste and night soil. Urban compost contains 1.0 % nitrogen, 1.0 % P2O5 and
1.5 % K2O.
3) Vermi compost: Vermi compost is the organic manure obtained by the use of
earthworms for composting of organic residues. Earthworms can consume all
kinds of organic matter. It is estimated that 100 tons of moist organic matter can
be converted by earthworms into 30 tons of compost. Organic materials undergo
complete biochemical changes in the intestines. It helps in efficient recycling of
animal wastes, agriculture residue and industrial wastes. The excreta together
with their cocoons and undigested feed make up vermicasting. The castings of
earthworms are rich in nutrients (N, P, K, Ca and Mg) and bacterial and
actinomycetes population. The average nutrient content of vermi-compost is 0.6-
1.20 % N, 1.34-2.20 % P 2O5, 0.4-0.67 % K2O, 0.44 % CaO and 0.15 % MgO. It
has been estimated that earthworms add 230 kg N/ ha/ year in grasslands and
165 kg N/ha/year in woodland sites. Earthworms increase the nitrate production
by stimulating bacterial activity and through their own decomposition.
-2-
4) Sludges: The suspended solids removed from wastewater during
sedimentation and concentrated for further treatment and disposal are called
sludge or biosolids. The sludge that settles at the bottom in secondary sewage
treatment process is called activated sludge. It has the remarkable property of
bringing about the rapid oxidation of the organic matter present in fresh sewage.
The sludge contains 3 - 6 % N, 2 % P2O5 and 1 % K2O on dry-weight basis.
5) Green manures: Green manuring is the process of growing of a quick

growing crop and ploughing it to incorporate it into the soil. The green-manure
crop supplies organic matter as well as additional nitrogen particularly if it is a
legume crop, which has the ability to acquire nitrogen from the air with the help
of its root nodule bacteria. A leguminous crop producing 8 - 25 tons of green
manure ha-1 will add about 60 - 90 kg of nitrogen when ploughed under. This
amount would equal an application of 3-10 tons of FYM on the basis of organic
matter and its nitrogen contribution.
6) Oil cakes: Oil cakes are the by-products of oil seeds crops. After extracting
oil form oil seeds, the left residue of seeds is called oil cake. Oil cakes are the
important and quick acting organic nitrogenous manure. It also contain small
amount of phosphorous and potassium. The amount of nitrogen varies with the
type of oil cake. It ranges from 2.5 % in mahua cake to 7.9 % in decorticate
safflower cake. In addition to nitrogen, all oil cakes contain small quantities of
phosphorus (0.8 - 2.9 %) and potash (1.1 - 2.2 %).
7) Press mud: Press mud is a waste product from the sugar industry and used as
manure. For every tone of sugar cane approximately 30 - 40 kg pressmud is
produced. At the time of purification of sugar cane juice sufficient amount of
filth is obtained which contained excess of phosphorus and lime. It contains 8 %
organic matter, 0.5 % N and 1.3 % P and 60-75 % calcium carbonate.
8) Bone meal: Bone meal is both phosphatic manure and fertilizer and slowly
available to crop. It is made from the bones of animals which have been used as
food. It is valued for its phosphorous and calcium content. It is prepared by
drying and crushing of bones after collection from the slaughter houses without
any treatment which is used as manure. The bone meal contains on an average of
3-4 % N and 20-25 % P2O5. Steamed bone meal is white grayish light weight
powder material. It is Ca3(PO4)2 and it is commonly referred as bone phosphate
of lime. The steamed bone meals contain 1 – 2 % N and 25 – 30 % P2O5.
-3-
Table 1. Average nutrient (%) contents of bulk organic manures
Sl. No. Organic manures N P2O5 K2 O
1. Farm yard manure (FYM) 0.80 0.41 0.74
2. Poultry manure 2.87 2.93 2.35
3. Rural compost 1.22 1.08 1.47
4. Urban compost 1.24 1.92 1.07
5 Vermicompost 1.60 2.20 0.67
Table 2. Average nutrient contents (%) of sewage and sludge

Sl. No. Sewage/ sludge N P2O5 K2 O
1. Sewage (raw) 2.0 - 3.0 - -
2. Sludge (primary) 2.0 - 3.5 1.0 - 5.0 0.2 - 0.5
3. Sludge (activated) 4.0 - 7.0 2.1 - 4.2 0.5 - 0.7
Table 3. Nutrient contents (%) of oil cakes

Sl. No. Source N P2O5 K2 O
I Non-edible oil cakes
1. Karanji (Pongamia pinnata) cake 3.9-4.0 0.9-1.0 1.3
2. Neem (Azadirachta indica) cake 5.2 1.0 1.4
3. Castor cake 5.5-5.8 1.8 1.0
4. Mahua (Bassia latifolia) cake 2.5-2.6 0.8 1.8
5. Rapeseed cake 5.1 1.8 1.0
6. Linseed cake 5.5 1.4 1.2
II Edible oil cakes
1. Coconut cake 3.0-3.2 1.8 1.7
2. Cotton cake 3.9 (6.5)* 1.8 (2.8)* 1.6 (2.1)*
3. Groundnut cake 4.5 (7.8)* 1.7 (1.7)* 1.5 (1.4)*
4. Niger cake 4.8 1.8 1.3
5. Safflower cake 4.8 (7.8)* 1.4 (2.2)* 1.2 (2.0)*
6. Sesame cake 6.2 2.0 1.2
Table 4. Nutrient content of some of the concentrated organic manure

Sl. No. Concentrated organic manure N P2O5 K2 O
1 Blood meal 10-12 1.2 1.0
2 Meat meal 10.5 2.5 0.5
3 Horn and hoof meal 13.0 0.3-1.5 -
4 Raw bone 3-4 20-25 -
5 Steamed bone 1-2 25-30 -
6 Fish meal 4-10 3-9 1.8
-4-
Fertilizers
Fertlisers are any natural/ manufactured materials, which are solid/ liquid
added to the soil in order to supply one/ more plant nutrients. It refers to N, P2O5
and K2O which are the constituents of fertilizers. Fertilizers contain these
elements in the form of soluble and readily available forms of nutrients. The
term fertiliser is generally applied to commercially manufactured material other
than lime and gypsum.
Liquid fertilizer
Liquid fertilizer is one in which the plant nutrients (NPK) and other
materials are completely dissolved.
Properties of fertilizers
The physical properties of a fertilizer are almost as important as the
nutrient content of fertiliser. The properties of fertilizers are i) colour, ii) particle
size iii) density iv) granule hardness v) moisture content/ hygroscopicity vi)
solubility vii) nutrient content. It determines how easily and uniformly the
fertilizer spreads during application. Fertilizers with poor physical properties
form lumps or dust, flow badly, accumulate too much water or become
segregated. The important physical properties of fluid fertilizers are density,
viscosity and pH. The strength of the gelling agent is also important. It should be
strong enough to keep the solids in suspension, but not so strong that the liquid is
too thick to be pumped and poured.
i) Colour
Fertilisers such as muriate of potash and super phosphate are produced
from naturally occurring minerals. Some fertilizers are extracted and purified
from natural deposits in the earth. The colour of fertilizers varies depending on
where they were extracted, and the degree of purification. For example, muriate
of potash can be either red, white or colorless crystals. The colour of a fertilizer
indicates the impurities or adulterants of the fertilisers.
ii) Particle size

Particle diameter is the usual measurement of particle size. Particles in a
particular fertilizer have a range of different diameters. This range is called the
particle size distribution. In a fertilizer, smaller particles dissolve in water faster
and releases nutrients quickly. Particle size also affects application and storage
of the fertilizer.
-5-
iii) Density
Density compares the weight of fertilizer to the volume. It depends on
how closely packed the particles are. A low density fertilizer will take up more
space than the same weight of a high density one. This has implications for
storage and is important when calibrating machinery.
iv) Granule hardness

Fertilizer particles need to be hard enough to withstand the pressures of
handling and storing them. Granule hardness will depend on the chemical
composition of the fertilizer as well as its other physical properties such as the
shape of the particles and how much moisture they contain. Hard particles also
make fertilizers less dusty.
v) Moisture content/ hygroscopicity

Most fertilizers absorb water to a certain extent. If they take in too much
water, however, it can be problematic. Moisture absorption depends on the
chemical composition of the fertilizer, environmental conditions and the shape
and size of the particles. Granules with larger surface areas absorb relatively
more water. Critical relative humidity (CRH) is the level of humidity required
for the fertilizer to absorb water. Fertilizers with high CRH values can be
handled and stored in wetter environments. If the CRH is too low, the fertilizer
can clump together and be difficult to spread, and will need to be stored more
carefully to prevent it from getting wet.
Specifications of fertilizers
To control the quality of fertilizers, the Fertiliser (Control) Order, 1985
has laid down specification for the fertilizers. The following parameters of the
specifications are as follows:
i. Moisture, % by weight, maximum
ii. Total nutrient content % by weight ( % N, % P 2O5, % K2O, % Zn, % Mn,
% Cu, % Fe, % Mo, % Mg), minimum
iii. Forms of nutrients % by weight (% NH4, % NO3, % NH3, % urea, %
water soluble P2O5, % citrate soluble P2O5, % water soluble K2O),
minimum/ maximum
iv. Impurities % by weight (% free acid (sulphuric acid/ phosphoric acid), %
As2O3, % biuret, % NaCl, % Ca(NO3)2, % Cl, % MgO, % MgCl2, ppm
oil), maximum
v. Particle size are decided depending on granular size of the fertilizers.
-6-
Classification of fertilizers and manures
A. Based on individual criteria’s/ property
1. Nature of source/ origin of the manure
i) Natural manures
If manures formed through natural processes are known as natural
manures.
Ex.: FYM and minerals deposits (Chilean salt petre, Narweyan salt petre, rock
phosphate).
ii) Artificial manures

If manures are synthetically prepared so they are called as artificial
manures.
Ex.: Compost, vermi-compost, biocompost, synthetic fertilizers.
2. Nature of the materials present/ presence or absence of carbon in the

fertilizer
i) Organic manures
The manures contain carbon in the structure are said to be organic
manures.
Ex. Organic manures, urea and calcium cyanamide.
ii) Inorganic manures

The manures do not contain carbon in the structure are said to be
inorganic manures. Ex. Fertilizers
3. Number of nutrient element present in fertilizer

i) Straight manures
These are synthetically manufactured inorganic fertilizer containing one
major plant nutrient.
Ex. AS, AC, CAN, ASN, SSP, MOP, SOP
ii) Complex/ compound manures

These are synthetically manufactured inorganic fertilizer containing two
or more plant major nutrients. It is obtained by mechanical blending of 2 or more
straight fertilizer. Each granule contains specified proportion of nutrient. The
complex fertilizers are either incomplete/ complete fertilizer.
a) Incomplete manures: The fertilizer with contains two plant nutrients
obtained by manual mixing of two or more straight fertilizer.
Ex. Ammonium phosphate (MAP, DAP), potassium nitrate.
-7-
b) Complete manures: A fertilizer material containing all the three plant
nutrients viz., N, P2O5 and K2O.
Ex. 19:19:19.
4. Physiological property of the fertiliser

The fertilisers are classified based on the residue left after application of
fertiliser to the soil.
i) Acidic fertiliser
Fertilizer capable of increasing the acidity (decreasing pH) of the soil by
continued applications. The amount of calcium carbonate required to neutralize
the acid residue is referred as equivalent acidity and expressed as kg CaCO3/ 100
kg of fertiliser.
Ex. AS (110 kg), AC (128 kg), ASN (93 kg), AN (60 kg), urea (80 kg)
ii) Basic fertiliser

Fertilizers which increase the pH of the soil on continued use by leaving a
basic residue in the soil. The basic residue is expressed as equivalent basicity
and expressed as kg CaSO4.2H2O/ 100 kg of fertilizer.
Ex. Sodium nitrate (29 kg), calcium nitrate (21 kg), CaCN2 (63 kg)
iii) Neutral fertiliser

Fertilisers which do not leave neither acidity/ alkalinity in the soil by
continued application is said to be neutral fertilizers.
Ex. Calcium ammonium nitrate
5. Amount of nutrient content in the fertiliser

i) Low analysis fertilizer
The fertilizers containing less than 25 % of plant nutrients are called low
analysis fertiliser.
Ex: Chilean salt petre (16 % N), AS (20.6 % N), SSP (16 % P2O5).
ii) High analysis fertilizer

The fertilizers containing more than 25 % of plant nutrients are called
high analysis fertiliser. Ex: Urea (46 % N), SSP (45-48 % P2O5), TSP (48 %
P2O5), SOP (50 % K2O), MOP (60 % K2O).
-8-
B. Manures and fertilisers are classified based on the chemical nature
(origin, properties and functions)
Organic manures
Bulky Concentrated
Natural Synthesised Plant origin Animal origin Processed

(FYM, (Compost, (Oil cakes) (Blood meal, (Basic slags,
Sewage, Vermi-compost, Edible: Ground bone meal, Press mud
Sludge, Urban compost nut, sesamum; Horn & hoof Biogass
GM, ) Non-edible: meal) slurry)
Caster, neem)
Fertilisers
Nitrogenous Phosphatic Potassic Compound Complex Mixed
Nitrogenous
Inorganic Organic
Ammonium Nitrate Ammonium & Amide Plant origin Animal origin

(AS, AC) (PN, SN) Nitrate (AN, (Urea, (Oil cakes, (Blood meal,
ASN, CAN) CC) press mud) Guano)
Phosphatic
Natural Treated/ Industrial Synthetic

(Bone Processed by-product (MAP, DAP)
meal, R/P) (SSP, TSP) (Basic slag)
Potassic
Natural Processed Synthetic

(Sylvite, kyanite, wood ash) (MOP, SOP) (PN, PP)
-9-
Nitrogenous fertilizers
1) Ammonium sulphate (21% N): Ammonium sulphate availability has
increased in recent years primarily because it is a by-product of some industries.
Entire nitrogen is in ammonium form. It is a good material for high pH soils (pH
> 7) and can be used where sulphur deficiency is suspected. If applied to alkaline
or calcium soils, it should also be incorporated to eliminate potential ammonia
volatilization losses. It has the disadvantage of being the most acidifying form of
N fertilizer which requires more limestone to neutralize the acidity formed by
the N fertilizer. The cost of ammonium sulphate is usually greater than urea
because of its lower analysis and higher transportation costs.
2) Ammonium chloride (26 % N): It is sometimes called muriate of ammonia.

It is commercially prepared by combining ammonia with hydrochloric acid and
the resultant product, ammonium chloride is found to have very good physical
condition. This fertilizer is also obtained as a by-product of the Solvay’s process
of making sodium carbonate. The commercial sample is a white, crystalline salt
containing 26 % N in the ammoniacal form. The fertilizer is suitable for many
crops except for those, which are sensitive to high chlorine content. It is
physiologically acidic fertilizer.
3) Ammonium nitrate (33 % N): Ammonium nitrate is decreasing in

popularity because of storage problems associated with fire and explosive
hazards. It is an excellent material for many purposes; however, one half of the
N is in nitrate form, which makes it immediately susceptible to potential
leaching and denitrification losses after application.
4) Calcium ammonium nitrate (26 % N): It is produced by granulating

concentration ammonium nitrate solution with limestone or dolomite in a
granulator. It is neutral fertiliser and contains 50 % N in NH4 form and
remaining in NO 3 form.
5) Ammonium sulphate nitrate (26 % N): It is a double salt of ammonium

sulphate and ammonium nitrate. It is also known as Leuna salt petre or
sulphonitrate in Europe. It is a combination of 62.5 % ammonium sulphate and
37.5 % ammonium nitrate and has a nitrogen content of 26 %.
6) Sodium nitrate (16 % N): Sodium nitrate contains N in the nitrate form and
is similar to potassium nitrate and calcium nitrate in its reaction in soils. It is
-10-
used primarily in the vegetable industry when a readily available source of
nitrate N is desired.
7) Calcium nitrate (16 % N): Calcium nitrate contains N in the nitrate form,
which is highly susceptible to leaching and denitrification losses as soon as it is
applied. It is used most extensively in the fruit and vegetable industry where a
readily available source of nitrate N may be desirable.
8) Potassium nitrate (13 % N): Potassium nitrate is used as both K source and
N source. All of the N is in the nitrate form and is subject to leaching and
denitrification as soon as it is added to soil. It is used primarily in the fruit and
vegetable industry as readily available sources of N and K.
9) Urea (46 % N): Urea was the first organic compound synthesized from
inorganic substances by German Chemists by Wohler in 1828. It is the most
widely used dry nitrogen fertilizer. When urea applied to the soil, it is converted
to ammonia which reacts with water to form ammonium within 2 - 3 days. Some
volatilization of ammonia can occur when urea is surface applied.
10) Calcium cyanamide (26 % N): It is a calcium compound used as fertiliser,

first synthesized in 1898 by Frank and Caro. It is formed when calcium carbide
reacts with nitrogen. It is commercially known as nitrolim. When calcium
cyanamide contact with water decomposes and liberates ammonia.
11) Anhydrous ammonia (82 % N): Anhydrous ammonia is a liquid under high
pressure and must be injected at least six inches deep into a moist soil because it
becomes a gas once it is released from the tank. In soil, ammonia reacts with
water to form the ammonium (NH4+) ion, which is held on clay and organic
matter. Anhydrous ammonia is generally the cheapest source of N; however, the
method of application is less convenient and requires more power to apply than
most other liquid or dry materials.
12) Aqueous ammonia (21 % N): Aqueous ammonia is a liquid under low
pressure and must be incorporated into the soil to prevent the loss of free
ammonia to the atmosphere. It is possible to lose all of the free ammonia if it is
not incorporated. Aqueous ammonia has advantages over anhydrous ammonia:
placement need not be as deep, and high-pressure applicators are not required.
-11-
Phosphate fertilizers
1) Single superphosphate (16 % P2O5): It is also referred to as ordinary
superphosphate, is no longer used in large quantities. Because of its lower
analysis and high transportation costs, it has been replaced by concentrated
superphosphate (46% P2O5) and the ammonium phosphates. One of the
advantages of single superphosphate was its significant sulfur content. As
consumption of this material has slowly decreased, concerns over the need for
sulfur have come primarily from the fertilizer industry.
2) Concentrated superphosphate (46% P2O5): It is also known as triple

superphosphate, is being used in direct application as well as in granulated
processes and in bulk blending with other materials. Consumption is less due to
the competitiveness of diammonium phosphate (18-46-0) and monammonium
phosphate (11-48-0). These materials have better storage properties and are more
desirable for bulk blending, particularly where N is required in the final product.
3) Monoammonium phosphate (11-48-0): MAP is a dry material being used

for bulk blending or direct applications. Monoammonium phosphate has lower
ammonium content and may be less injurious to germinating seeds than
diammonium phosphate. The general agronomic effects of diammonium and
monoammonium phosphates are equal for most soils.
4) Diammonium phosphate (18-46-0): DAP is a dry material being used

extensively for bulk blending and for direct application where soils do not need
K or where K is broadcast. It has the advantage of being highly water soluble,
having a high analysis and often a price advantage. Diammonium phosphate has
an acid effect upon the soil similar to anhydrous ammonia. Because of the high
ammonium content, this material can cause germination injury if used in direct
contact with the seed.
5) Polyphosphates: Polyphosphates differ slightly from the more common

orthophosphate fertilizers. Nearly all of the liquid fertilizers containing P are of
the polyphosphate type. Polyphosphates are composed of a series of
orthophosphate molecules connected by the process of dehydration (removal of
water). Commercial ammonium polyphosphates are usually a mixture of ortho-
and polyphosphate. With prolonged storage, polyphosphates will hydrolyse to
orthophosphates. Solutions of ammonium polyphosphate most commonly made
are 10-34-0 and 11-37-0. The most common dry polyphosphate is 13-52-0.
-12-
6) Rock phosphate: Rock phosphate has virtually disappeared from the market
because of its very low water solubility and high transportation costs. Rock
phosphate may, however, supply sufficient P for good crop growth where soils
are moderately acid and where decomposing organic matter is abundant. Today,
rock phosphate is generally processed before it is used as a fertilizer. The
phosphate mineral in soil is found to occur as tricalcium phosphate Ca3(PO4)2 in
combination with either CaCO3, CaF2, Ca(OH)2 or CaCl2. The P2O5 content
ranges from in fresh ore : 16 – 25 % and weathered ore : 23- 32 %.
7) Basic slag: It is a by-product from the steel industry. During the steel
manufacture, the phosphorus in the iron ore is removed to get a high quality steel
as the steel containing more than 2 % P which is brittle. If any flux added to
remove the impurities which is recovered after mixing is said to be slag. The
basic slag is a heavy dark powder and is alkaline. The availability of phosphorus
is found to increase with the fineness of the product as well as with silica content
and decrease as the fluoride content increase. The phosphate is found to be
present in a double silicate form with lime [(CaO)5P2O5SiO2] but some consider
it as tetra calcium phosphate (Ca4P2O5) and still others consider it is a basic
silicon oxy apatite. It is more useful for acid soils.
Potassium fertilizers
1) Muriate of potash (60 % K2O): Potassium chloride also referred to as
muriate of potash, is the major source of K. Potash varies in colour from pink or
red to white depending on the mining and recovery process used. White potash,
sometimes referred to as soluble potash, is usually higher in analysis and is used
primarily for making liquid starter fertilizers.
2) Sulphate of potash (50 % K2O): Potassium sulphate also referred to as

sulphate of potash, is used to a limited extent on crops such as tobacco, potatoes
and a few vegetable crops where chloride from potassium chloride might be
undesirable. Potassium sulphate in some research studies has improved specific
gravity of potato tubers. Potassium sulphate may also be source of sulphur.
3) Potassium nitrate (44 % K2O): It is also known as nitrate of potash, is being

used primarily on high value crops such as celery, tomatoes, potatoes, leafy
vegetables and a few fruit crops. It has a low salt index and provides nitrate N
which may be desirable for these specialty crops.
-13-
Table 5. Nutrient composition of some selected fertilizer materials
Fertilizer materials Solubility Nutrient composition (%)
(%) N P2O5 K2O Ca Mg S
Nitrogen (N)
Ammonia, anhydrous 100 82 - - - - -
Ammonia, aqueous 100 16-25 - - - - -
Ammonium sulphate 100 21 - - - - 23.7
Ammonium chloride 100 26
Ammonium nitrate 100 33.5 - - - - -
Ammonium sulphate nitrate 100 26 - - - - 15.1
Calcium ammonium nitrate 100 26 - - 7.3 4.4 -
Calcium nitrate 100 15 - - 19.4 1.5 -
Potassium nitrate 100 13 - 44 - - -
Sodium nitrate 100 16 - - - - -
Urea 100 46 - - - - -
Calcium cyanamide 100 21 - - 38.5 - -
Ureaform Variable 38 - - - - -
Sulphur-coated urea Variable 35 - - - - 21
Phosphate (P)
Single superphosphate (SSP) 85 - 18-20 - 20.4 - 11.9
Concentrated superphosphate 87 - 42-50 - 13.6 - 1.4
Monoammonium phosphate 90+ 11 48 - 1.1 - 2.2
Diammonium polyphosphate 95+ 16-21 48-53 - - - -
Ammonium polyphosphate 100 10-15 34-62 - - - -
Bone meal - 2-4.5 22-28 - 20-25 - -
Basic slag 12 - 20 - 40 - 50
Rock phosphate <1 - 30-36 - - - -
Potash (K)
Muriate of potash 100 - - 60-62 - - -
Potassium sulphate 100 - - 50 - 1.2 17.6
Potassium nitrate 100 13 - 44 - - -
-14-
Ex. No. 2 Date:
Determination of nitrogen in organic manures
Principle
A known quantity of powdered manure/ compost sample is digested with
conc. sulphuric acid in the presence of digestion mixture by heating in a
digestion chamber. Under these conditions, ammonium sulphate is formed from
organic (protein) nitrogen and non-protein nitrogen compounds in the manure/
compost. The digested sample is distilled in the presence of alkaline medium and
ammonia released is trapped in boric acid with mixed indicator which is then
titrated against std. acid. The nitrogen content of the manure is calculated by
using the relationship of 1 mL of 1 N H2SO4 = 0.014 g of nitrogen (N)
Reactions
R-NH2-COOH + H2SO4 (NH4)2SO4
(NH4)2SO4 + NaOH Na2SO4 + NH3 + H2O

3NH3 + H3BO4 (NH4)3BO4
(NH4)3BO4 + H2SO4 (NH4)2SO4 + H3BO4
Reagents
1. Conc. sulphuric acid
2. Sodium hydroxide (40 %) solution: Dissolve 40 g of NaOH in about 80
mL water and make up the volume to 100 mL.
3. Boric acid (4 %) solution: Dissolve 40 g of boric acid in hot distilled
water, cool and then make up the volume to 1 L.
4. Mixed indicator solution: Mix 0.1 g of bromo cresol green with 0.07 g of
methyl red and dissolve this mixture in 100 mL ethanol.
5. Std. sulphuric acid (~ 0.1 N) solution: Dilute 2.8 mL of conc. H2SO4 is
diluted to 1000 mL of distilled water and then standardise it against Std.
sodium carbonate solution.
6. Digestion mixture: Mix 100 parts of potassium sulphate, 20 parts of
copper sulphate and 1 part of selenium (Se) powder and grind it to get
fine powder.
7. Std. sodium carbonate (0.1 N) solution: Dissolve 5.3 g of Na2CO3 in 500
mL of distilled water and then make up the volume to 1 L.
-15-
Procedure
I. Digestion of the sample
1. Weigh 1 g of powdered manure/ compost sample into Kjeldahl’s
digestion flask.
2. Add 2 - 3 g of digestion mixture and about 20 mL of conc. sulphuric acid.
3. Digest the contents in a digestion chamber over a low flame till a light
bluish green residue is obtained. Then cool the contents and make up the
volume to 100 mL with distilled water.
II. Distillation of the sample

4. Pipette out 10 mL of the digested sample into a distillation flask and add
about 100 mL distilled water.
5. Measure about 25 mL of 4 % boric acid in a receiving flask. Care should
be taken that the delivery tube is dipped in boric acid during distillation.
6. Add about 10 mL of 40 % sodium hydroxide to the distillation flask and
distillate the contents.
7. After complete distillation, disconnect the receiving flask.
III. Titration of the sample

8. Titrate the contents of receiving flask against std. sulphuric acid till it
becomes pink in colour.
9. Note down the titre value (TV) and calculate the nitrogen (%) in manure.
Calculations
1 mL of 1 N H2SO4 = 0.014 g of nitrogen (N)
TV x N of acid x 0.014 x Vol. of digested sample x 100

Nitrogen (%) =
Wt. of sample x Aliquot taken
Note
To trap the ammonia during distillation, std. sulphuric acid can be used
instead of boric acid. The volume (V1) and concentration (N1) of the sulphuric
acid taken for trapping of ammonia is crucial in calculation. The entire content in
the receiving flask after distillation (trapping) should be titrated (TV) against std.
alkali (N2) using methyl red indicator.
[V1 x N1 - TV x N2] x 0.014 x Vol. of digested sample x 100
Nitrogen (%) =
Wt. of sample x Aliquot taken
-16-
Ex. No. 3 Date:
Determination of phosphorus in organic manures
Principle
The nutrients in the manure/ compost is digested with diacid on sand bath
till digested material turns to either colour less or whitish. The phosphorus in the
aliquot of the digested material in presence of vanadium (V5+) and molybdenum
(Mo6+), orthophosphates forms a yellow coloured phospho vanado molybdate
complex which can be read using spectrophotometer 430 nm.
Reagents
1. Di acid mixture: Mix the nitric acid and perchloric acid in the ratio of 9:4.
2. Std. phosphorus (100 ppm) solution: Dissolve 0.44 g of dried (40oC)
potassium dihydrogen phosphate in 400 mL of distilled water. Then add
25 mL of 7 N H2SO4 and make up the volume to 1 L with distilled water.
3. Vanadomolybdate reagent (Barten’s reagent): Separately dissolve 25 g of
ammonium molybdate in 400 mL of hot distilled water and 1.25 g of
ammonium metavanadate in 300 mL of boiling distilled water. Cool the
content's and add 250 mL of Conc. HNO3. Mix the ammonium molybdate
solution and ammonium metavanadate solution and make up the volume
to 1 L.
Procedure
I. Digestion
1. Weigh 1 g ground manure/ compost sample in 100 mL conical flask.
2. Add 5 mL of conc. nitric acid, mix the contents by swirling and keep it
over night for pre digestion
3. Add 10 mL of di-acid mixture and mix the content of the flask by
swirling.
4. Keep the flask at low heat on hot plate in a digestion chamber and slowly
raised to higher temperature until the production of red nitrite fumes
ceases, continue digestion until the volume is reduced to about 5 mL.
5. The completion of digestion is confirmed by the snow white residue or
when the liquid become colorless.
6. After cooling make up the volume with glass distilled water.
7. If acid digest cannot be subjected to analysis immediately, then the
volume should be made using 6 N HCl.
8. Use aliquots of digested solution for the determination of P, K, Ca, Mg, S,
Fe, Mn, Zn and Cu.
-17-
II. Preparation of the standard curve
1. Pipette out 100 ppm P solution to a series of 50 mL volumetric flasks to
get a concentration of 0, 5, 10, 15, 20 and 30 ppm P solution.
2. Add 10 mL of vanadomolybdate reagent, shake and make up the volume.
3. Read colour intensity at 430 nm after 30 minutes.
4. Plot the absorbance against concentration and draw the standard curve.
III. Manure sample

1. Pipette out 5 mL of digested sample into a 50 mL volumetric flask
2. Add 10 mL of vanadomolybdate reagent, shake and make up the volume.
3. Read colour intensity at 430 nm after 30 minutes.
4. Compare the unknown sample absorbance with standard curve
Observations
1. Weight of sample taken =Wg =1g
2. Total volume of di acid digestion extract = V1 mL = 250 mL
3. Volume pipetted out = V2 mL = 10 mL
4. Volume made up = V3 mL = 50 mL
5. Concentration of P in the solution = Y ppm = OD x Av. Slope
6. Av. Slope = conc/ OD
Standard curve of phosphorus

Sl. Conc. P Vol. to be pipetted Transmittance Absorbance/ Slope
No. (mg/ L) from 100 ppm of (%) Optical density
P (mL)
1. 0 0
2. 2.5 1.25
3. 5 2.5
4. 10 5.0
5. 20 10.0
6. 30 15.0
Sample I
Sample II
Calculations
Graph ppm × Vol. of digested sample × Vol. made up × 100
Phosphorus (%) =
106 × weight of sample × aliquot taken
-18-
Ex. No. 4 Date:
Determination of potassium in organic manures
Principle
Flame photometry is also known as flame emission or flame atomic
emission, the sample in solution, is sprayed into a flame to vaporize, atomize,
and excite the sample. The excited atoms of the element of interest emit light at
certain discreet wavelengths, which characteristic of that element. Light of the
wave length of interest is separated from reminder of emitted radiations and its
intensity is measure. The intensity measurement can be related directly to the
concentration of the element of interest usually by comparing with the measured
intensities of a standard or series of standards.
Reagents
1. Std. potassium (1000 ppm) solution: Weigh 1.91 g of dried KCl into a
1000 mL volumetric flask and make up the volume (stock solution A).
2. Std. potassium (100 ppm) solution: Pipette out 100 mL of 1000 ppm of K
into a 1000 mL volumetric flask, dilute with distilled water and make up
the volume (stock solution B).
Procedure
I. Preparation of standard solution
1. From 100 ppm K solution, various standards are prepared ranging from 5
to 40 ppm K by taking 2.5, 5, 10, 20 mL in 50 mL of volumetric flask.
2. Make up the volume to 50 mL with distilled water
3. Adjust the galvanometer to read 0 for blank and 100 for 40 ppm K
solution. Then introduce the standards and record the readings.
4. Construct the standard curve with the readings recorded for various
standard solutions.
II. Manure sample

5. Transfer about 5 mL of the digested sample solution to a vial,
6. Feed the sample into the aspirator and note down the galvanometer
reading.
7. Deduce the concentration of potassium in the solution from the standard
curve
8. Calculate the K in percent of the given organic manure sample.
-19-
Observations
1. Weight of sample taken =Wg =1g
2. Total volume of the digested sample = V1 mL = 250 mL
3. Volume pipetted out = V2 mL = 10 mL
4. Concentration of K in the solution = Y ppm = OD x Av. Slope
5. Av. Slope = conc/ OD
Standard curve of potassium

Conc. of K Vol. to be pipetted Flame photometer Slope
(ppm) from 100 ppm (mL) reading
0 0
5 2.5
10 5
20 10
40 20
Sample I
Sample II
Calculations
Graph ppm × Vol. of digested sample × Vol. made up x 100

Potassium (%) =
106 × weight of sample × Aliquot taken for dilution
-20-
Ex. No. 5 Date:
Study of principles of fertiliser sampling
The important feature of FCO is in sampling of the fertilizer i.e., drawing

samples. The procedure for drawl of fertilizer samples as per the Schedule II,
Part “A” are,
I. Selection of bags for sampling
A. Sample collection from packages or bags
1. All bags in a single consignment of material of the same grade and type
from a single batch constitute a lot.
2. If a consignment is containing different batches, the bags of each batch
shall constitute a separate lot.
3. If a consignment is drawn in a continuous process, 2000 bags or 100
tonnes of the material shall constitute lot.
Table 6. Number of bags to be selected from a lot depends upon the size of the
lot
Lot size (N) No. of containers Lot size (N) No. of containers
to be selected (n) to be selected (n)
1 < 10 1 6 600 – 800 6
2 10 -100 2 7 800 – 1000 7
3 100 – 200 3 8 1000 – 1300 8
4 200 – 400 4 9 1300 - 1600 9
5 400 – 600 5 10 > 1600 10
All the bags of a lot should be arranged in a systematic manner. Start

counting from any bag randomly, go on counting as a, 2, 3, … upto r and so on, r
being equal to the integral of N/n. Thus for every rth bag counted shall be
withdrawn and all bags shall constitute the sample bags from where the sample
is to be drawn for preparing a composite sample.
1. Sampling from the big gowdans/ high stacking

If the above procedure for selection of bags is not possible to be adopted,
the sample should be drawn from the randomly selected fertilizer bags from
different layers, from top and from all open sides in a zig-zag fashion.
-21-
2. Sampling from the small gowdans
All the fertilizer bags of the same grade and type of each manufacturer
though received on different dates shall be segregated and properly stacked. All
bags of same grade and type of fertilizer manufactured by a particular
manufacturing unit may be considered as one lot based on their physical
conditions and the sample shall be drawn as per procedure laid down in selection
of bags for sampling and drawn of samples from bags.
3. Sampling from the damaged stocks

a) In case of torn or lumpy bags, damaged fertilizer bags or seepings, the
stock should be arranged according to identifiable lots. From each lot the
number of bags shall be selected as per procedure for selection of bags for
sampling. If the bags allow the use of sampling probe conveniently, the
samples should be drawn by sampling probe.
b) In case it is not possible to use the sampling probe, the bags may be
opened and fertilizer material mixed together uniformly by hammering
the big lumps or putting pressure, if reqired, andthen samples drawn by
using suitable sample device.
II. Sampling tools

a) Sampling probe
The appropriate instrument to be used by the inspectors for collection of
representative fertilizer sample is called sampling probe. The probe may be
comprised of slotted single tube with solid cone tip made up of stainless steel or
brass. The length of the probe may be 60 – 65 cm and the diameter of the tube
may be 1.5 cm and the slot width may be 1.2 – 1.3 cm. The probe may be used if
the physical condition of the fertilizers and packing materials permits its use.
b) Stainless steel or brass cups

In case of high density polyethylene packings and also when the fertilizer
material is not free flowing, the use of sampling probe may not be possible. In
such a case, selected bags for drawing samples may be opened and the fertilizers
may be taken out of the bags and spread on a clean surface and samples drawn
with the help of a stainless steel or brass cup.
III. Drawal of samples from bags

i) Using sampling probe: The sampling probe is inserted into the bag from
one corner to another diagonally and when filled with fertilizer, the probe
-22-
is withdrawn and fertilizer is emptied in a container and made into one
composite sample.
ii) If the bags do not permit the use of sampling probe, empty the contents of
the bags on a level, clean and hard surface and draw a composite sample
by the process of quartering as described under preparation of composite
sample and sampling probe.
iii) In case of chelated micro-nutrients and mixtures of micro-nutrients, the

three identical containers of the batch, grade, type and manufacturer, shall
be selected which shall constitute the composite samples, provided it is
not possible to draw a composite sample of the size given under weight of
one sample.
IV. Preparation of composite samples

i) If the composite sample collected from the different selected bags is
larger than required weight, its size shall be reduced by method of
quartering.
ii) Spread the composite sample on a level, clean, hard surface, flatten it out
divide in into four equal parts. Remove any diagonally opposite parts.
Mix the two remaining parts together to form a cone, flatten out the cone
and repeat the operation of quartering till a composite sample of required
weight is obtained.
iii) One sample of the fertilizer shall have the approx. weight of 100 g for
straight fertilizer, 400 g for other fertilizers and mixtures of fertilizer and
50 g for chelated micronutrients fertilisers
V. Preparation of samples for lab analysis

1. The composite sample obtained above shall be spread out on a clean, hard
surface and divided into three approximately equal portion of 250 g.
Each of these samples shall constitute the test sample.
2. Each test sample shall be immediately transferred to a suitable container

and each bag shall also be properly labelled. Each test sample container
shall then be sealed.
-23-
3. Out of the three samples, one sample shall be sent to the in charge of the
laboratory notified by the Govt. Another sample shall be given to the
manufacturer or importer or dealer or the purchaser as the case may be.
The third sample shall be sent by the inspector to his next higher authority
for keeping in safe custody. The packing of sample/ sealing and filling of
Forms ‘P’, ‘J’, ‘K’.
VI. Laboratory analysis

The fertilizer ate tested for various parameters as per the specifications of
fertilizers as per the FCO, 1985.
VII. Time limit

The time limit fixed for collection, analysis and action taken will be 7, 30
and 15 days if the complaints are received/ adulterants are expected.
VIII. Precautions while drawing fertilizer samples

The following measures and precautions shall be observed.
1. Samples shall not be taken at a place exposed to weather.
2. Sampling instruments shall be clean and dry when used.
3. The material being sampled, the sampling instruments and the containers
for samples shall be well protected from contamination.
4. To draw a representative sample, the contents of each containers selected
for sampling shall be mixed as thoroughly as possible by suitable means.
5. The sample shall be placed in suitable, clean, dry and air tight glass or
other suitable containers
6. The sample containers shall be in such size that are almost completely
filled by the sample.
7. Each sample containers shall be sealed air tight after filling and marked
with full details of sampling, date of sampling etc.
8. Sample shall be stored in cool places.
-24-
Collection of compost or manure samples
The sampling of compost or manures is an essential aspect of process
monitoring, quality control, marketing, labelling of product and regulatory
compliance. Sampling decisions require an understanding of the need for data
collection, especially how to sample and when to collect samples. There are
three types of sample collection for compost sampling.
1. Point sampling
The point sampling is site-specific sample collection from within the
general mass is used to identify and quantify points of extreme variability, hot
spots or problem zones. Point sampling alone should not be used unless special
conditions exist.
2. Composite sampling
Composite sampling is a single sample for laboratory analysis composed
of multiple, well-blended point or sub-sample uniformly distributed throughout
the entire volume that , after mixing, accurately represents an average or median
value of the properly or trait of interest for a batch or general mass.
3. Stratified sampling
Stratified sampling is a modified composite sampling and is used to
document gradients and define heterogeneity as a function of position within the
bulk or general mass of sampled material, where the general mass is subdivided
into separate zones and series of point-samples are collected and composited
within each zone. Stratified sampling should be used when heterogeneity of
compost is unknown and when regulatory constraints require knowledge of the
relative spatial and temporal variability. This is most often based upon the
standard deviation and mean.
-25-
Ex. No. 6 Date:
Study of qualitative tests for fertilizers
Qualitative tests are analysis to detect different radicals present in the

fertiliser solution which forms the basis for identification of the type of
fertilisers. The radicals present in the fertiliser or manures may be either anions
(NO3-, PO43-, SO42-, Cl-) or cations (NH4+, K+, Ca2+, Na+). Qualitative tests
forms, the basis for subsequent quantitative analysis of complex fertilisers.
Principle
A small quantity of fertiliser solution (approx. 2 mL) are taken in the test
tube and add appropriate reagents for the test designated, look for the reaction
products which forms the basis for the presence of the radicals. If the test is
positive, confirms the presence of that radical and negative test indicate the
absence of the radical in the fertiliser solution.
Preparation of fertiliser solution

Dissolve 20 g of fertiliser solution in around 400 mL of distilled water
and filter the fertiliser solution and make up the volume to 500 mL.
Reagents
1. Nessler’s reagent: Dissolve 3.5 g of potassium iodide in 100 mL of
distilled water and 4 % mercuric chloride solution with stirring until a
slight red precipitate remains (325 mL). Then introduce the stirring a
solution of 120 g of sodium hydroxide in 250 mL of water and make up
to 1 L with distilled water. It is a 0.09 mol/L solution of potassium tetra
iodomercurate (K2[HgI4]) in 2.5 mol/L potassium hydroxide.
2. Ferrous sulphate (10 %) solution: Dissolve 10 g ferrous sulphate in 100
mL of distilled water.
3. Conc. Sulphuric acid
4. Conc. Nitric acid
5. Ammonium molybdate (20 %) solution: Dissolve 20 g ammonium
molybdate in 100 mL of distilled water.
6. Sodium hydroxide (10 %) solution: Dissolve 10 g sodium hydroxide in
100 mL of distilled water.
7. Acetic acid
8. Tartaric acid (10 %) solution: Dissolve 10 g of tataric acid in 100 mL of
distilled water.
-26-
9. Picric acid (1 %) solution: Dissolve 1 g of picric acid in 100 mL of
distilled water.
10. Sodium cobaltinitrite (5 %) solution: Dissolve 5 g sodium cobaltinitrite in
100 mL of distilled water. Or Separately weigh 35 g sodium nitrite and 20
g of cobalt nitrate dissolve in 100 mL of distilled water
11. Dil. Hydrochloric acid (5 %) solution: Mix 5 mL of hydrochloric acid in
12. Barium chloride (10 %) solution: Dissolve 10 g barium chloride in 100
mL of distilled water.
13. Ammonium oxalate (20 %) solution: Dissolve 20 g ammonium oxalate in
14. Buffer solution: Dissolve 6.8 g of ammonium chloride in 25 mL distilled
water. Add 57 mL of ammonia and dilute to 100 mL with distilled water.
15. Uranyl zinc acetate
16. Silver nitrate (0.1 N) solution: Dissolve 1.7 g of silver nitrate in 100 mL
of distilled water.
1) Test for ammonical nitrogen

a) Take 2 mL of fertiliser solution in a test tube, add 2 mL of alkali and heat it,
the smell of ammonia is an indication of ammonium.
b) Take 2 mL of fertiliser solution in a test tube, place the glass rod on the mouth
of the test tube which is dipped in conc. hydrochloric acid, the formation of
dense white fumes confirms the presence of ammonium.
c) Take 2 mL of fertiliser solution in a test tube, add drop by drop of Nesslers

reagent, formation of ammonium dimercuric iodide, which is reddish brown
precipitate or yellow colour confirms the presence of ammonium ion.
NH4+ + 2[HgI4]2 + 4OH HgO·Hg(NH2)I + 7I + 3H2O

(NH4)2SO4 + 2NaOH 2NH3 + Na2SO4 + H2O
2NH3 + 2K2HgI4 NH2Hg2I3 + 4KI + NH4I
2) Test for nitrate nitrogen

a) Take 2 mL of fertiliser solution in a test tube, add copper foil, add 2 mL of
sulphuric acid and heat it, formation brown gas of nitrite, which is an indication
of nitrate.
-27-
b) Take 2 mL of fertiliser solution in a test tube, add 1-2 mL of ferrous sulphate,
shake the contents and add conc. sulphuric acid slowly through the sides of test
tube, formation of brown ring (Fe·NO·SO4) at the junction of two liquids
(middle of the solution) will confirms the presence of nitrate.
4KNO3 + 2H2SO4 2K2SO4 + 4HNO3

4FeSO4 + 2H2SO4 2Fe2(SO4)3 + H2
4HNO3 2H2O + 3O2 + 2NO
2Fe2(SO4)3 + 2H2 + 4NO 4Fe·NO·SO4 + 2H2SO4
2KNO3 + 8FeSO4 + 5H2SO4 3Fe2(SO4)3 + 2FeSO4NO + 2KHSO4 + 4H2O
3) Test for phosphate

Take 2 mL of fertiliser solution, add 1 – 2 drops of dil. nitric acid and add few
drops of ammonium molybdate. Shake the contents, formation of ammonium
phospho molybdate, which is a canary yellow precipitate confirms the presence
of phosphate.
Ca(H2PO4) 2 + 2HNO3 Ca(NO3)2 + 2H3PO4

H3PO4 + (NH4)2MoO4 + 21HNO3 (NH4)3PO4.12MoO3 + 21NH4NO3 + 12H2O
4) Test for potassium

a) Dip the cobalt glass rod with fertiliser solution and place the rod on the flame,
the flame turns to crimson red indicates the presence of potassium.
b) Take 2 mL of fertiliser solution, add 1 – 2 mL of dil. sodium hydroxide, heat

and expel ammonia. Cool it and then add 1 – 2 drops of acetic acid followed by
few drops of sodium cobaltinitrite. Shake the contents, formation of di potassium
sodium cobaltinitite which is a yellow precipitate confirms the presence of
potassium.
KCl + Na3Co(NO2)6 (K2Na)Co(NO2)6 + 2NaCl
c) Take 2 mL of fertiliser solution, add 1 – 2 mL of picric acid, shake the

contents, formation of potassium picrate, which is a yellow precipitate confirms
the presence of potassium.
KCl + C6H2(NO2)3OH C6H2(NO2)3OK + HCl
-28-
d) Take 2 mL of fertiliser solution, add 1 – 2 mL of tartaric acid, shake the
contents, formation of calcium tartarate, which is a white precipitate confirms
the presence of potassium.
KCl + HOOC(OH)CH-CH(OH)COOH HOOC(OH)CH-CH(OH)COOK + HCl
6) Test for calcium

a) Dip the glass rod with fertiliser solution and place the rod on the flame, the
flame turns to brick red colour indicates the presence of potassium.
b) Dip the cobalt glass rod with fertiliser solution and place the rod on the flame,
the flame turns to light green colour indicates the presence of potassium.
c) Take 2 mL of fertiliser solution, add 1 – 2 drops of dil. hydrochloric acid, add

1- 2 drops of buffer, 1 – 2 drops of ammonium oxalate. Shake the contents,
formation of calcium oxalate, which is a white precipitate confirms the presence
of calcium.
CaSO4 + H4N-OOC-COO-NH4 (COO)2-Ca + (NH4)2SO4
7) Test for chloride

Take 2 mL of fertiliser solution, add 2 – 3 drops of silver nitrate. Shake the
contents, formation of silver chloride, which is a white precipitate confirms the
presence of chloride.
KCl + AgNO3 AgCl + KNO3
8) Test for sodium

i) Dip the glass rod with fertiliser solution and keep it on the flame, if it turns to
yellow, indicates the presence of sodium.
ii) Take 2 mL of fertiliser solution, add drop by drop of uranyl zinc acetate and
shake the contents. Allow it to settle, formation of sodium uranyl zinc acetate,
which is greenish yellow precipitate confirms the presence of sodium.
NaNO3 + 3ZnUO2(CH3COO)4 + CH3COOH NaZn(UO2)3(CH3COO)9·6H2O

2Zn(CH3COO)2 + HNO3
-29-
Ex. No. 7 Date:
Study of identification of adulterants in fertilizers
Fertilizer adulteration is explained by The Fertilizer (Control) Order,

1985 of India as follows: A fertilizer shall be deemed to be adulterated, if it
contains any substance the addition of which is likely to eliminate or decrease its
nutrient contents or make the fertilizer not conforming to the prescribed
standard.
The adulterants may be of two kinds as follows:

1. Materials other than fertilizers: Materials other than fertilizers, such as
common salt, gypsum, lime, rock phosphate, soda ash, dolomite, earth, sand,
clay etc. these materials may be sold as fertilizers, such as coloured sand
may be sold as muriate of potash, granulated earth may be sold as
diammonium phosphate or the materials may be mixed with fertilizers. For
example, common salt may be mixed with ammonium sulphate.
2. Cheap fertilizer materials: Cheap fertilizer materials, such as single super

phosphate, muriate of potash etc. These fertilizers may be sold as costly
fertilizers. For example, granulated single super phosphate may be sold as
diammonium phosphate. Muriate of potash may be sold as sulphates of
potash. Also, these cheap fertilizers may be mixed with costly fertilizers. For
example, cheap muriate of potash may be mixed with costly sulphate of
potash.
Preparation of test sample and reference sample

1. The composite sample obtained above shall be spread out on a clean, hard
surface and divided into three approximately equal portions each of the
weight as specified in “weight of one sample”. Each of these samples shall
constitute the test sample.
2. Each test sample shall be immediately transferred to a suitable container.

The sample should be kept in suitable, clean, dry and air tight glass or
screwed hard polythene bottle of about 400 g capacity or in a thick gauged
polythene bag. This should be put in a cloth bag which may be sealed with
the Inspector’s seal after putting inside the detailed description as specified
in Form ‘J’. Identifiable details may also be put on the cloth bag like
sample No./ Code No. or any other details which enables its identification.
-30-
Each sample bag should be sealed air tight after filling and marked with
details of sample, type and brand of fertilizer, name of dealer/ manufacturer
and the name of Inspector who has collected sample. If possible, seal of the
manufacturer/ dealer or purchaser as the case may be, may also be affixed.
3. One sample so sealed shall be sent to the Incharge of the Laboratory

notified by the State Government under clause 29 or Central Fertilizer
Quality Control and Training Institute, Faridabad or Regional Fertilizer
Control Laboratories at Bombay, Madras or Kalyani (Calcutta) for analysis
and the second given to the manufacturer or dealer or the purchaser as the
case may be. The third sample shall constitute the reference sample and
shall be sent by the Inspector to his next higher authority for keeping in
safe custody for production in court, if required.
Quick tests of fertilizers

The identification of adulterants in fertilizers are done similar to that of
qualitative tests of fertilizers. There are two types of tests are performed to know
the fertilizer adulterants. These may be physical tests and chemical test. The
physical tests includes size, shape, colour, moisture, solubility and cold tests.
Some of the tests are listed in the table can be used for finding the adulterants in
fertilizers.
I. Physical test
1. Shape, size and colour
Generally the granulated fertilisers have same size, shape and colour.
Ex: Urea has white colour with round shape, 16:20 has irregular shape grains.
2. Moisture
Fertilisers should not have excess moisture. This may be tested by feel of
the fertiliser by fingers.
3. Solubility test
Some fertilisers are completely soluble in water.
Ex: Urea, Ammonium Sulphate, Ammonium Chloride, MOP, Zinc Sulphate,
Magnesium Sulphate, water soluble fertilizers (100 %).
4. Cold effect
Some fertilsers when dissolved in water give cold effect.
Ex. Urea, MOP, Ammonium Chloride, CAN, 15:15:15
Table 7. Guidelines to detect adulterants in fertilizers
-31-
Sl. No. Details of procedure Adulterants/ if Adulterant/ if not
duplicate duplicate
1. Urea
1. 1 g fertilizer + 5 mL Undissolved particles Dissolved completely
distilled water will settle at the Cooling effect will be
bottom there
Cooling effect will
not be there
2. 1 g fertilizer + 5 mL White particles White particles does not
distilled water + 2 appear appear
mL AgNO3 solution
3. 1 g fertilizer + 5 mL Undissolved particles Fertilizer dissolves
distilled water when appear completely
heated
2. Diammonium phophate
1. 1 g fertilizer when Swelling of crystals Crystals will swell and
heated on tin sheet does not occur sticks to the bottom
2. Fertilizers when Will not be strong Strong
pressed
3. 1 g fertilizer + burnt No smell of ammonia Smell of ammonia gas
lime when rubbed gas
4. 1 g fertilizer + conc. Will not dissolve Dissolves
HNO3
5. 1 g fertilizer + 5 mL Yellow coloured Yellow coloured
distilled water + 2 particles does not particles appear
mL AgNO3 solution appear
3. Complex fertilizers (20:20)

1. 1 g fertilizer + 5 mL White mixed yellow White mixed yellow
distilled water + coloured particles coloured particles
ferric chloride does not appear appears
solution
2. 1 g fertilizer + burnt No Pungent smell Pungent smell
lime when rubbed
-32-
4. Muriate of potash
1. 1 g fertilizer + 5 mL Undissolved particles Undissolved particles
distilled water appear does not appear
2. 1 g fertilizer + 5 mL No Cooling effect Cooling effect
distilled water
mL cobalt nitrate appear and only colour
solution of the solution
5. Complex fertilizers (Nitrogen – Potash)

1. 1 g fertilizer + burnt Pungent Smell No Pungent smell
lime when rubbed
mL ferric chloride appear
solution
mL cobalt nitrate appear
solution
6. Zinc sulphate
1. 1 g fertilizer + 5 mL When particles does White particles
distilled water + 2 not dissolve the appear, if excess
mL conc. sodium chemical fertilizer is quantity (10 mL) of
hydroxide solution adulterated. NaOH is added to the
solution and if
particles dissolve the
fertilizer confirmed as
zinc sulphate
-33-
Ex. No. 8 Date:
Determination of ammonium, nitrate and total nitrogen in

nitrogenous fertilisers
Principle
Ammonium salts are reacted under alkaline medium (or magnesium
oxide) and the mixture is steam distilled, the ammonia is quantitatively liberated.
The liberated ammonia is then trapped in boric acid with mixed indicator. The
amount of ammonia absorbed in boric acid is determined by titrating with std.
sulphuric acid. From the volume of std. sulphuric acid used for titrating
ammonium borate is used for calculation of nitrogen content in the fertiliser.
When Devarda’s alloy is added, hydrogen liberated reduces the nitrate to

ammonia which is then liberated by alkaline steam distillation. The liberated
ammonia is absorbed in boric acid with mixed indicator. The amount of
ammonia absorbed in boric acid is determined by titrating with std. sulphuric
acid. From the volume of std. sulphuric acid used for titrating ammonium borate
is used for calculation of nitrogen content in the fertiliser.
Reactions
(NH4)2SO4 + 2NaOH Na2SO4 + 2NH3 +2H2O
NH4+ + OH- NH3 + H2O
H3BO3 + 3NH3 (NH4)3BO3
2(NH4)3BO3 + 3H2SO4 3(NH4)2SO4 + 2H3BO3
NH4NO3 + Mg(OH)2 Mg(NO3)2 + 2H2O + NH3

2(NH4)3BO3 + 3H2SO4 3(NH4)2SO4 + 2H3BO3
Zn + 2NaOH Na2ZnO4 + 2[H]

NO3 + 9[H] NH3 + 3H2O
2(NH4)3BO3 + 3H2SO4 3(NH4)2SO4 + 2H3BO3
Reagents
a. Sodium hydroxide (40 %) solution: Dissolve 40 g of NaOH in 100 mL of
distilled water.
b. Std. sulphuric acid (~ 0.1 N) solution: Dilute 3.0 mL of conc. sulphuric
acid in 1 L of distilled water and standardise with sodium carbonate.
-34-
c. Std. sodium carbonate (0.1 N) solution: Dissolve 5.29 g of AR grade
sodium carbonate in 1 L of distiled water and standardise sulphuric acid.
d. Devarda’s alloy: Mixture of Al, Cu and Zn in the ratio of 50: 45:5.
e. Magnesium oxide (freshly ignited)
f. Boric acid (4 %) solution: Dissolve 40 g of boric acid in 1 L of distilled
water. Add 5 mL of mixed indicator to boric acid and the colour of the
contents should be pink, if not, add few drops of dil. HCl, until the bluish
colour of the indicator weakness towards pink.
g. Mixed indicator solution: Dissolve 0.5 g bromocresol green and 0.1 g of
methyl red in 100 mL of ethyl alcohol.
h. Fertiliser solution: Weigh 1 g of the fertiliser sample into a 250 mL
volumetric flask, dissolve with distilled water and make up the volume.
Procedure
I) Ammonium nitrogen (NH4-N)
1. Connect the condenser of the distillation unit to water supply.
2. Pipette out 25 mL of the fertiliser solution into the distillation flask, add
400 mL of distilled water. Add few pieces of porcelain chips.
3. Measure 25 mL of 4 % boric acid with mixed indicator into a 250 mL
receiving flask.
4. Dip the tip of receiving end of the distillation unit with boric acid.
5. Add 10 g of freshly ignited MgO and distil until the distillate runs free of
ammonia, the liberated ammonia is absorbed in boric acid.
6. Titrate against std. sulphuric acid till the colour turns to pink, using the
titre value, ammonium nitrogen content is calculated.
II. Total nitrogen

1. Pipette out 25 mL of the fertiliser solution into the distillation flask.
Dilute it with water to about 400 mL. Add few bits of porcelain.
2. Measure 25 mL of 4 % boric acid with mixed indicator into a 250 mL
receiving flask.
4. Add about 4 g of Devarda’s alloy and 10 mL of 40 % NaOH and distil
until the distillate runs free of ammonia, the liberated ammonia is
absorbed in boric acid.
5. Titrate the ammonium borate present in the boric acid against std.
sulphuric acid till the colour turns from blue to pink.
6. Using the titre value, total nitrogen content is calculated.
-35-
Observations
i. Weight of fertilizer sample taken = Wg
ii. Volume of the fertiliser solution = V1 mL
iii. Volume of aliquot pipetted out into kjeldhal flask = V2 mL
iv. Vol. of std. sulphuric acid used for ammonium nitrogen = X1
v. Normality of the sulphuric acid = N1
vi. Volume of std. sulphuric acid used for total nitrogen = X2
Calculations
1 mL of 1 N H2SO4 = 0.014 g of nitrogen (N)
X1 x N1 x 0.014 x V1 x 100
NH4 – N (%) =
W x V2
X2 x N1 x 0.014 x V1 x 100
Total- N (%) =
W x V2
NO3 - N (%) = [Total – N - NH4 – N]
-36-
Ex. No. 9 Date:
Determination of amide nitrogen (NH2 -N) in nitrogenous fertilisers
Principle
Urea contains nitrogen in amide (organic) form. The amide nitrogen is
converted in to ammonical nitrogen (amino group into ammonium sulphate) by
digesting with sulphuric acid. The digested material is transferred to distillation
flask. In an alkaline medium, the ammonical nitrogen in the digested sample is
liberated through distillation and absorbed in known excess of standard acid
(N/10 sulphuric acid).The excess acid is back titrated against standard alkali
(N/10 KOH) using methyl red indicator and from the volume of standard acid
used for absorbing the liberated ammonia the per cent of N is calculated.
Reactions
CO(NH2)2 + 2H2O (NH4)2CO3
(NH4)2CO3 + H2SO4 (NH4)2SO4 + CO2 + H2O
(NH4)2SO4+2NaOH Na2SO4 + 2NH3 +2H2O
+ -
NH4 + OH NH3 + H2O
H2SO4 + 2NH3 (NH4)2SO4
H2SO4 + 2NaOH Na2SO4 + 2H2O
Reagents
a. Conc. sulphuric acid
b. Digestion mixture: Mix potassium sulphate and copper sulphate in 10:1
ratio.
c. Sodium hydroxide (40 %) solution: Dissolve 40 g of NaOH in 100 mL of
distilled water.
d. Std. sulphuric acid (0.1 N) solution: Dilute 3.0 mL of conc. H2SO4 in 1 L
of distilled water and standardise with sodium carbonate.
e. Sodium carbonate (0.1 N) solution: Dissolve 5.29 g of AR grade Na2CO3
in 1 L of distilled water.
f. Std. alkali (0.1 N) solution: Dissolve 5.6 g of potassium hydroxide in 1 L
of distilled water and standardise with standard acid.
g. Methyl red indicator: Dissolve 0.5 g methyl red in 100 mL of ethyl
alcohol.
h. Fertiliser solution: Weigh 1 g of the fertiliser sample into a 250 mL
volumetric flask, dissolve in distilled water and make up the volume
-37-
Procedure
I. Digestion of the sample
1. Pipette out 10 mL of the solution in to a Kjeldhal flask
2. Add 30 mL of conc. sulphuric acid and mix the contents well
3. Add 2 g of the digestion mixture.
4. Digest the contents till the digest becomes green
5. Make up the volume to 100 mL with distilled water.
II. Distillation of the sample

6. Connect the condenser of the distillation unit to water supply.
7. Pipette out 25 mL of digested sample into distillation flask.
8. Add 200 mL of distilled water and add few bits of porcelain pieces.
9. Measure 50 mL of std. sulphuric acid into a 250 mL receiving flask.
11. Add 25 mL of 40 % NaOH. Heat the contents to boiling. The evolving
ammonia is absorbed in the std. acid taken in a receiving flask. Continue
the distillation until the distillate runs free of ammonia.
12. When the distillate runs free of NH3, detach the delivery tube; rinse it
with distilled water and collect the rinsing to the receiving flask.
III. Titration of the sample

13. Back titrate the excess of std. sulphuric acid against std. alkali (red colour
changes to straw yellow). From the amount of std. sulphuric acid used for
absorbing ammonia, the N content is calculated.
14. Note down the quantity of std. potassium hydroxide used for the
neutralisation of unreacted std. sulphuric acid.
Observations
i. Weight of fertilizer sample taken =Wg
ii. Total vol. of the fertiliser solution = 250 mL
iii. Vol. of aliquot pipetted out into Kjeldhal flask = 10 mL
iv. Vol. of digested sample = 100 mL
v. Vol. of aliquot taken for distillation = 25 mL
vi. Vol. of std. sulphuric acid pipetted into the receiving flask = X mL
vii. Vol. of std. potassium hydroxide used for back titration = Y mL
Calculations
(X x N1 – Y x N2) x 0.014 x V1 x 100
Nitrogen (%) =
W x V2
-38-
Ex. No. 10 Date:
Determination of phosphorus in phosphatic fertilizers
Principle
The monocalcium phosphate, dicalcium phospahte and tricalcium
phospahte in phosphatic fertilisers are extracted with water, citric acid and
hydrochloric acid (6 N). The phosphorus in solution is precipitated as
ammonium phosphomolybdate in nitric acid medium. The precipitate is filtered,
washed with potassium nitrate till free of acid and dissolved in known excess of
alkali and the unreacted alkali is back titrated against sulphuric acid using
phenolphthalein as indicator. From the volume of alkali consumed for dissolving
ammonium phosphomolybdate, phosphorus content of the sample is calculated
using the relationship of 1 mL of 1 N NaOH is equal to 0.00309 g of P2O5.
Reactions
CaHPO4 + (NH4)2C6H6O7 (NH2)2HPO4 + CaC6H6O7
Ca3(PO4)2 + 4HCl Ca(H2PO4)2 + 2CaCl2
Ca(H2PO4)2 + 24(NH4)2MoO4 + 23HNO3 (NH4)3PO4.12MoO3 + 21NH4NO3 + Ca(NO3)2 + 12H2O
(NH4)2HPO4 + 12(NH4)2MoO4 + 23HNO3 (NH4)3PO4.12MoO3 + 23NH4NO3 + 12H2O
(NH4)3PO4 + 12(NH4)2MoO4 + 24HNO3 (NH4)3PO4.12MoO3 + 24NH4NO3 + 12H2O
(NH4)3PO4.12MoO3+ 23NaOH 11K2MoO4 + (NH4)3MoO4 + NaNH4HPO4 + 11H2O
From the equation, it is seen that 23 molecule of sodium hydroxide

(NaOH) is equivalent to 1 molecule of ammonium phosphomolybadate
[(NH4)3PO4.12MoO3] is equivalent to 1 molecule of phosphorus [P] and also
equal to half molecule of phosphorus pentaoxide [P2O5].
23 NaOH = [(NH4)3PO4.12MoO3] = P = ½ P2O5
31 g P 142 g P2O5
40 g NaOH in 1000 mL = =
23 2 x 23
31 g P 142 g P2O5
1 mL of 1 N of NaOH = =
23 x 1000 2 x 23 x 1000
1 mL of 1 N of NaOH = 0.0013 g P = 0.00309 g P2O5

-39-
Reagents
a. Ammonium citrate solution: Dissolve 370 g of citric acid in 500 mL of
distilled water and neutralise with 345 mL of ammonium hydroxide so
that it attains a pH of 7.0 and make up the volume to 1000 mL.
b. HCl (6 N): Dilute 250 mL of conc. hydrochloric acid in 500 mL of
volumetric flask and slowly add distilled water and make up the volume.
c. Dil. ammonia: Dilute 100 mL in 500 mL of distilled water.
d. Conc. nitric acid
e. Ammonium nitrate
f. Ammonium molybdate (20 %) solution: Dissolve 20 g of ammonium
molybdate in 100 mL of distilled water.
g. Potassium nitrate (3 %) solution: Dissolve 30 g of potassium nitrate in 1
L of distilled water
h. Sodium hydroxide (0.1 N) solution: Dissolve 4 g of sodium hydroxide in
i. Sulphuric acid (0.1 N) solution: Dilute 3.0 mL of conc. H2SO4 in 1 L of
distilled water and standardise with sodium carbonate.
j. Phenolphthalein: Dissolve 0.5 g of phenolphthalein in 100 mL of alcohol.
Procedure
I. Extraction of phosphorus
a) Water soluble phosphorus
1. Weigh 1 g of fertiliser and transfer it to a Whatman No.40 filter paper
fitted on to a suitable funnel.
2. Leach the fertiliser by adding 40 - 50 mL of distilled water for 5 times,
allowing each portion to completely drain before adding the next portion.
3. Collect the washings into a 250 mL volumetric flask.
4. Make up the volume with distilled water after adding a few drops of conc.
nitric acid if the filtrate is turbid.
5. Retain the filter paper along with the residue for the estimation of citrate
soluble phosphorus.
b) Citrate soluble phosphorus

1. Add 100 mL of neutral citric acid solution to the residue left over on the
filter paper after washing with water in a 600 mL beaker and heat the
contents on a water bath at 65oC for 60 minutes.
2. Filter it rapidly using a suction pump, wash it with 200 mL of distilled
water and make up the volume to 250 mL.
-40-
c) Total phosphorus
1. Weigh 2 g of super phosphate and transfer it into a 250 mL conical flask.
Add 50 mL of 6 N HCl and digest for 45 minutes on a sand bath.
2. Cool it and filter through whatman No. 40 filter paper. Wash the contents
till it is free from chloride.
3. Collect the entire filtrate and make up the volume to 500 mL.
II. Precipitation of phosphorus

1. Pipette out 10 mL of the extractant to each of 250 mL beaker and add
about 20 mL of distilled water.
2. Add NH4OH till the solution is alkaline, followed by dilute nitric acid
until it is distinctly acidic.
3. Add about 2 g of solid NH4NO3 and warm the contents to about 70ºC on a
water bath.
4. Add 20 mL of the ammonium molybdate slowly to the aliquot of
phosphate solution and gently stir the contents of the beaker.
5. Keep the thermostat maintained at 65ºC for half an hour and allow the
canary yellow precipitate to settle, leaving a clear supernatant liquid.
III. Filtration of phosphorus

1. Filter through Whatman No.40 filter paper by transferring only the
supernatant liquid and retaining as much of the precipitate in beaker.
2. Wash the precipitate with potassium nitrate (3 %) solution with 5-6 times.
Add the next instalment of potassium nitrate solution to the filter paper
after the previously added solution drained off completely. Repeat the
process until the litmus runs free of acid.
(Note: Test by collecting half test tube of the filtrate and by adding a drop
of std. alakli and a drop of phenolphthalein changes to pink colour shows
free of acid).
IV. Titration of phosphorus

1. After making the precipitate acid free transfer the filter paper along with
the precipitate to the same beaker in which precipitation was done and
dissolve the yellow precipitate by adding known excess of std. sodium
hydroxide.
2. Add 2-3 drops of phenolphthalein and titrate against std. sulphuric acid.
3. From the actual amount of std. alkali required to react with the precipitate
is used to calculate the percentage of phosphorus.
-41-
Observations
Sl. No. Particulars WSP CSP TP

i. Weight (g) of the fertiliser taken = W W W
ii. Total volume of leachate (mL) = V1 V3 V4
iii. Aliquot taken (mL) = V2 V4 V6
iv. Amount of std. alkali consumed (mL) to = X1 X2 X3
dissolve the ammonium phosphomolybdate
precipitate
v. Amount of std. sulphuric acid (mL) used for = Y1 Y2 Y3
back titration of std. NaOH
Calculations
1 mL of 1 N NaOH = 0.00309 g P2O5
(X1 x N1 – Y1 x N2) x 0.00309 x V1 x 100

Water soluble P2O5 (%) =
W x V2
(X2 x N1 – Y2 x N2) x 0.00309 x V3 x 100

Citrate soluble P2O5 (%) =
W x V4
(X3 x N1 – Y3 x N2) x 0.00309 x V5 x 100

Total P2O5 (%) =
W x V6
Acid soluble P2O5 (%) = [Total – (Citrate soluble + water soluble)]
Alternate procedure
The method of estimation of phosphorus in fertilizer as detailed above is
not accurate and time consuming. The phosphorus in fertilizer is estimated as
done in the determination of phosphorus in manure by taking the suitable aliquot
of 5 mL of extracted sample.
-42-
Ex. No. 11 Date:
Determination of potassium in potassic fertilisers
Principle
In the absence of sulphate and cations (Ca2+, Mg2+, Fe2+ and NH4+), when
potassium is treated with perchloric acid, an alcohol insoluble compound
potassium per chlorate will formed which can be weighed and the percentage of
potassium can be determined.
So, 138.45 g of KClO4 = 39 g K = 39 x 1.2 g K2O
39 39 x 94
So, 1 g of KClO4 = = = 0.34 g K2O
138. 5 138. 5 x 78
Reagents
a. Conc. hydrochloric acid
b. Barium chloride (10 %)
c. Perchloric acid (20 %)
d. Ammonium oxalate
e. Ammonium hydroxide
f. Alcohol (95 %) saturated with potassium perchlorate
Procedure
I. Preparation of the sample (removal of sulphate and cations)
1. Take 1 g of the fertilizer sample into a 250 mL volumetric flask and make
up the volume and mix well to get homogenise.
2. Pipette out 25 mL of above prepared solution into the beaker, add 10 mL
of conc. HCl and warm the contents in the beaker for 10 min.
3. Add barium chloride drop by drop, into the boiling solution until there is
no further precipitation of barium sulphate
4. Bring the contents of the flask to alkaline with ammonium hydroxide.
5. Precipitate the calcium and any excess of barium by adding ammonium
oxalate solution.
6. Cool the contents, dilute with distilled water and filter the contents
through a dry filter paper. Evaporate the filtrate to dryness in a basin.
7. Cool the residue, moisten with conc. HCl and again evaporate to dryness.
Dissolve the residue with distilled water.
-43-
II. Precipitation of potassium with perchloric acid
1. Transfer the solution obtained as described above into a basin and add
about 7 mL of perchloric acid
2. Evaporate the contents over a bath until white fumes are copiously evolve
3. Cool and redissolve the precipitate in a little quantity of hot water
4. Add 1 mL of perchloric acid and again evaporate it to the fuming stage
5. Cool the precipitate and add 20 mL of alcohol
6. Allow the precipitate to settle and filter the supernatant liquid
7. Redissolve the precipitate in the filter paper and basin with hot water and
add 2 mL of perchloric acid, evaporate to the fuming stage
8. Cool the precipitate and add 20 mL alcohol and stir it thoroughly
9. Allow the precipitate to settle and remove the supernatant liquid through
sintered glass
10. Wash the precipitate by decantation method using 5 mL of water solution
until the precipitate is free from acid (Wash solution: Prepare saturated
potassium perchloride in 95 % alcohol. Keep the solution over solid
potassium perchloride and filter when even needed for use)
11. Dry the precipitate (potassium perchlorate) at 100oC and weigh
12. Calculate the potassium (K2O) by multiplying the weight of the
precipitate by 0.34.
Observations
i. Weight of fertilizer sample taken = Wg
ii. Volume made up = V1 mL
iii. Volume of aliquot pipetted out in beaker = V2 mL
iv. Weight of the precipitate = Xg
Calculations
X x V1 x 0.34
K2O (%) =
W x V2
Alternate procedure
The method of estimation of potassium in fertilizer as detailed above is
not accurate and time consuming. The potassium in fertilizer is estimated as
done in the determination of potassium in manures after preparing the fertilizer
solution (1 g/ 250 mL) as detailed above and make dilution (1 mL of fertiliser
solution is made up to 50 mL) which can read by the flame photometer.
-44-
Ex. No. 12 Date:
Determination of calcium in fertiliser/ amendments
Principle
A known weight of fertiliser containing calcium is extracted with boiling
hydrochloric acid (1:1). The calcium in the extracted solution is titrated against
std. EDTA solution in the presence of mureoxide/ Patton – Reeders indicator.
Reagents
1. Std. EDTA (0.01 N) solution: Dissolve 1.86 g of EDTA in 900 mL
distilled water and make up the volume to 1000 mL. Standardise EDTA
with std. calcium solution
2. Std. calcium solution: Dissolve 0.50 g portion of pure dried CaCO3 in
0.2 N HCl. Solution is boiled to expel the CO2 and dilute to 1 L.
3. Sodium hydroxide (10 %) solution: Dissolve 10 g portion of NaOH in
about 90 mL distilled water and dilute to the 100 mL.
4. Mureoxide indicator: Mix 0.2 g of mureoxide with 40 g of powdered
potassium sulphate.
5. Patton & Reeders reagent
Procedure
I. Extraction
1. Weigh 1 g of fertiliser into 250 mL of conical flask
2. Add 50 mL of HCl (1:1) and boil the contents
II. Determination of calcium

1. Take 5 mL of extracted fertiliser sample in a porcelain dish and dilute
with 10 mL distilled water.
2. Add 5 mL of 10 % NaOH (pH of sample solution would reach > 12).
3. Add about 0.5 g of mureoxide indicator/ Patton & Reeders reagent.
4. Titrate the contents against std. EDTA with stirring until it becomes violet
in colour. Note down the burette reading.
Calculations
TV × N of EDTA × 0.02 × Vol. of digested sample x 100

Calcium (%) =
weight of sample × Aliquot taken
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Ex. No. 13 Date:
Determination of sulphur in fertilisers/ amendments
Principle
A known weight of sulphur containing fertiliser/ amendment is extracted
with boiling HCl (1:1). The released ‘S’ in the solution is precipitated by barium
ions as barium sulphate. This turbidity developed by barium sulphate is then
determined by turbidimeter. Turbidimetric analysis is based on measuring the
weakening intensity of a luminous flux when it passes through a solution
containing particles in suspension.
Reagents
1. Acid seed solution (20 ppm of S): Dissolve 0.109 g of potassium sulphate
in some volume of 6 N HCl and make up the volume to 1000 mL.
2. BaCl2 crystals (20-60 mesh size)
3. Stabilizing reagent: Dissolve 0.25 g gum acacia in 100 mL of water or
mix 20 mL of glycerol with 80 mL of alcohol.
4. Std. sulphur solution (100 ppm S): Dissolve 0.54 g of potassium sulphate
in 1 L of distilled water.
Procedure
I. Extraction
1. Weigh 1 g of fertiliser into 250 mL of conical flask
2. Add 50 mL of HCl (1:1) and boil the contents
II. Preparation of standard curve

1. Take 0, 2.5, 5, 10, 15 and 20 mL of 100 ppm S solution in separate 50 mL
volumetric flasks.
2. Add to each 1 mL acid seed solution and 1 mL stabilizing agent.
3. Dilute the contents to about 40 mL
4. Add to each, 1 g of barium chloride, mix well and make up the volume.
5. Record the turbidity of these solutions at 420 nm within 20 min.
6. Plot the turbidance against concentration of solutions and draw the curve.
Fertiliser sample
1. Take 10 mL of digested sample in a 50 mL volumetric flask.
2. Follow as in the standard curve preparation
3. Record the turbidity or % transmission at 420 nm within 20 min.
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Standard curve of sulphur
Sl. Conc. S Vol. to be pipette Transmittance Absorbance/ Slope
No. (mg/ L) from 100 ppm of (%) Optical density
S (mL)
1. 0 0
2. 5 2.5
3. 10 5
4. 20 10
5. 40 20
Sample I
Sample II
Calculations
Graph ppm × Vol. of digested sample × Vol. made up x 100

Sulphur (%) =
106 × Weight of sample × aliquot taken
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Ex. No. 14 Date:
Determination of zinc in fertilisers/ amendments
Principle
A known weight of fertiliser containing zinc is extracted with boiling
hydrochloric acid (1:1). The zinc in solution can be determined by using Atomic
Absorption Spectrophotometer (AAS).
Principle of AAS
When a solution having a metallic species is introduced into a flame the
solvent evaporates and vapors of metallic ions are obtained. The light radiation
emitting from a hallow cathode lamp (light source) absorbed by the ground state
atoms will be proportional to the number of atoms in the flame. So in AAS, the
amount of light absorbed is determined as the amount absorbed is directly
proportional to the concentration of the element.
Reagents
a. Hydrochloric acid (1:1): Dilute equal volume of conc. hydrochloric acid
and water.
b. Zinc standard (1000 ppm Zn): Dissolve 0.4398 g of ZnSO4.7H2O in glass
distilled water and dilute to 1 L. Dilute this to get 100 ppm and prepare
working standards ranging from 0 to 5 ppm.
Standard curve preparation

1. Prepare the appropriate standards as mentioned in the standard solution
preparation
2. Adjust the instrument to read zero after feeding blank solution.
3. Feed different concentrations of zinc and obtain the readings
4. Plot the values on a graph sheet and construct the standard graph.
Procedure
1. Weigh 1 g of fertiliser into a 250 mL volumetric flask, add 50 mL of HCl
(1:1) extractant and dissolve the contents and make up the volume.
2. Feed the clear sample to the instrument having an appropriate hallow
cathode lamp and record the readings.
Calculation
Graph value × volume of the extractant x 100
Zinc (%) =
106 x Weight of the fertiliser
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Ex. No. 15 Date:
Study of Agrochemicals
Agrochemicals/ Agrichemicals/ Agricultural chemicals is a generic term

for the various chemical products used in agriculture. In most cases,
agrichemical refers to the broad range of pesticides, including insecticides,
herbicides and fungicides. It may also include manures, fertilizers, hormones and
growth regulating substances.
Pesticides
Pesticide is derived from Greek word pestis which means to annoy.
The definitions of pesticides are as follows:
1. A pesticide is a substance or mixture of substances used to kill a pest.
2. According to Environmental Protection Agency (EPA) defines “A
pesticide is any substance or mixture of substances intended for
preventing, destroying, repelling, or mitigating any pest”.
3. A pesticide may be a chemical substance, biological agent (virus or
bacteria), antimicrobial, disinfectant or device used against any pest.
Pest
Pest is any organisms which destroys crop plants and include insects,
mites, microbes (fungus, bacteria and virus), weeds, nematodes and rodents.
In India, with the introduction of high yielding varieties, the pesticide

consumption increased from 3 g/ ha in 1955 to 6 kg/ ha in 2000. Many factors
like phytotoxicity, harmful to non-target organisms and degree of persistence of
the residues of the chemical on the crops have also to be considered while
selecting any chemical for use.
Classification of pesticides/ agrochemicals

It is important to understand the classification of pesticides, since it
greatly assists in the understanding of the subject. The naming and classification
system of pesticides varies greatly; major groups may be based on the type of
organism they control such as insecticides (insects), fungicides (fungi) and
herbicides (plants). The subdivisions are based on chemically related compounds
like organochlorine, organophosphorous, organonitrogen, triazine, pyrethroid.
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I. Based on the target organism
Agro-chemicals used for controlling pests can be divided into different
groups based on the nature of pests to be controlled.
Table 8. Classification of pesticides
Target organism Pesticides Examples
1 Insects : Insecticides Endosulfan, Malathion, Carbaryl,
carbofuran, pyrethroids
2 Arachnids : Acaricides Dicofol, tetradifon, chlorofenzon,
(Mites) azinphos (methyl), binapacryl
3 Fungi : Fungicides Manoczeb, zineb, propineb, captan, folpet,
edipheriphos, carbendazim, metalaxyl
4 Bacteria : Bactericides Streptomycin, Streptocycline, Agrimycin
–100, Tetracyclines Aurecomycin,
Chloromphenicol,
5 Algae : Algicides Dichlone, dichlorofen, diuron
6 Weeds/ plants : Herbicides 2, 4-D, butachlor, benthiocarb,
pendimethalin, atrazine, fluchloralin,
anilophos, paraquat
7 Mollusk’s : Molluscides Metaldehyde, Nitrosamide, copper
(gastropods, or Limacides sulphate, pentachlorophenoate and
snails, slugs) Trifenmorph
8 Nematodes : Nematicides Dichloropropane Dichloropropene,
dibromochloropropane, (Nemagon),
ethylene dibromide, aldicarb,
phorate,fensultothion, carbofuran mocap,
thioxazim, disulfoton, oxamyl
9 Rodents : Rodenticides Zinc phosphide, warfarin, thallium
or Zococides sulphate, alpha-naphthol Thiourea and
bromodialone
10 Birds : Avicides Tetra methyl thiuram disulfide (TMTD)
Anthra quinine
II. Based on the chemical composition

The classification of pesticides based on their chemical nature is rather
complex. The pesticides have been classified into two major divisions, viz.,
inorganic and organic insecticides.
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1. Inorganic
Inorganic pesticides do not contain carbon as part of their chemical
composition. These compounds usually have relatively low molecular weights.
Several inorganic salts (white and crystalline) are classified in this category of
pesticides. A few inorganic pesticides have been used for more than 1000 years
but their use increased dramatically from 1850 to 1950. The popularity of many
inorganic pesticides declined after the development of more effective and less
persistent organic pesticides. Several inorganic compounds have toxic properties
and, therefore, humans have been using them as pesticides for centuries.
Table 9. Common inorganic pesticide

Main group/ sub group/ example Major use
1. Sulphur compounds
Elemental sulphur (S) Fungicide
Lime sulphur (CaS5) Fungicide
Sulphuric acid (H2SO4) Herbicide
Sulfuryl flouride (SO2F2) Herbicide
Ammonium sulphamate (NH4SO3NH2) Herbicide
2. Arsenic compounds
Realgar (As2S2), Insecticide
Orpiment (As2S3) Insecticide
Arsenic oxide (As2O3) Rodenticide
Arsenic acid (H3AsO4) Rodenticide
Paris green, [Cu(CH3COO)2·3Cu(AsO2)2] Insecticide
London purple [(Ca3(AsO3)2) + (Ca3(AsO4)2)] Insecticide
Lead arsenate (PbAsO4), Insecticide
Calcium arsenate (Ca3(AsO4)2) Insecticide
Chromated copper arsenate (As2O5 + CrO3 + CuO) Fungicide
3. Fluorine compounds
Sodium fluoride (NaF) Insecticide
Sodium fluosilicate (Na2SiF6) Insecticide
Sodium fluoaluminate (Na3AlF6) Insecticide
Sulfuryl flouride (SO2F2) Herbicide
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4. Thallium compounds
Thallium sulphate [Ti(SO4)x] Rodenticide
5. Zinc compounds
Zinc phosphide (Zn3P2) Rodenticide
6. Copper compounds
Bordeaux mixture [CuSO4 + Ca(OH)2] Fungicide
7. Mercury compounds
Mercuric chloride (HgCl2) Fungicide
Mecurous chloride (Hg2Cl2) Fungicide
8. Sodium compounds
Sodium chloride (NaCl) Herbicide
Sodium hypochloride (NaOCl) Fungicide
Sodium chlorate (NaClO3) Herbicide
Sodium azide (NaN3) Fumigant
Sodium tetra borate (Na2B4O7·5H2O) Herbicide
2. Organic pesticides
Organic pesticides are a diverse group of chemicals. They contain carbon
in the structure and complex molecules. Some of the organic pesticides are of
minerals, produced naturally by certain plants, animals, microorganisms and
organic pesticides have also been synthesized by chemists. The organic
pesticides are broadly divided into biopesticides and synthetic pesticides.
a) Biopesticides
Biopesticides are certain types of pesticides derived from such natural
materials as animals, plants, bacteria and certain minerals. For example, canola
oil and baking soda have pesticidal applications and are considered
biopesticides. Biopesticides fall into three major classes:
1) Microbial pesticides
Microbial pesticides consist of a microorganism (e.g., a bacterium,
fungus, virus or protozoan) as the active ingredient. Microbial pesticides can
control many different kinds of pests, although each separate active ingredient is
relatively specific for its target pests.
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2) Plant incorporated protectants (PIPs)
Plant incorporated protectants are pesticidal substances that plants
produce from genetic material that has been added to the plant. For example,
scientists can take the gene for the Bt pesticidal protein, and introduce the gene
into the plant's own genetic material. Then the plant, instead of the Bt bacterium,
manufactures the substance that destroys the pest.
3) Biochemical pesticides
Biochemical pesticides are naturally occurring substances that control
pests by non-toxic mechanisms. Biochemical pesticides include substances, such
as insect sex pheromones, that interfere with mating, as well as various scented
plant extracts that attract insect pests to traps.
Common bio-pesticides
1. Animal origin
i) Nereistoxin (cartap): Marine animals, like Lumbrianerias heteropoda, L.
braviciara, against insects.
2. Plant origin
i) Nicotine and Nornicotine (Tobacco, Nicotina rustica), Anabasine or
neonicotine (Anabasis aphylla), Rotenoids (Derris, Lonchocarpus, and
Tephrosia), Pyrethroids (Chrysanthemum cinerariaefolium) against insects.
ii) Isoflavonoid compounds, such as glyceollin, phaseolin, and pisatin in soybean,

garden bean, and pea, respectively, phenolic lactone juglone, a product of
several walnut species, Wyerone, an acetylenic acid derivative produced by
legumes have been implicated in protection of crops from pathogens.
iii) Sesquiterpenoid lactone, artemisinin from Artemisia annua L Terpenoid

allelochemical 1,8-cineole, with the common name of cinmethylin,
Toxaphenereg., a mixture of chlorinated camphene derivatives, was sold as a
herbicide. Plants have been not much exploited as sources of herbicides.
iv) Asteraceae, the photodynamic compound alpha-terthienyl has been shown to

account for the strong nematicidal activity of the roots. Marigolds (Tagetes
spp.), rattlebox (Crotalaria spectabilis), chrysanthemums (Chrysanthemum
spp.), castor bean (Ricinus communis), Neem (Azardiracta indica) and many
members of the family Asteraceae (Compositae) have the active principles of
nematicidal activity has not been discovered.
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3. Micro-organisms
i) Bacteria: Bacillus thuringiensis and Agrobacterium radiobacter against certain
insects.
ii) Fungi: Trichoderma against Rhizoctonia solanii, Beauveria bassiana against

aphids, fungus gnats, mealy bugs, mites, thrips, whiteflies
iii) Virus: Nuclear Polyhedrosis Virus (NPV) for Gypsy moth, Tussock moth,
Pine sawfly and Granulosis virus (GV) for codling moth.
iv) Protozoans: Nosema locustae against European cornborer caterpillars,

grasshoppers and mormon crickets.
v) Nematodes: Steinernema feltiae, Heterorhabditis heliothidis against larvae of a

wide variety of soil-dwelling and boring insects.
v) Antibiotics: Antibiotics are substances produced by certain microorganisms

that inhibit or kill other microorganisms.
Ex. Streptomycin, Streptocycline, Agrimycin, Tetracyclines
b) Synthetic organic pesticides

Synthetic organic pesticides are manufactured in laboratory and marketed
by a chemical company. Synthetic pesticides are generally grouped into similar
chemical classes such as organo-chlorines, organophosphates, pyrethroids,
carbamates, nicotinoids, quinines, amides, traizines, uracils etc. During the last
60 years new synthetic pesticides have become more pest specific, exhibit lower
toxicity and are less environmentally damaging. While synthetic pesticides have,
without doubt, contributed to an abundant and cheap food and fibre supply they
present a certain amount of risk to human and environmental health.
Table 10. Common synthetic pesticides

1. Dinitrophenols: Binapacryl, Dinocap
2. Thiocyanates: Lord, Thanite
3. Organochlorines: BHC, DDT, Endo-sulfan
4. Organophosphorus: Chloropyrifos, Phorate, TEPP
5. Organosulphur: Tetradifon, propargite,ovex
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6. Carbamates: Carboryl, Carbofuran, Aldicarb
7. Dithiocarbamates: Mancozeb, Zineb, Propineb
8. Quinones: Chloranil, Dichlone,
9. Halogenated hydrocarbon: Chloropicrin, Methyl bromide
10. Organotins: Duter, Brestan
11. Organomercurials: Agrosan, Ceresan, Emison
12. Phenols: Dinitro-sec-butylphenol
13. Heterocyclic N : Captan, Folpet, Difolaton
14. Oxathins: Plantavax, Vitavax
15. Aliphatic carboxylic: TCA, Dolapan, Kenopan
16. Aromatic carboxylic: 2,4 D, Silvex, Fenac, DCPA
17. Benzonitrile: Dichlobenil, Bromoxynil
18. Phenyl urea: Fenuron, Monuron, Diuron, Linuron
19. Uracil: Bromacil, Isocil, Terbacil
20. Pthalic acids: Chlorothal, Endothal
21. Phenols: Pentachlorophenol (PCP), 4,6-Dinitro-ortho-cresol
(DNOC), Dinosam (DNAP), Dinoseb (DNBP)
22. Methyl anilines: Benefin, Pendimethalin, Trifluralin
23. Amides: Alachlor, Butachlor, Delachlor, Propanil
24. Traizines: Atrazine, Simazine, Propazine, Prometone
25. Dipyridyls: Paraquot, Diquot, Difenzoquat
26. Phenyl carbamtes: Carbetamide, Barban, Asulam
27. Thiocarbamates: Thiobencarb, Cycloate, Vernolate
28. Diphenyl ether: Bifenox, Fluorodifen, Oxyfluorafen
29. Organoarsenic: DMAA, MSMA, DSMA
30. Phosphono amino acids: Glyphosate, Glufosinate
31. Sulfonylurea: Chlorsulfuron, Bensulfuron,
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IV. Based on the toxicity
Toxicity is the property of the pesticide when used in small quantities to
affect the normal activity of the organism and cause in to be poison to death. The
LD50 is one way to measure the short-term poisoning potential (acute toxicity) of
a material.
LD50 (Lethal Dose)

LD50 is the amount of a material, given all at once, which causes the death
of 50 % (one half) of a group of experimental animals. The acute toxicity is
determined by testing the pesticides (chemicals) against various mammals
generally rats or mice. It is usually expressed as the amount of chemical
administered as mg per kg of the body weight of the test animal.
The LD50 can be found for any route of entry or administration but dermal
(applied to the skin) and oral (given by mouth) administration methods are the
most common. Dermal toxicities are slightly less than the oral values while
intravenous toxicities are higher than the oral figures the smaller is the LD50
value the more toxic is the chemical so that the toxicity of the chemical can be
graded by the LD50 values.
Table 11. Toxicity classes as per Insecticide Act (1968) in India

Classification of the LD50 LD50 Colour on the Symbols & words
Insecticides (Oral) (Dermal) label
1 Extremely toxic 1-50 1-200 Bright red Skull & Cross-
bones "POISON"
2 Highly toxic 51-500 201-2000 Bright yellow POISON
3 Moderately toxic 501-5000 2001-20000 Bright blue DANGER
4 Slightly toxic > 5000 > 20000 Bright green CAUTION
Table 12. LD50 (mg kg-1) (oral for rats) values of the some of the pesticides
Pesticides Group name LD50
1. DDT Organochlorine 87
2. Dieldrin Organochlorine 40
3. Methoxychlor Organochlorine 5,000
4. Endosulfan Organochlorine 80-110
5. Parathion Organophosphate 13
6. Dichlorvos Organophosphate 80
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7. Dimethoate Organophosphate 500-600
8. Melathion Organophosphate 1375
9. Fenitrothiop Organophosphate 740
10. Aldicarb Carbamate 1
11. Carbofuron Carbamate 11
12. Carbaryl Carbamate 307
13. Pyrethrins Botanicals 200
14. Rotenone Botanicals 60
15. Nicotine Botanicals 83
Pesticide formulations
A pesticide formulation can be defined in a broad sense as a physical
mixture of one or more biologically active ingredients (chemicals) with inert
ingredients in a definite proportion so as to make it more effective, safe,
economical and easy to use. It is a process through which a small quantity of an
active ingredient (a.i.) is formulated into a final product to be used by the
farmers/ consumers to control insect pests and diseases. The purpose of
formulation is the dilution of high concentration pesticide to an applicable level
at which it is toxic to target pests but non toxic to non target species and
environment.
Classification of pesticide formulations

Pesticide formulations are generally classified into liquid and solid form.
1) Liquid formulations are emulsifiable concentrate (EC), oil concentrate (OC),
oil solution (OS) and aqueous concentrate.
2) Solid formulations include dust (D), water dispersible powder (WDP),
granules (G) and water soluble powder (WSP).
New generation formulations

It is further improvement in developing of more eco-friendly formulations
have been developed recently.
1) The new solid formulations are drift-less dust, dry flowables or dispersible
granules, floating granules, fine granules and encapsulated granules with
controlled release.
2) The new liquid formulations developed include wet flowable (suspension

concentrate), aqueous emulsions, micro emulsions and suspoemulsions.
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a) Emulsifiable concentrates (EC): Emulsifiable concentrates contain a
surfactant or emulsifier for easy dilution with water for spray application. The
solvent system must be immiscible with water to produce uniform emulsion
lasting throughout the spraying period. Commonly used solvents are xylene,
aromatic naphtha or aliphatic kerosene type. Solvents may be chosen based on
flash points so as to reduce possible risks of fire during transportation and use.
This is a most popular formulation usually available for most of the pesticides.
b) Oil concentrates (OC): Oil concentrates contain high concentration of active

ingredients and used undiluted for ultra low volume (ULV) applications but can
also be diluted conveniently with hydrocarbon solvents as and when needed.
c) Oil solutions (OS): Oil solutions contain pesticides in low concentration

usually below 5 % by weight. These formulations are generally used for
household or institutional insect/ pest control measures. These are odourless,
colourless and contain non-staining high flash point solvents to minimise the fire
hazard.
d) Dust (D): These are finely powdered pesticides which are formulated to field
strength varying from 10 % depending upon the potency of the pesticide and the
rate of application. The particle size is usually less than 30 µm diameter. The use
of dust has been limited by their tendency to drift downward and they are mostly
used for seed dressing.
e) Wettable powder (WP): These are similar to dusts except that they are
formulated for dilution with water into final spray. The quality is judged by the
rapidity of wetting and stay in suspension when mixed with water for field
application. The proper choice of wetting agents is to enhance the wetting power
and good suspensibility which can be maintained by reducing the particle size.
Surfactants of the dispersant class are added to prevent the agglomeration of the
particles resulting in sedimentation. WP is frequently used for the slurry
treatment of seeds. In general wettable powder formulations are not compatible
with other types of formulations specially with emulsions causing sedimentation.
f) Granules (G): The granular pesticides are different from powdered pesticides
according to the mesh size. The mesh size starts from 4 mesh to 80 mesh. The
granular pesticides are generally free flowing and do not cake during storage and
there is no problem of drift during application, hence easy to handle. Since the
activity depends on the release of the a.i., the granules should have fast or slow
-58-
disintegration after entering the system. Granules are more effective as
prophylactic application when weather conditions are unfavourable for spray.
Pesticide analysis
The analytical techniques of pesticides are divided into two categories
based on the amount of pesticide present or the nature and type of analysis.
1. Pesticide formulations analysis
2. Pesticide residues analysis
The methods of analysis of pesticides are done as per National and

International standards with following major protocols of Bureau of Indian
Standard (BIS), Collaborative International Pesticide Analysis Council (CIPAC),
World Health Organisation (WHO), Food and Agricultural Organisation (FAO),
Association of Official Analytical Chemists (AOAC).
1. Pesticide formulation analysis

Formulation analysis is the examination of a product as supplied for use
in pest control for its physical and chemical properties. As such, examination of
the product can be required in its concentrated form or in a diluted form as
directed for application purposes. The quantity of pesticide is present in
formulations is greater than that present in a sample for residue analysis. The
formulation analysis is done in Govt. laboratories to check the quality control of
the pesticides. The pesticide molecules may be contain functional group like
chlorine, phosphorus, sulphur, nitrogen, copper, mercury, zinc, manganese, iron
etc. These groups can be analysed through titrimetry, colorimetry/
spectrophotometry are used. If the laboratory is equipped with gas
chromatography and high performance liquid chromatography can also be used.
2. Pesticide residue analysis

Pesticide residue analysis is the analysis of trace levels of a chemical in a
material arising from the application, directly or indirectly, of a pesticide. The
pesticide residue levels are in the g range and require sensitive and selective
methods of determination. The methods of analysis of pesticide residues are
colorimetry/ spectrophotometry, gas chromatography and high performance
liquid chromatography. In addition, the use of GC-Mass spectroscopy and LC –
MS are employed.
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Ex. No. 16 Date:
Determination of active ingredient in BHC
Principle
The compound containing organically bound chlorine is quantitatively
dehydrochlorinated with alcoholic potassium hydroxide. A mole of BHC on
hydrolysis yields three moles of chloride which is estimated. The free chloride is
estimated separately without hydrolysis. The chloride is determined by titration
with silver nitrate in the presence of alum indicator. After deducting the free
chloride, the per cent BHC is calculated using atomic weight and molecular
weight of the pesticide.
Reagents
a) Ethyl alcohol (95 %)
b) Acetone
c) Alcoholic potassium hydroxide (1 N): Dissolve 56 g in 1000 mL of
ethanol.
d) Nitric acid (4 N): Dilute 252 mL of conc. nitric acid in 1000 mL distilled
water.
e) Silver nitrate (0.1 N): Dissolve 16.99 g of crystallized silver nitrate and
make up to 1 L.
f) Ammonium thiocyanate (0.1 N): Dissolve 7.612 g of ammonium
thiocyanate in 1000 mL of distilled water
g) Ferric ammonium sulphate (alum) indicator: Dissolve 10 g of ferric
ammonium sulphate in 100 mL of water containing 10 mL of Conc. nitric
acid. Boil vigorously for a few minutes to expel the oxides of nitrogen.
Cool and make upto 100 mL with water.
h) Nitrobenzene
Procedure
Part A – Determination of hydrolysable chlorine
1) Weigh out accurately an amount of the formulation to contain about 0.2 g
of BHC into a 250 mL conical flask.
2) Add 25 mL alcohol and shake for a few minutes to dissolve the BHC
3) Add 10 mL of 1 N ethanolic KOH and reflux gently at 10-15oC for 20
min.
4) Allow the flask to cool and wash down the condenser with a small
quantity of distilled water.
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5) Disconnect the flask and add slowly 25 mL of 4 N HNO3 followed by 75
mL of distilled water + 25 mL AgNO3 + few drops of ferric ammonium
sulphate.
6) Shake the mixture vigorously and titrate with ammonium thiocyanate to
faint pink colour (Volhard’s method).
Part B – Determination of free chloride

1) Weigh accurately about the same amount of the formulation (10 mg) and
transfer to 250 mL conical flask.
2) Add 25 mL of ethanol and shake for a few minutes to dissolve the BHC.
3) Add 25 mL of 4 N HNO3 followed by 10 mL 1 N ethanolic KOH + 75
mL water + 25 mL AgNO3 + few drops of ferric alum indicator.
4) Shake the mixture vigorously and titrate with ammonium thiocyanate to a
faint pink colour.
Calculations
1 mL of 1 N AgNO3 = 35.46 mg of chloride
(B1 - TV1) x N x 3.546 x 100

Chlorides after hydrolysis (%) =
W1
B1= Vol. of std. ammonium thiocyanate consumed by 25 mL of Std. AgNO3

TV1 = Vol. of std. ammonium thiocyanate consumed by excess AgNO3 in
sample after hydrolysis
N= Normality of ammonium thiocyanate
W1= Weight of sample taken for hydrolysis (g)
(B – TV2) x N x 3.546 x 100

Free chloride (%) =
W2
B2= Vol. of std. ammonium thiocyanate consumed by 25 mL of Std. AgNO3

TV2 = Vol. of std. ammonium thiocyanate consumed by excess Std. AgNO3 in
the sample before hydrolysis
N = Normality of ammonium thiocyanate
W2 = Weight of the sample taken for the determination of free chloride (g)
BHC (%) = (A-B) x 2.73
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Ex. No. 17 Date:
Determination of active ingredient (copper) in copper fungicides
Principle
Copper is determined by titration of the iodine liberated on the addition of
potassium iodide to the weak acidic solution. The absorption of iodine on the
cuprous iodide precipitate is avoided by the addition of ammonium thiocyanate.
The iodine so liberated is titrated with sodium thiosulphate. The copper in the
copper fungicide is calculated using the relation 1 mL of 1 N of Na2S2O3 is
equivalent to 63.57 mg copper.
Reactions
2Cu(OH)2.CuCl2 +4KI 4CuI + 4KCl + 2I2 + 4H2O
2Na2S2O3 + I2 Na2S4O4 + 2NaI
Reagents
1. Con. Nitric acid
2. Urea
3. Sodium carbonate
4. Potassium iodide
5. Dilute acetic acid (10 %): Dilute 10 mL of acetic acid in 100 mL of
distilled water
6. Ammonium thiocyanate
7. Sodium thiosulphate (0.1 N): Dissolve 25 g Na2S2O3.5H2O in bioled
distilled water make upto 1000 mL. Add 3.8 g of borax or 0.1 g of
anhydrous sodium carbonate to stabilise the solution.
8. Starch: Make a paste of 0.5 g of soluble starch in cold water; pour into
100 mL of boiling water, boil for 5 min and cool (add 2 g of boric acid or
0.5 mg of mercuric iodide per 100 mL solution.
Procedure
1) Weigh accurately a quantity of the material containing 0.2 g of copper
into a 500 mL conical flask.
2) Add 5 mL of distilled water, 5 mL nitric acid, shake and warm the
mixture to reduce the volume to about 5 mL.
3) Add 30 mL of distilled water to this and boil for 5 minutes.
4) Remove the flask from flame and add 1 g urea and boil the mixture again
for about 10 minutes.
-62-
5) Cool the flask to room temperature.
6) Add sodium carbonate in small quantities till a faint permanent precipitate
or blue colour is obtained.
7) Add dilute acetic acid drop wise until the blue colour of the precipitate
dissolves.
8) Add 2 g potassium iodide and titrate the brown solution immediately with
std. sodium thiosulphate till a pale straw colour is obtained.
9) Add about 2 mL of freshly prepared starch indicator solution and 1 g of
ammonium thiocyanate and continue the titration till the blue colour just
disappears.
Calculations
1 mL of 1 N sodium thiosulphate = 63.57 mg Cu
V x N x 63.57 x 100
Copper (%) in Copper oxychloride =
W
Where V = volume of std. sodium thiosulphate solution used

N = normality of sodium thiosulphate
W = weight of the material taken (g)
-63-
Ex. No. 18 Date:
Determination of active ingredient in 2,4-D
Principle
The sodium salt and others are converted into the acid derivative by
treating with hydrochloric acid. The phenoxy acid is extracted and estimated.
Reagents
1) Dil. Hydrochloric acid (5 %): Dilute 5 mL with 100 mL of distilled water
2) Diethyl ether
3) Absolute alcohol (neutral)
4) Std. sodium hydroxide (0.1 N): Dissolve 4 g of sodium hydroxide in 1 L
of distilled water and standardise with sodium carbonate.
5) Std. sodium carbonate (0.1 N): Dissolve 5.3 g of Na2CO3 in 500 mL of
distilled water and then make up the volume to 1 L.
6) Methyl red indicator: Dissolve 0.5 g of methyl red in 100 mL of ethyl
alcohol.
I. 2,4 – D sodium and amine salt

Procedure
1) Weigh accurately and quantity of the material so as to contain about 1 g
of 2,4-D and dissolve it in minimum quantity of water.
2) Acidify the solution with dil. Hydrochloric acid
3) Transfer the mixture completely to a 125 mL separating funnel using
minimum quantity of water.
4) Extract the aqueous phase with 3 successive portions of 25 mL of diethyl
ether.
5) Combine the ether extracts (75 mL) in the second separatory funnel and
wash with water until the ether solutions is free of chloride ions.
6) Transfer the ether solution to a pre-weighed 150 mL flask and distil the
ether.
7) Dry the flask with the residues 2,4-D at 105oC ± 2oC for half an hour, coal
and weigh again.
8) The residues represent the separated acid.
9) Dissolve the dry residue in 10 mL neutral absolute alcohol and dilute it
with 10 mL of water.
10) Add 2 - 3 drops of methyl red indicator and titrate with the std. alkali.
-64-
Calculations
1 mL of 1 N of NaOH = 22.1 meg of acid
V x N x 22.1
Extractable acid (%) =
W
W1 x 1000
Equivalent weight of the acid =
VxN
Where V = Volume of the std. sodium hydroxide solution

N = Normality of alkali
W = Weight of sample (g)
W1 = Weight of the dry residue obtained (g)
II. 2,4-D – ester

Procedure
1) Weigh accurately an amount of the sample to contain 3.5 - 4.5 g of 2, 4 D
2) Hydrolyse by refluxing for 1 hour with 25 mL of 1 N NaOH and 10 mL
of alcohol.
3) Transfer to a 250 mL separating funnel with 75 mL of distilled water and
extract with 30 mL of diethyl ether.
4) Draw the aqueous layer into a 100 mL volumetric flask
5) Wash the ether layer 2 times with 10 mL portion of water and draw the
aqueous layer into the same volumetric flask and make up to the mark.
6) Pipette out 25 mL of the aliquot and proceed as before.
(Note: If the ether is ethyl ester, the extraction of the sample with ether
after refluxing need not be carried out)
7) Carry out a blank determination on a mixture of 60 mL ethanol and 90
mL ether.
Calculations
(S - B) x N x 4 x 22
% 2,4-D ester =
W
Where S = Volume in mL of std. NaOH used for the sample

B = Volume in mL of std. NaOH used in blank
N = Normality of NaOH
W = Mass of the sample (g)
-65-
I Semester, 2010 -11
Course Teacher
Dr. T.H.Hanumantharaju
Associate Professor
Introduction
Fertilizers and manures are the king pins of improved
technology contributing about 50 to 60 per cent increase
in productivity of food grain in India, irrespective of soil
and agroecological zone
The high yielding varieties produce dramatic increases in
yields though conversion of chemical energy of fertilizers
and manures into biomass with higher grain : straw ratio.
For the land short countries, use of fertilizers provide the
best strategy for land saving.
But for this strategy, India and China would have
required to put 2-3 times more area under cereals to
produce the same quantity of foodgrains in 1992 as was
produced in 1961
Course Objectives
To understand the manures, Fertilizers and Agro-
chemicals used in agricultural production
To comprehend the different methods of manure
preparation, their classification and nutrient
composition
To study the manufacturing methods of fertilizers,
their classification and nutrient composition
To learn the previsions under fertilizer control order
to ensure quality of fertilizers
To understand the classification of agro-chemicals ,
and mode of action
Syllabus
Refer: Course Curriculum 2007
supplied to you at the time of admission

Lecture 1
Introduction to the course, Reference books and
scheme of evaluation
Organic manure- definition, classification of manure

Lecture 2
• Bulky organic manures :
Definition, FYM
• Compost: Composting
definition, factors affecting
composting, principles of
composting, essential
requirement for
composting, Method of
composting – Indore
method, Bangalore
method, NADEP method,
VAT or Japanese method of
composting.
Lecture 3
• Vermicomposting
• Green Manures : Definition
of green manuring, Types of
green manuring- Green
manuring in sity and green
leaf manuring. Compostition
of green manuring crops.
• Concentrated Organic
manures: Definition, Oil
cakes, Bone meal, fish meal,
woodash. Types of oil cakes
and their composition.
• Sewage and sludge:
Definition, types and their
composition.
Lecture 4
• Fertilizers- Definition,
differences between organic
manures and fertilizers,
• Classification of fertilizers:
Straight fertilizers, complete
fertilizers, imcomplete
fertilizers, mixed or complex
fertilizers. Classification
based on nutrient content of
individual fertilizers –
Nitrogenous fertilizers,
Phosphatic fertilizers and
potassic fertilizers.
Lecture 5- 7
Manufacturing and properties of nitrogenous fertilizers
• Fixation of elemental nitrogen -

ammonia Synthesis, cyanamide
process and direct oxidation of
nitrogen.
• Manufacturing of ammonium
sulphate and their properties
• Manufacturing of ammonium
nitrate and their properties.
• Manufacturing of calcium
ammonium nitrate and their
properties.
• Manufacturing of urea and their
properties.
• Biuret content in urea
Lecture 8 - 9
• Manufacturing and
properties of phosphorus
fertilizers: SSP – batch
process and continuous
process.
• Manufacturing process and
properties of potassium
fertilizers : MOP, SOP –
Decantation process,
Lecture 11
• Manufacturing/preparation of complex
fertilizers.
• Advantages and disadvantages of such
mixtures
• Compatibility
Lecture 12
• Fate of ammonium sulphate in soils.
• Fate of urea in soils.
• Fate of SSP and Rock Phosphate in soils.
• Fate of MOP and SOP in soils.
Lecture 13
• Fertilizer Use efficiency – time and method of
applications.
• Soil Amendments- Definition, liming material,
gypsum
Lecture 14
• Fertilizer control order

Lecture 15-18
Agrochemicals
• Definition and classification
• mode of action of agrochemicals;
Botanical insecticides, Synthetic
organic insecticides Major
classes,
• properties and uses of some
insecticides, herbicides,
fungicides, nematicides,
acaricides and rodenticides,
• Compatibility of fertilizers with
pesticides,
• insecticides act
Manures
The word manure is derived from French
“Manoeuvrer” which refers to ‘work with soil’ that
is why the word tillage and manure which
synonyms as it is clear by the statement of Jethro
Jull (1700 BC) ‘Tillage is manure’.
The word manure is also originated from

Latin ‘manuren’ means work with hand.
Organic manures
• Manures may be defined as materials which are
organic in origin, bulky and concentrated in
nature and capable of supplying plant nutrients
and improving physical properties
• Manures do not have a definite chemical
composition
• Mainly produced from animal, plant and organic
wastes and by products
• Examples- FYM (Farm Yard Manure), compost,
Green manures etc.
Classification of Manures
Organic manure
Bulky OM Concentrated O M
Blood Bone Oil Others

meal meal cakes
Well decomposed
Green Plant tissue
animal, plant & Non-edible to Edible to
(Un-decomposed)
other org. residues Cattle Cattle
Mahua, Mustard,
Green manures neem oil and
FYM, Dhaincha, cakes groundnu
Compost Glyricidia, other t oil cakes
leguminous crops
Bulky v/s Concentrated OM
Bulky OM Concentrated OM
• Bulky in nature • Less bulky
• Supply large amount of • Supply small amount of
organic matter organic matter
• Contain less amount of • Contain more amount
plant nutrients
of plant nutrients
• Mainly derived from
animal, plant and other • Mainly derived from
organic wastes and raw materials of animal
green plant tissues or plant origin
Characteristics of Organic Manures
Either bulky or concentrated in nature and supply
• Plant nutrients in small amounts When applied to soil it
• Organic matter in large amounts will act as follows
1. Supply primary, secondary and micro nutrients (After mineralization)
2. Application improve soil physical, chemical and biological properties
3. It stimulates the activity of different of soil micro-organisms- as a
source of energy
4. It improves buffering capacity and exchange capacities of soil and also
influences the solubility of soil minerals as well as mineral nutrients in
soil.
5. It also forms chelates which helps in plant nutrition (prevent nutrient
loss
6. It also regulates the thermal regimes of the soil
Bulky organic manures
Manures which are bulky in nature and

supply large quantities of organic matter but
small quantities of plant nutrients
These materials needs to be applied in large
amount due to low plant nutrient content
Organic matter application improves soil
condition.
Farm manures
Most animal manure is faces. The common forms of

animal manure include farm yard manure (FYM) or farm
slurry (liquid manure). FYM also contains plant material
(straw), which has been used as bedding for animals and has
absorbed the feces and urine. Agricultural manure in liquid
form, known as slurry, is produced by more intensive
livestock rearing systems where concrete or slats are used,
instead of straw bedding. Animal manures may also include
other animal products, such as hair, feathers, blood, meat and
bone.
Farm Yard Manure (FYM)
The term FYM refers to the well decomposed mixture of
dung, urine, farm litter (bedding material) and left over
or used up materials from roughages or fodder
The FYM collected daily from the cattle shed consisting
of raw dung and part of the urine absorbed in the
refuse.
Newly collected and stored FYM is fresh as against well
decomposed FYM which has been stored for a
sufficiently longer period to allow its decomposition to
completion
FYM Consists of two components- Solid phase i.e. dung
and bedding material and liquid phase i.e. Urine.
Material N (%) P (%) K (%)

Cattle dung fresh 0.3 – 0.4 0.1 – 0.2 0.1 -0.3
Cattle urine 0.9 – 1.2 traces 0.5 -1.0
Bedding materials 0.2 – 1.6 0.12 – 1.57 0.5 – 2.17
FYM 0.4 – 1.5 0.3 – 0.9 0.3 -1.9
Methods of preparation (storage) of FYM
The method of collection and storage is the most
important factor which decides the final composition of the
manure. The following are recognized methods of storing the
FYM.
1) Heap method
It is most commonly adopted method by the farmers. Every
day sweepings, cow dung and litter can be collected and
heaped at any fixed place. After about 6 - 9 months, the rotten
manure is used as a nutrient carrier. Normally the urine is not
properly utilised as it gets lost the barn itself because of
katcha floor. According to an estimate that about 30-35 %
nitrogen, 20-25 % phosphorous and 2-6 % potassium are lost
during the preparation of manure due to leaching, washing
and volatilisation.
Fig. Heap method of farm manure preparation
2) Trench/ pit method
a) The trench method is also called as Dr. C.N.Acharya method. In
this method, trenches of 6-8 m length, 1.5 - 2 m width and 1.0 - 1.25
m depth are prepared.
b) Mixture of dung and urine soaked litter is deposited in layers in
trenches until it becomes about 50 cm above ground layer.
c) The filling of the pit should be sectional and when each section of
1.3 m in length is filled to about 45 cm above the ground level and
plastered with 2.5 cm layer of a mixture of mud and dung in equal
proportions. Before plastering, 4 to 5 buckets of water should be
added to the manure pit.
d) Plastering conserves moisture and nitrogen and also prevents
housefly nuisance. The manure becomes ready for use in about 4 to
5 months after plastering.
e) Usually 10-12 tons of FYM is obtained per trench per year for 2
adult animals. It is possible to prepare by this process 7-8.5 m3 of
manure. Well rotten farm yard manure contains 0.4 to 1.5 % N, 0.3-
0.9 % P2O5 and 0.3-1.9 % K2O.
Fig. Pit method of farm manure preparation
Preparation
Open a trench of 6m long, 2 m wide and 1 m deep in a suitable
and convenient place
Sufficient quantity of dry litter is spread as bedding material
in the evening- for absorption of urine
The bedding material soaked with dung and urine is collected
everyday and placed in a trench
The trench is filled up section wise and up to a height of about
0.5 m above the ground level
When the trench is filled to a height of about 0.5 m above the
ground level, the top of the heap should made dome shape
Then it is plastered with a slurry of cow dung and earth
It may give 5-6 t of good quality manure per year per head of
cattle.
Super phosphate applied @ 25 kg/t of manure over each layer
of urine soaked litter and dung checks N loss and increase P
content.
Factors affecting the composition of manure
Source of manure: Sheep (1, 0.32 and 0.98 % N, P2O5 &
K2O) and poultry (1.35, 0.65 & 0 .32 % )are somewhat richer
in plant nutrients than cow(0.45, 0.12 & 0.34 %), horse
(0.68,0.2 & 0.6 %) and pig (0.58, o.32 & 0.49) manure
Species of animals: ruminant v/s non-ruminants
Types of food consumed by animals: Richer the food in
proteins, the richer will be the manure in N.
Age and condition of animals: Manure of young animals is
not so rich like that of matured animals (Because young
ones retain more nutrients for their growth)
Nature and amount of litter: Composition varies with
nature and amount of litter used
Functions of the animal: Milch animal v/s draft animal
Handling and Storage
of manure:
1. Loss of K occurs if any
drainage is allowed to
escape from the
manure heap
2.Improper handling
and storage leads to
losses of plant
nutrients from the
manure
Losses of FYM
1) During handling
FYM contains solid (dung) and liquid (urine). Approximately 50,
60 and 90 % N, P and K are present in dung respectively and
remaining part in urine. After decomposition of manure, in spite of
proper handling 50 % N and K and 33 % P is destroyed.
a) Dung
It is used as fuel by making dried dung cakes or to clean the
kachcha floor. Greater looses occurs when animals grazing in the
field.
b) Urine
Most of the floors of the cattle sheds in India are kachcha floor
which absorb most of the urine containing excess of nitrogen. Thus
excess of nitrogen is lost as ammonia.

(NH4)2CO3 + 2H2O 2NH4OH + H2CO3
2NH4OH NH3 + H2O
Losses of FYM
2) During storage
In India, FYM is collected in open area as lumps. The lump is
not covered due to which excess of nitrogen is lost by sun light
and rain water. Losses occur as follows:
a) Volatilisation
Due to decomposition of FYM, several vaporised compounds
formed are lost in gaseous form as indicated in the losses
occurred in urine.
b) Leaching
Leaching generally occurs in Kachcha pits, most of the
nutrients are dissolved in water leach down in the lower part of
the soil. The nutrients are soluble in water and about 50 % of
N and P and 10 % K is water soluble which is lost by leaching.
Types of manures
Depending upon the type of animal excreta
used for the preparation of manures, the manures
are classified as
1. Cattle manure
2. Poultry manure
3. Piggery manure
4. Horse manure
5. Sheep and goat manure
Poultry manure is a rich source of nutrients compare
to others. Sheep/ goat contains higher amount of organic
matter compare to others excreta. Next to poultry, sheep
manure is fairly rich, cattle and buffaloes dung is poor in
nutrient content.
Reinforced FYM
The preservatives are added to manures to conserve and avoid
nutrient losses from the manure, especially nitrogen are said to be
reinforced FYM. Gypsum and super phosphate have proved most
promising in preventing the escape of ammonia. Gypsum has been
found especially effective as an ammonia absorbing agent. Super
phosphate contains monocalcium phosphate (16 % P2O5) and gypsum
(50- 60 %). Super phosphate besides absorbing ammonia, supplies
additional phosphorous and thus improves the crop producing capacity
of the manure. The phosphorus content in FYM is relatively low, the
addition of super phosphate increases the phosphorus content. Hence,
higher quantities intended to supply the needed to supply the quantity of
phosphorus will result in wastage of nitrogen in most soils. The super
phosphate can be sprinkled either in the cattle shed or on the manure
heap.
(NH4)2CO3 + CaSO4 (NH4)2SO4 + CaCO3
(NH4)2CO3 + Ca(H2PO4)2 + CaSO4 2(NH4)2SO4 + Ca3(PO4)2 + CO2 + H2O

Table Chemical composition of FYM
Components Minimum Maximum Average
1. pH 7.80 7.90 7.80
2. Organic material (%) 8.54 58.60 33.52
3. Mineral matter (%) 54.19 91.46 72.82
4. Nitrogen (%) 0.35 1.88 1.13
5. Phosphorus (%) 0.12 2.40 1.25
6. Potash (%) 0.17 2.20 5.31
7. Lime (%) 1.11 11.02 5.74
8. Magnesium (%) 0.58 2.19 1.13
9. Organic carbon (%) 1.49 30.90 11.48
10. C/N ratio 4.5 18.30 9.50
11. Copper (ppm) 1.89 8.06 4.63
12. Zinc (ppm) 2.41 10.81 2.26
13. Manganese (ppm) 47.90 100.70 93.65
14. Boron (ppm) 0.03 0.11 0.06
Characteristics of farm yard manure
1. Moisture
FYM is made up of 75 % moisture. In general, moisture
content of FYM is 50-80 % and dry matter 20-50 %.
2. Supply of nutrients
FYM will supply plant nutrients, viz., 0.50 % N, 0.25 % P2O5
and 0.50 % K2O. It supplies most of micronutrients required by
the plants. In FYM, on an average, contains Cu (4.6 mg/ kg),
Zn (2.3 mg/ kg), Mn (93.7 mg/ kg) and B (0.06 mg/ kg).
3. Unbalanced nutrient proportions

FYM is poor in NPK content, particularly P2O5. So, it is
considered as unbalanced. FYM is mixed with super
phosphate or rock phosphate before addition to the field, so
P2O5 content can be increased, then it is rein-forced. It also
supplied secondary and micronutrients.
Characteristics of farm yard manure
4. Residual effect
In FYM, nutrients are present in complex form as proteins

or microbial tissues. During the process of decomposition, the
microbial tissues are decomposed and form a source of
nitrogen. In well decomposed FYM, about ½ N and K, 1/6 P
are readily available to first crop, remaining part will left in the
soil for the succeeding crops. In well decomposed FYM, the
C:N ratio is 12-15:1, in partly decomposed FYM, C:N ratio is 20
: 1. In such case, the residual effect is more for 2 - 3
succeeding crops.
Application of FYM
The rate of FYM application depends upon crop, soil and
availability. Generally 20 - 25 tons ha-1 FYM is suitable for most
of the crops. More FYM can be applied in light textured soils
compared to heavy textured soils. FYM is added at the time
field preparation, 25 – 30 days before ploughing. The FYM
may be applied in the form of small heaps at short distances,
spread/ broadcasted as in thin layer before ploughing and
which is then mixed by ploughing.
DEFINITION
Webster’s Dictionary
defines compost as the
following:
Pronunciation: 'käm-"pOst,
A mixture that consists
largely of decayed
organic matter and is
used for fertilizing and
conditioning land”
The US Composting Council defines compost as:
•Compost is the product resulting from the controlled biological
decomposition of organic material that has been sanitized
through the generation of heat and ‘processed to further reduce
pathogens’ (PFRP), and stabilized to the point that it is beneficial
to plant growth.
•Compost bears little physical resemblance to the raw material
from which it originated.
•Compost is an organic matter source that has the unique ability
to improve the chemical, physical, and biological characteristics
of soils or growing media.
• It contains plant nutrients but is typically not characterized as a
fertilizer.
Composting - Definition
The Practical Handbook of Compost Engineering
defines the composting process as:
"The biological decomposition and stabilization of
organic substrates, under conditions that allow
development of thermophilic temperatures as a result of
biologically produced heat, to produce a final product
that is stable, free of pathogens and plant seeds, and can
be beneficially applied to land."
DEFINITION
Compost is the stabilized
and sanitized product of
composting which is
beneficial to plant growth
DEFINITION
Compost, substance composed mainly of partly decayed organic
material that is applied to fertilize the soil and to increase its
humus content; it is often used in vegetable farming, home
gardens, flower beds, lawns, and greenhouses. Compost usually is
made from plant materials (e.g., grass clippings, vegetable tops,
garden weeds, hay, tree leaves, sawdust, and peat) together with
manure and some soil; lime, superphosphates, and nitrogen
fertilizers are often added with manure to reinforce the compost
and hasten its decomposition.
A mixture of decaying organic matter, as from leaves and manure,
used to improve soil structure and provide nutrients.
Compost is the decomposed remnants of organic materials (those
with plant and animal origins). Compost is used in gardening and
agriculture, mixed in with the soil to improve its structure (by
increasing its organic content) and fertilizing quality.
Composting is a controlled bio-oxidative
process that
1. Involves a heterogeneous organic

substrate in the solid state
2.Evolves by passing through a
thermophilic phase and temporary
release of phyto-toxins and
3. Leads to the production of CO2,water,
minerals and stabilized organic matter
(compost)
Stages of composting
Consolidation Active stage Curing stage
Stages of composting
Process of Composting
The humification of organic material under most
conditions occurs in three stages:
1. Mesophilic stage.
This is the initial stage of decomposition,
lasting for about a week,
during which sugars and other simple
carbohydrates are rapidly metabolized.
This is an exothermic process and may
cause an increase in temperature by 40°C.
2. Thermophilic stage.
This is the second stage,
lasting for about two weeks,
during which the temperature may rise to
about 50 to 75°C.
Such a drastic increase in temperature is
accompanied by the decomposition of cellulose
and other resistant materials.
It is important that the material be thoroughly
mixed and kept aerated during this stage.
3. Curing stage
The temperature decreases during this final stage
and
the material being composted is recolonized by
mesophillic organisms,
which often produce plant-growth stimulating
compounds.
At the completion of this process, the plant or other organic
parts (leaves, roots, etc.) are no longer identifiable in the
compost. The humification of organic material is characterized
by an increase in concentration of humic acids from
approximately 4 to 12 percent, and a decrease in the C/N ratio
from thirty in the original material to about ten in the final
product
At completion
1. the plant or other organic parts (leaves, roots,
etc.) are no longer identifiable in the
compost.
2. There is an increase in concentration of
humic acids from approximately 4 to 12
percent, and
3. decrease in the C/N ratio from thirty in the
original material to about ten in the final
product
Ingredients for the preparation comes from the
following two sources
1. Farm refuse – Stubbles, crop residues, weeds,
hedge clipping etc.
2. Town refuse – night soil, dustbin refuse, etc
Selection of site
Should be near the cattle shed OK and source of
wastes
?
Should be easily approachable for inspection
Comparatively at higher elevation (to avoid water
stagnation)
Should be located away form main road (to prevent
lead contamination by automobiles)
Factors affecting composting
• Moisture Content
• Aeration
• Temperature
• pH
• C:N ratio
• Particle size
Recommended conditions for rapid composting
Conditions for rapid Reasonable Preferred

composting range range
1. C:N ratio 20:1 - 40:1 25:1 - 30:1
2. Water content (%) 40 – 65 50 – 60
3. Oxygen 5 5 -15
concentration (%)
4. pH 5.5 – 8.5 6.5 - 8.0
5. Temperature ( F) 110 –150 130 – 140
6. Time (months) 6 8-12
Principles of composting
Narrowing down of the C:N ratio to a
satisfactory level (10:1 or 12:1)
The total destruction of harmful
pathogens and weed seeds
Stabilization
Essential requirements for composting
Bulky organic refuse

A suitable starter
Moisture
Air
1. Bulky organic materials
Agril. Farm wastes: Crop residues, forest litter,
sugarcane trash, groundnut waste, mushroom spent
waste, cattle shed waste, poultry wastes, sericulture
wastes, rice straw etc.
Weeds: Water hyacintha, Ipomea, Parthenium, cassia
etc.
Agril. & Industrial wastes: Rice bran, rice husk,
bagasses, molasis, pressmud, tobacco waste, cotton
mill waste, arecanut husk waste, coir dust, fruit and
vegetable processing wastes, paper and pulp industry
sledges, coffee pulp etc.
City wastes: city refuse, sewage sludge, Bone meal,
Fish meal, Feather meal etc.
Method of composting
Materials
• Carbonaceous materials : 60 – 70 %
• Nitrogenous materials : 30 – 35 %
• Minerals : 2-3 %
• Inoculants/starter :1%
Carbonaceous Materials
• Normally wastes with wider C/N ratio

• Acts as basic bulk material
• Straws, coir wastes, shredded branches,
all dried residues etc.
Nitrogenous Materials
• Normally wastes with narrow C/N ratio
• Rich in nitrogen
• Animal wastes, green foliage, green
manure crops, blood meal, fish wastes,
biogass slurry etc.
2. Starter
Organic : Cowdung slurry, cattle urine, old

compost, mixed microbial culture etc.
Inorganic: Ammonium sulphate, Sodium
nitrate, Lime, etc.
Minerals
• Wood ash : 20-25 kg
• Rock phosphate : 20-25 kg
• Rock dust/bore well soil : 15-20 kg
• Lime powder : If basic material is acidic
and/ contains high amount of lignin at @ <
0.5 %
Inoculants
• Old compost or
• Vermicompost
• Bio-fertilizers, bio-control agents etc.
3. Water
Addition of enough water to keep the

moisture content of the material at a level
around 60 per cent.
4. Air
Turning
Inserting pipes with holes in the compost
Giving proper ventilation from all sides of the
compost structure
Pumping air using blowers
Size of the heap
Bottom : 16' x 6'
Top : 14' x 4'
Height : 5'
14'
4'
5'
6'
16'
Method of filling compost pit
Sprinkle minerals
Cow dung slurry as thin layer
Nitrogenous materials – 4-5"
One layer
Spread old compost or any starter

material
Cow dung slurry as thin layer
Carbonaceous materials – 5-6"
Compost filling
Coir dust as base material

Compost filling
Carbonaceous layer Cowdung slurry layer

Compost filling
Nitrogenous layer Cowdung slurry

Compost filling
Sprinkle Minerals – Wood ash, rock phosphate and rock dust

Compost filling
Continue the layering till it reaches 5' height

Compost filling
Compost heap covered with a poly sheet

Composting structures
Compost pit prepared using local materials

Composting structures
Compost pit prepared using stone slabs

Precautions to be taken while composting
Before composting all the carbonaceous

materials should be wetted sufficiently with
water.
Maintain the moisture content to 60 % by
sprinkling water periodically
Give turning to the compost to facilitate good
aeration. First turning after 25-
25-30 days, second
on 45 days
Compost will be ready to use after 60-
60-90 days.
Adverse effect of immature compost
1. Biological blockage of soil available nitrogen by
immobilization causing serious Nitrogen deficiencies in
crops..
crops
2. Decreasing oxygen concentration in soil creates a
strong reducing environment at rhizosphere zone,
thereby increasing the solubility of heavy metals in the
soil, which may become toxic to plant roots
roots..
3. The presence of phytotoxic substances fundamentally
ammonia, ethylene oxide and organic acids (acetic acid,
prop ionic acid, valeric acid, butyric acid) inhibits seed
germination..
germination
4. Presence of weed seeds will cause serious problems
after application to main field
field..
Composition of a well matured
quality compost
Properties
Temperature Stabilized
Odour No obnoxious or disagreeable

odour
Colour Dark brown or almost balck
pH Between 6.5 and 7.5
Electrical Conductivity Max. 1dS m-1
Moisture Max. 20 - 25 %
Composition of a well matured
quality compost
Major nutrients
Nitrogen 1-3 %
Phosphorous 0.5 – 1 % (P2O5)
Potassium 1- 3 % (K2O)
Organic Carbon Min. 20 %
C : N ratio 10 to 15
A. TRADITIONAL METHODS
Anaerobic Decomposition
A.1 The Indian Bangalore method
A.2 Passive Composting of Manure Piles
Aerobic decomposition through Passive Aeration

A.3 The Indian Indore method
A.3.1 Pit method
A.3.2 Heap method
A.4 Chinese Rural Composting

A.4.1 The pit method
A.4.2 High temperature compost
Large Scale Passive Aeration

A.5 Windrow Composting
A.5.1 Turned Windrows
A.5.2 Passively aerated windrows
B. RAPID COMPOSTING METHODS
Shredding and Frequent Turnings

B.1 The Berkley Rapid Composting Method
Use of Mineral Nitrogen Activator

B.2 North Dakota State University Hot Composting
Use of Effective Micro-organisms (EM)

B.3 EM based Quick Compost Production Process
Use of Cellulolytic Cultures

B.4 IBS Rapid Composting Technology
B.4.1 IBS Rapid Composting
B.4.2 IBS Rapid Commercial Production
B.4.3 Rapid Rice Straw Composting
Use of Forced Aeration

B.5 Aerated Static Pile
Controlled Systems with Forced Aeration and Accelerated
Mechanical Turnings
B.6 In-Vessel Composting
B.6.1 Bin Composting
B.6.2 Rectangular Agitated Beds
B.6.3 Silos
B.6.4 Rotating Drums
B.6.5 Transportable Containers
Use of Worms
B.7 Vermicomposting
B.7.1 Vermicomposting in Philippines
B.7.2 Vermicomposting in Cuba
B.7.2.1 Worm troughs in a row
B.7.2.2 Windrows
B.7.3 Vermiculture in India
1. ADCO process : Hutchinson and Richards (1921), Rothamsted,
England.
2. Activated process : Fowler and Redge (1922), started at IISc,
Bangalore, but completed at HBTI, Kanpur.
3. Indore method : Howard and Wad, (1926), Plant Industry Institute,
Indore.
4. Bangalore method : C.N. Acharya, (1939), Chemistry Department, IISc,
Bangalore
5. Coimbatore method : Manickam (1967), Dept. of Soil Science, TNAU,
Coimbatore.
6. NADEP method : Naryan Devrao Pandri Pandey, a farmer from
Madhya Pradesh developed this method
7. Japanese method :
8. Windrow method :
9. Vermicomposting :
Choice of the method is based on availability of ingredients and convenience

1. ADCO (Agricultural Development Company) process
The ADCO process was developed by Hutchinson and

Richards (1921), Rothamsted, England. The composition of
ADCO powder is not known, but may contain 60 kg of
ammonium sulphate, 30 kg super phosphate, 25 kg of muriate
of phosphate and 50 kg of limestone in 1 ton of compost. They
use ADCO powder for rapid decomposition. The plant refuse
which can not fed to cattle is used. The refuse material is
spread uniformly on the floor to a thickness of 9 – 12". Then
the ADCO powder is sprinkled at 7 % of material. This can be
repeated normally 6 layers or till the height reaches to 1.8 m
from the ground and periodically turned and moistened for
quick decomposition. It can be allowed for 3 – 4 months. It is
aerobic and heap method. However, the method is not gain
popularity and hence not being used because high
temperature does not permit uniform decomposition.
2. Activated process
The activated process was developed by Fowler and
Redge (1922), started at Indian Institute of Science (IISc),
Bangalore, but completed at Harcost Butler Technology
Institute, Kanpur. In this method, instead of ADCO powder, use
some inoculums or activator to decompose the material quickly.
It is aerobic and heap system. The activator is prepared by
depositing 1.8 m long, 0.6 m height heap of leaves, grass,
weeds, kitchen garden wastes and straw etc. Now cow dung
slurry is prepared by mixing 40 kg of dung in 100 L of water and
this slurry is used to soak the composting material. The starter
should be dung, urine, urine mixed earth, sewage and sludge
etc. The material is turned at every 30 days intervals and
moistened. After 3 – 4 months, the entire mass is converted
into brown colour. They called it as starter, 1/3 of it is used for
compost making. This way composting matter of every new
heap is mixed with this activator for quick decomposition.
Indore Method
This is the first aerobic method and was
developed by Albert Howard and Y. D.
Wad at the Institute of Plant Industry,
Indore between 1924 and 1931.
In this method animal dung is used as
catalytic agent along with all other plant
residues and wastes available on the farm
Indore Method
• MATERIALS
Stalks of cotton, maize, millet and the pulses. (Ideally they
should be chopped to a particle size below 2 inches).
• CONSTRUCTION
1. Start building the heaps by laying a lattice of old branches at
the bottom.
2. Divide the base area of the heap into a 6 (roughly equal)
transverse sections,
3. five of which are filled and one left vacant.
4. Make each section of 7 layers (figure 1) of 9 inch thickness.
5. In a 9 inch layer, have 4 inches of dry waste, 3 inches of green
weeds and leaves, 2 inches of manure and a sprinkling of urine-
earth-wood ash. (The layering process is illustrated in figure-2).
Make ventilation holes after completing two
layers of a section.
Take a 6-8 ft long pole with a 2 inch diameter
and probe vertically through the working,
gradually increasing the size of the hole to 4
inches by waggling the pole.
See that the pole remains in its position and
ensure that the air- vent continues to the top of
the completed section.
The first pole should be at a distance of not
more than 2 feet from the heap, with a
maximum distance of 4 feet between two
successive holes.
• Continue building of the section up to a
height of 5 feet, after establishing the air
vents.
• Build five sections in the similar manner,
leaving the sixth one vacant (The sixth one
is utilized while turning the heap).
• Water the heap, lightly, just after
completion and again the next morning.
WORKING
• The central portion of the compost heap gets heated to
its maximum temperature, within one week of its
completion.
• The material in the cooler region composts slowly and the
weeds, seeds and diseased material may not be
completely decomposed.
• Hence, it is vital to turn the heap so that the cooler top,
bottom and sides get mixed back into the middle of the
new heap, once the temperature at the centre begins to
drop.
• Turning also facilitates thorough mixing of the ingredients
and their aeration.
WORKING
• Carry out the first turning two weeks after
construction of the heap.
• Put the top 9 inches from section 5 into the floor
of section 6, mixing it in the process.
• Cover it with the next 9 inch layer and water it. Re-
establish the air vents before proceeding further.
• Switch section 4 to Section 5, once Section 5 is
completely turned over into Section 6.
• Keep turning over each section into the next one,
leaving Section - I blank (figure -4).
WORKING
• Carry out the second turning after 3 weeks.
• A third turning is realized only if the original
materials are recognizable, after 9 weeks.
• It takes around 12 weeks for final composting,
though a little longer during monsoons.
• The final product has a pliable texture, an earthy
smell and is dark brown or grey in colour.
• This matured compost is half of its original
volume as it simply shrinks due to the cooling
process.
Indore pit method
• Raw materials
• The raw materials used are mixed plant residues, animal dung
and urine, earth, wood ash and water.
• All organic material wastes available on a farm, such as weeds,
stalks, stems, fallen leaves, prunings, chaff and fodder leftovers,
are collected and stacked in a pile.
• Hard woody material such as cotton and pigeon-pea stalks and
stubble are first spread on the farm road and crushed under
vehicles such as tractors or bullock carts before being piled.
• Such hard materials should not exceed 10 percent of the total
plant residues.
• Green materials, which are soft and succulent, are allowed to
wilt for two to three days in order to remove excess moisture
before stacking; they tend to pack closely when stacked in the
fresh state.
Indore pit method
• Raw materials
• The mixture of different kinds of organic material
residues ensures a more efficient decomposition.
• While stacking, each type of material is spread in layers
about 15 cm thick until the heap is about 1.5 m high.
• The heap is then cut into vertical slices and about 20-
25 kg are put under the feet of cattle in the shed as
bedding for the night.
• The next morning, the bedding, along with the dung
and urine and urine-earth, is taken to the pits where
the composting is to be done.
Pit site and size
• The site of the compost pit should be at a level
high enough to prevent rainwater from
entering in the monsoon season;
• it should be near the cattle shed and a water
source.
• A temporary shed may be constructed over it
to protect the compost from heavy rainfall.
• The pit should be about 1 m deep, 1.5-2 m
wide, and of a suitable length.
Filling the pit
• The material brought from the cattle shed is
spread in the pit in even layers of 10-15 cm.
• A slurry made from 4.5 kg of dung, 3.5 kg of
urine-earth and 4.5 kg of inoculum from a 15-
day-old composting pit is spread on each layer.
• Sufficient water is sprinkled over the material
in the pit to wet it.
• The pit is filled in this way, layer by layer, and
it should not take longer than one week to fill.
• Care should be taken to avoid compacting the
material in any way.
Turning
• The material is turned three times while in the
pit during the whole period of composting:
• the first time 15 days after filling the pit
• the second after another 15 days and
• the third after another month.
• At each turning, the material is mixed
thoroughly and moistened with water.
Labour intensive
Bangalore Method
This method of composting was developed at Bangalore in
India in 1939 By C. N. Acharya, IISc.
It is recommended where night soil and refuse are used for
preparing the compost.
It is initial aerobic process (8-10 days) later semi-anaerobic
The method overcomes many of the disadvantages of the
Indore method,
such as the problem of heap protection from adverse weather,
nutrient losses from high winds and strong sun,
frequent turning requirements, and fly nuisance.
However, the time required for the production of finished
compost is much longer.
The method is suitable for areas with scanty rainfall.
Pit preparation
Trenches or pits about 1 m deep are dug; the
breadth (2m) and length of the trenches (30’
to 20’) can vary according to the availability
of land and the type of material to be
composted.
Site selection is as per the Indore method.
The trenches should have sloping walls and
a floor with a 90-cm slope to prevent
waterlogging.
Filling the pit
Organic residues (15 cm) and night soil (5 cm) are put in
alternate layers.
After filling, the pit is covered with a layer of refuse of 15-20 cm.
The materials are allowed to remain in the pit without turning
and watering for three months.
During this period, the material settles owing to reduction in
biomass volume.
Additional night soil and refuse are placed on top in alternate
layers and plastered or covered with mud or earth to prevent loss
of moisture and breeding of flies.
After the initial aerobic composting (about eight to ten days),
the material undergoes anaerobic decomposition at a very slow
rate.
It takes about six to eight months to obtain the finished product.
Merits
No turning is given as in case of aerobic methods
Simple and easy to manipulate
High temp developed (upto 70°C) in the initial 2 to
3 weeks destroys the harmful pathogen, fly maggots
and also removes disagreeable odour
It requires only ½ to 1/3 of the water used in the
aerobic method
There is higher recovery of manure (one and half
times) than aerobic method
Demerits
It involves digging of trenches hence
increased cost
It takes nearly 4-6 months to get
stabilized manure
5) Coimbatore method
The Coimbatore method was developed by Manickam
(1967), Tamil Nadu Agriculture University. This method
involves digging a pit (3.6 m long 1.8 cm wide 0.9 cm
deep) in a shaded area (length can vary according to the
volume of waste materials available). Farm wastes such as
straw, vegetable refuse, weeds and leaves are spread to a
thickness of 15-20 cm. Wet animal dung is spread over this
layer to a thickness of 5 cm. Water is sprinkled to moisten the
material (50-60 % of mass). This procedure is repeated until
the whole mass reaches a height of 60 cm above ground. It is
then plastered with mud, and anaerobic decomposition
commences. In 4 weeks, the mass becomes reduced and the
heap flattens. The mud plaster is removed and the entire
mass is turned. Aerobic decomposition commences in at this
stage. Water is sprinkled to keep the material moist. The
compost is ready for use after 4 months.
NADEP method of composting
Developed by a Farmer
Sri. Narayan Rao
Pandhari Pande in
Maharastra
This method envisages
composting with min
use of cattle dung
Decomposition by
aerobic method with
natural flow of air
Construction
The method requires construction of a tank measuring
3m x 1.8 m or 3.6 m x 1.5 internally with 25 cm thick
perforated brick wall all around in mud or cement
mortar to a height of 0.9 m above ground.
The above ground-perforated structure facilitates
passage of air for aerobic decomposition.
The floor of the tank is laid with bricks.
The tank is covered above with a thatched roof. This
prevents loss of nutrients by seepage or evaporation
and the contents are not exposed to sun and rain.
Raw Materials
The ingredients for making compost
are agro-wastes, animal dung and soil
in the ratio of 45:5:50 by weight.
Filling
The ingredients are added in layers starting with vegetable
matter followed by dung and soil in that order (45:5:50 by
weight).
Each layer can be about 45 kg vegetable matter, 5 kg of
dung mixed in 70 l of water and 50 kg of soil so that 30
layers will fill the tank.
For convenience the number of layers could be reduced to
half this number by doubling the quantities of ingredients
in each layer.
Tree loppings and green manure crops can also be used to
fill up the tank if sufficient farm wastes are not available at
time.
Filling
The nutrients produced in the manure are absorbed by the
soil layers thus preventing their loss.
About 22-50 L of water is to be sprinkled twice a week after
the tank is loaded.
The material loaded has to be left in the tank for about 100 to
120 days for complete decomposition of the material.
One tank can be used three times a year.
With production of 3 tons to 3.5 tons of compost produced
per cycle about 9 to 10 tons of compost can be made annually
from one tank.
It is advisable to sprinkle cultures like Trichoderma,
Azatobacter and PSB in layers to enhance the speed of
composting process.
Disadvantages
There are certain inconveniences experienced by the farmers
adopting this method. These include
difficulty in following the filling procedure as recommended,
requirement of labour is more compared to traditional methods,
filling is difficult during the raining period,
expenditure on transport of silt when the unit is away from the
field. As the process needs 1.5 t of soil for every cycle, this results
in removing soil.
Advantages
•However, if the tanks are installed in the same field where agro-
wastes are generated and manure to be used, this is not a limiting
factor.
•It is very simple to construct and easier to operate.
•In this method compost can be prepared with minimum quantity
of cow dung use and hence, it can be considered as very versatile
model.
Vat or Japanese method
It is an advanced method
of composting.
Vats of 8-10m length, 1.2m
width and 1.0m height are
constructed using stone
slabs / bricks / stones.
Temporary vats can be
constructed using casurina
or bamboo poles or
coconut fronds.
The floor of the vat is
compacted or plastered to
minimize leaching losses
of nutrients.
Space is provided in the
sidewalls of vat at intervals
of about 1m for aeration.
The vat is filled layer by layer leaving a
minimum of 1m space at one end of the vat.
Organic wastes rich in lignin or cellulose filled
in the bottom layer.
The second layer by leafy or proteinaceous
material or by any green or threshing yard
wastes. Cow dung slurry, rock phosphate and
bioinoculant viz., P solubilizers or N fixers forms
the 3rd, 4th and 5th layers. The layers are
repeated till the brim of the vat. Then the
surface is plastered with soil and dung slurry.
The material should be turned once in 20-
25days compost will be ready in 90-100days.
Advantages and Disadvantages
There are certain inconveniences experienced by the
farmers adopting this method.
These include difficulty in following the filling procedure
as recommended
requirement of labour is more compared to traditional
methods,
filling is difficult during the raining period
expenditure on transport of silt when the unit is away from
the field. As the process needs 1.5 t of soil for every cycle,
this results in removing soil. However, if the tanks are
installed in the same field where agro-wastes are generated
and manure to be used, this is not a limiting factor.
It is very simple to construct and easier to operate.
In this method compost can be prepared with minimum
quantity of cow dung use and hence,
it can be considered as very versatile model.
Karnataka Compost Development
Corporation ltd
Hosapalya, Bangalore, established in 1975-76
Developed a system of composting from city garbage
Plastics, glass, rubber and debris are separated
The heaps are arranged as windrows with periodical
turnings
Under aerobic condition BIOAGRO (0.5 TO 0.9 %
NPK) compost is produced
Neem cake, rock phosphate and gypsum are added to
produce BIOAGRORICH COMPOST
Recycling/ composting
Step 1. Collection and transportation
The recyclable materials are collected from a drop-off
centre, than transported to a compost yard.
Step 2. Sorting & Separation

Separate glass, plastic, metal and other non degradable
from the waste and use only organic waste.
Step 3. Sherdding and pulversing

Chop/ cut into appropriate size of 10 cm .
Step 4. Digestion/ Composting

Open windrow or closed windrow method of composting
Step 5. Processing of compost

Drying, sieving, granulating and bagging
Step 6. Marketing
Sell the compost to needy farmers
AEROBIC COMPOSTING PROCESS
Mixed MSW Or
Preferably Segregated
Biodegradable Waste
Turning schedule for

the MSW
Day 1- Stacking
Stack in Parallel /
Semi Circular Rows on a raised,
impervious and sloping ground
Turning on days :5,10,15,20,
25,30,35
Ensure following parameters for

rapid composting
• 40% moisture content
• PH : 6 –7.5
• C/N Ratio : 25-35
• Temperature 60- 70oC Day 40- Removal of
mature compost
MECHANICAL COMPOSTING
WASTE
SEPERATION & SALVAGE

(REMOVAL OF PLASTICS, METAL, GLASS etc)
PRETREATMENT(SIZE REDUCTION,SCREENING etc)
CONTROLED DECOMPOSITION
MATURATION/STABILATION
COMPOST
MECHANICAL COMPOSTING (Contd..)
Metallic Separator(metals),Ballistic Separator (glass&metal),

Hammer or Rasp mills (Size reduction for faster
decomposition).Front end loaders/windrows reshifters for turning
windrows (5days).
One month – green or clean compost. 1-2 more months for

cellulose stabilisation-ripe compost.
Indian waste does not warrant separators due to negligible

metals &glasses. Manual separation preferable. Artificial aeration
is not necessary due to favorable conditions. size reduction after
stabilisation.
Environment measures: shed or providing of impermeable base(

concrete or 50cm thick compact clay)with 1to 2per cent slope
and circled by lined drains for collection of leach ate or surface
run-off. Pre&post process rejects shall be sent to landfills after
recovery of recyclables.
1. Collection and transportation
2. Open windrow composting
4. Turning, watering
5. Processing of compost
SEMI-MECHANISED AEROBIC COMPOSTING
MERITS
Large quantities of Mixed MSW can be
processed on a small piece of land
Highly useful product for crop improvement
Value addition to waste resource
Sustainable Approach
DEMERITS
Higher Capital, O&M Costs
Sound Marketing Arrangement Required
High Heavy Metals Concentration in Compost
General composting method
Many techniques like Indore technique, Bangalore technique,
Japanese technique etc., are available for composting, a generalized
technique of composting incorporating the virtues from all the methods is
given below:
1. Layers of organic waste material such as crop residues, garbage from
cities and rural areas and agro-industries, farm yard wastes, etc., are to
be piled on a flat concrete or stone platform above the ground, or
alternatively the farmers can stack these layers of organic waste in well
ventilated, shallow brick tanks above ground level.
2. The entire material has to be heaped or stacked in layers at one time.

The dimension of the tanks can be about 4 - 5' width and about 4'
height and of convenient length (depending on the amount of waste
material).
3. Sufficient moisture of about 60 % has to be maintained. To provide

proper aeration, the material in the heaps or tanks should be turned
periodically, once in 5 - 10 days, so that the aerobic process of
decomposition continues uninterrupted.
General composting method
4. Proper shelter may be provided to avoid weathering and leaching
due to rains.
5. The compost is obtained in 3 - 4 months with about 1 - 2 % N,

about 50 – 60 % of organic carbon and other essential macro and
micro nutrients.
6. The composition and nutrient content of the compost varies

depending on the composition of the organic waste used.
7. The process of decomposition can be enhanced by spraying cow

dung slurry or jaggery water.
8. Use of microbial cultures like Actinomycetes, Azatobacter and

other N fixing and P solubilizing bacteria as inoculants will also
hasten the process of decomposition and produce better quality
compost.
Benefits of Recycling
(1) Conserves resources for our children's future;
(2) Prevents emissions of many greenhouse gases and
water pollutants;
(3) Supplies valuable raw materials to industry;
(4) Creates jobs;
(5) Stimulates the development of greener technologies;
(6) Reduces the need for new landfills and incinerators
(about 30% of the MSW is disposed through recycling);
(7) Saves energy;
Table Average nutrient (%) status of bulky organic manures
Organic manures N P2O5 K2O
1. Farm yard manure (FYM) 0.80 0.41 0.74
2. Poultry manure 2.87 2.93 2.35
3. Rural compost 1.22 1.08 1.47
4. Urban compost 1.24 1.92 1.07
5. Mixed farm waste compost 0.87 0.59 2.22
6. Vermicompost 1.60 2.20 0.67

Vermicompost is the pure excreta of
the earthworms. It is the organic
humus containing major and micro
nutrients and microbes and
hormones.
VERMICOMPOSTING
The method of preparing compost with the
help of earthworm as natural bioreactor is
known as vermicomposting.
VERMICOMPOSTING
• Vermicomposting is a process of using earthworms for
conversion of bio-degradable wastes into compost.
• It is combined activity of microorganisms and earth worms.
• Earthworms consume organic matter and convert it into

worm casting.
• Temperature, moisture, aeration influence the

vermicomposting.
• It is useful for market waste and for households and

colonies on small scale.
• It is not much useful for mixed large municipal solid wastes.

Advantages of Vermicompost
• Natural source of macro and micronutrients

• Replenishes organic carbon to the
impoverished soils.
• Helps in the slow release of nutrients from the
manure and crubs the leaching of nutrients.
• Some of the secretions of worms and the
associated microbes act as growth promoters
• Increases water holding capacity of the soil.
• Improves physical, chemical and biological
properties of soil.
• Improves soil health
• Increases crop growth and yield.
Method for Vermicomposting
• Vermicomposting of wastes in field pit

• Vermicomposting of wastes on ground
heap method
VERMICOMPOSTING
PIT FOR SMALL
QUANTITIES OF WASTE
Materials required for
vermicomposting
Tank size :
For one tonne raw materials - 4 m3
(1m width x 1m depth x 4m length )
Earthworms : Eisenia foetida

Eudrilus eugeniae
Vermicompost Production Structures
L- 2', B-2', H-9" L-10 ' , B-4 ', H-1' H- 2 ' , D- 3 '
Model -1 Model-2 Model-3
L- 7 ', B- 4 ', H-2 ' L-20 ', B-4 ', H-1 ' L-16 ', B-3 ', H-4 '
Model-4 Model-5 Model-6

Eudrillus euginiae
Eisenia foetida
Perionyx excavatus
Feed Materials
Usable Non-usable
Cow dung and other Meat, eggs, oils, ghee,
animals dung, poultry milk food, decayed food
wastes, fruits and materials, garlic, acidic
vegetable wastes, green fruits/vegetables and other
leaves and plant wastes, non degradable wastes.
sugar mill wastes, Cakes,
other decomposable
wastes.
Materials required for Vermicomposting
• Farm wastes
• City waste, kitchen waste, vegetable market wastes etc.
• Fresh dung
• Waste: dung ratio 10:1
• Earth warm 1000-1200 adult worms (about 1 kg /q of waste)
• Common sp. Eisenia foetida & Eudrilus eugenia
Pre-digestion of organic waste
materials
The organic material is made into small
pieces
Treat with cow dung slurry @ 10 % (100 kg
cow dung per tonne of organic wastes)
Must be allowed to under go a preliminary
decomposition for about 3 weeks.
Regular watering has to be done as and
when required to maintain a moisture
content of 40-60%.
Cow dung /cow dung slurry
Dried straw/stubbles/S-cane trash
Mulch/soil small quantity
Cow dung /Bio-gas slurry
Green leaf /weeds etc
Farm waste/ dried waste

material

Coconut /arecanut fronds/ any
material which can hold water
Introducing of earth worms
Earth worms may be introduced in the composting

bed @ 1000 nos. per tonne of organic wastes.
Then beds should be covered properly using any
locally available plant materials or gunny bags.
Harvesting of vermicompost
1. In about 45 – 60 days the

compost will be ready.
2. Watering has to be stopped at

this stage to trigger the earth
worms to move down to the
bottom layers and to enable the
removal of granular vermicompost
free of earth worms.
•The harvested compost
is made into a cone shape
heap keeping inside a ball
of fresh cow dung.
•This heap is kept over
night so that all worms
will be attracted towards
fresh cow dung and
accumulated.
The compost is
separated from the cow
dung ball, shade dried
and sieved before
storing.
The separated earth

worms may be left in
fresh organic material.
Packed vermicompost ready for sale
Precautions while composting
• Earth worms are sensitive to temperature. Hence, earth
worms should be introduced in the worm bed after pre-
digestion of organic wastes (15-20 days).
• Regular watering of feed material should be done so as to
maintain a moisture content of 40-60 %.
• The vermicompost pits should be protected from sun light
and rain water by constructing a shed.
• Earth worms should be protected from rodents and ants.
• Make provision to remove the excess leachates (vermi
wash) from the tank.
Precautions
• Maintain the moisture at 50-60 %
level in the pit.
• Temperature between 25-28 ºC.
• Base material (FYM) should be
partially decomposed.
• Proper aeration should be provided
without disturbing the worms.
Composition of vermicompost and FYM
Nutrients Vermicompost FYM

N (%) 1.9-2.0 0.3 -0.5
C:N ratio 13.6 20.6
P (%) 0.6-0.9 0.2-0.4
K (%) 1.0 -1.5 0.3 - 0.5
VERMI COMPOSTING
• MERITS
– Highly useful product for crop improvement
– Value addition to waste resource
– Sustainable Approach
– Earthworms Consume 10 kgs to produce 1 kg of
vermicompost. This rich humus is a soil
conditioner
• DEMERITS
– Slow Process
– Sensitive process requires good segregation &
maintenance
– Sound Marketing Arrangement required
Biogas digested slurry
The use of biogas digested slurry as organic manure can

supplement the usage of chemical fertilizers. The effluent manure does
not produce any odour and hence does not create any pollution. The
biogas slurry is rich in nitrogen, the essential nutrient for plant growth.
Moreover, this nitrogen is in water soluble form and can be easily
absorbed by the plants.
The biogas slurry can also be mixed with biomass and composted.
The slurry being full of bacteria makes excellent composting material.
When a large mass of biomass waste with high carbon: nitrogen (C:N)
ratio is available, the slurry helps stimulate decomposition by acting as a
nitrogen primer. Earthworms could either be cultured in dry sludge or in
a compost pit. During the digestion process, gaseous nitrogen (N) is
converted to ammonia (NH3). In this water-soluble form the nitrogen is
available to the plants as a nutrient. The nutrient rich manure is obtained
if not only dung but also urine is digested.
Biogas digested slurry
Compared with solid sludge from fermented straw and grass, the
liquid slurry is rich in nitrogen and potassium. The solid fermentation
sludge is relatively richer in phosphorus. A mixture of solid and liquid
fermented material gives the best yields. The nutrient ratio of biogas
slurry is N:P2O5:K2O = 1:0.5:1. Fermented slurry with a lower C/N ratio
has better fertilizing characteristics.
The fertilization effect depends on the type of crop and on the soil.
When fermentation slurry is used as fertilizer for years, the soil structure
is improved. The proportion of organic materials in the soil is increased,
enabling the soil to store more water. If fermentation slurry is to be
stored before spreading on the field, it should be covered with earth in
layers. This reduces evaporative nitrogen losses.
Solid wastes and liquid wastes
Any material that is thrown away and/ or discarded as useless and
unwanted is considered as wastes. Depending upon the physical status of
the wastes, the wastes are either solid wastes or liquid wastes.
Classification of solid wastes

1) Domestic and municipal wastes: These include garbage and rubbish,
like paper, plastic and cloth from households, office, hostel and market.
2) Industrial wastes: The composition of industrial wastes depends on
type of products produced. The non-processed wastes are common to all
industries such as packaging, office and cafeteria wastes. Processed
wastes are more complex and specific to the industrial plants.
3) Agricultural wastes: These include cereals, millets and legumes straw,
such as paddy husk, sugarcane trash and other crop residues.
4) Special wastes: The waste materials which endanger public health and
seriously affect environment are: a) Radioactive wastes from atomic power
stations, labs and hospitals b) Toxic wastes such as pesticides, heavy
metals, pharmaceuticals c) Biological products such as antibiotics,
enzymes, pathogens.
Sewage
Sewage is the wastewater released by residences, businesses and
industries in a community. It is 99.9 % water, with only 0.1 % of the
dissolved and suspended solids. A measure of the strength of the
wastewater is biochemical oxygen demand (BOD). BOD measures
the amount of oxygen requires for microorganisms in 5 days to break
down organic matter present in sewage. Untreated sewage has a
BOD ranging from 100 - 300 mg/L. Sewage also contains nutrients
(nitrogen and phosphorus), minerals and metals. The nitrogen can
range from 12 - 50 mg/L and phosphorus can range from 6 - 20 mg/L
in untreated sewage.
Wastewater sludge typically contains organics (proteins,

carbohydrates, fats/ oils), microbes (bacteria, viruses, protozoa),
nutrients (phosphates and nitrates) and a variety of household and
industrial chemicals. The higher the level of heavy metals and toxic
compounds, the greater is the risk to humans and the environment.
Sludge
The solids removed from wastewater during

sedimentation and then concentrated for further treatment
and disposal are called sludge. Even in aerobic waste
treatment processes in which sludge is repeatedly recycled,
most of the sludge must eventually be removed from the
system. The task of treating and disposing of sludge
material is called sludge management. Sludges are
generated through the sewage treatment process.
Sewage/ sludge N P2O5 K2 O

1. Raw sewage 2.0 - 3.0 - -
2. Sludge ( primary) 2.0 - 3.5 1.0 - 5.0 0.2 - 0.5
3. Sludge (activated) 4.0 - 7.0 2.1 - 4.2 0.5 - 0.7
Sewage and sludge
Sewage and sludge are the products of sewerage
system adopted in cities
It includes both domestic and Industrial wastes
The liquid portion is sewage and solid portions
separated and/or obtained by treatment is
sludge
On an average sludge contains 1.5 to 3.5 % N,
0.75 to 2.0 P2O5 and 0.3 to 0.6 % K2O
Night-soil
Night-soil is the human excrement, i.e., solid and liquid. In
China, it has been directly applied to the land for more than 2000
years to improve the fertility of the soil. In Japan during 1951, night
soil supplied 15.5 % nitrogen, 5.1 % phosphoric acid and 11.8 %
potassium are applied to the soil.
Night-soil is a richer in N (5.5 %), P2O5 (4.0 %) and K2O (2.0 %)
as compared to FYM or compost. Human excrements are a
potential source of soil improvement, public health authorities in
many towns make the necessary arrangements for its conservation
and conversion into a form in which it can be safely used as a
manure.
The annual potential quantity of manurial ingredients in the
night-soil from India's present population of 600 million is estimated
at approximately 8.1 million tons of dry matter containing almost 0.4
million tons of nitrogen, 0.25 million tons of phosphoric acid and
0.17 million tons of potash.
In India, night-soil is applied to a limited extent directly to the soil in
trenches. Pits or trenches of 3.05 – 3.66 m long, 0.71 – 0.91 m wide and
0.22 – 0.28 m deep are made. In these pits, night soil is deposited and
covered over on the top with a layer of earth. This is known as poudrette
system, since the material formed in the trenches after they become dry, is
known as poudrette.
The dehydration of night soil, as such or after admixture with

absorbing materials, e.g. soil, ash, charcoal and sawdust, produces a
poudrette that can be easily used as a manure. The mixing of night-soil
with an equal volume of ash and 10 % powdered charcoal produces an
odourless material, containing 1.32 % potash. The addition of 40 - 50 % of
sawdust to the night-soil yields a dry, acidic poudrette which may contain 2
- 3 % nitrogen.
Drawbacks of poudrette system

•It gives out a bad smell,
•It is an anaerobic process of decomposition,
•Gasses are liberated,
•It leads to fly breeding,
•The poudrette manure is partially decomposed material.
Green manuring
It is a practice of ploughing or turning in to the soil
undecomposed green plant tissues for the purpose of
improving soil properties.
Types of green manures
Broadly the practice of green manuring in India can be

divided in to two types
1. Green Manuring in situ
2. Green leaf manuring
Green Manuring in situ
Is a system by which green manure crops are grown and
incorporated into the soil of the same field
(GM crop may be grown as pure crop or intercrop)
e.g. sunhemp, Dhaincha
Green Manuring through collection of

green tissues from other places
It refers to turning into the soil green leaves and tender
green twigs collected from outside the field to be green
manured
e.g. Glyricidia, karanja
Green manuring
Sesbania Crotalaria
B. Adding off-field organic material
Glyricidia Pongamia
C. Growing of cover crops
Cover crop refers to a field or forage crop grown

particularly to cover the soil. The cover crop also can be
later incorporated as green manure.
Cover crops mainly acts as a live mulch protecting the

soil from erosion possibilities.
Cover cropping is also practiced to benefit from any

fertilizer residues and available moisture in the soil.
Cover crops provide significant benefits to soil including

providing nutrients, nutrient cycling, weed control, soil
protection and soil improvement.
These benefits vary mainly based on the management

practices, and climate affecting the quantity and timing
of biomass produced.
The popular cover crops are short duration legume crops

like horse gram, black gram, green gram, cowpea etc.
C. Growing of cover crops
Cover crop of cowpea Forage grass as cover crop

Nutrient content of some important GM crops
Crop % Nutrient
N P K
Green Manuring in situ
Sunhemp 2.6 0.6 2.0
Dhaincha 3.3 0.7 1.3
Cowpea (fresh) 0.7 0.15 0.58
Horse gram (fresh) 0.33
Green gram 0.72 0.18 0.53

Nutrient content of some important GM crops
Crop % Nutrient (dry wt basis)
N P K
Green Leaf Manuring
Glyricidia 2.9 0.5 2.8
Honge (karanja) 3.7 2.4 2.4
Madhuca indica 1.7 0.5 2.0
Characteristics of an ideal GM crops
Must be deep rooted
Should have less nutrient and water requirement
for its own development
Must grow fast to produce abundant biomass
(green foliage)
Must be seculant
Should be a leguminous plant with high capacity
to fix the atmospheric N
Advantages of GM
Increases OM content of the soil thereby modify
the soil properties.
It stimulates the activity of SMO
Helps in returning the nutrient to the surface
layer from subsurface soil layer
Improves soil aeration, permeability, and
infiltration capacity of soil
Reduces soil loss by preventing runoff
Majority of GM crops are being leguminous, thus
help in fixing atmospheric N
Factor affecting decomposition
•Organisms: The bacteria, fungi, actinomycetes are responsible for
decomposition of green manures. Rapid decomposition can observed in
aerobic compared anaerobic condition.
•Temperature: Optimum temperature for decomposition is 30-35 C under

this condition the growth of organism will be more.
•Aeration: Multiplication of organism is more under aerobic condition and

decomposition is fast.
•Moisture: Decomposition of green manure and growth of organism water

is needed. The optimum amount of moisture in the green manure are
around 50 %.
•Soil factors: Optimum physical, chemical and biological factors are

necessary for decomposition. The decomposition is slower if soil contains
higher clay content.
•Green manures: If it is succulent quick decomposition can be expected

and in non- succulent crops slow decomposition is prevailed.
Concentrated Organic manures
Material of organic origin, derived from raw materials
of animal or plant without bulky in nature having no
definite composition of plant nutrients
E.g. , Oil cakes, fish meal etc.
Characteristics
Easier to handle
Have relatively higher plant nutrients
Less bulky
Quick acting when incorporated into soil
b) Press mud
It is a waste product from the sugar industry and used as manure.
For every tone of sugar cane approximately 30 - 40 kg press mud is
produced. At the time of purification of sugar cane juice sufficient
amount of filth is obtained which contained excess of phosphorus
and lime. It contains 8 % organic matter, 0.5 % N and 1.3 % P and
60-75 % calcium carbonate.
The major use of press mud has been developed in India is
biocomposting (trade name as Bioearth) where it is treated with the
spent wash from the distillery. The bio-compost is produced by
spraying spent wash on stacks of pressmud through biocomposting.
Steps of biocomposting
The steps of biocomposting are:
•Formation of windrows and reduction of moisture content from 70 to
50 % in 5 days and inoculation of microbial culture.
•Spraying of spent wash and homogenization of windrows for 30
days.
•Maturation period of 10 days to reduce moisture to 30 %.
Bio compost
Organic manure produced is rich in micronutrients and can
reduce the requirement of chemical fertilizers. It also provides
bacteria for nitrogen fixing, solubilisation of phosphates, humus that
will keep the soil healthy and develop the self-reclamation cycle.
The biocompost contains 25 - 30 % organic carbon, 1.2 - 2.0 %
nitrogen, 1.5 - 2.0 % phosphorous and 2.5 - 3.0 % potash. Press
mud is the used as soil amendment. It should be broadcasted
followed by ploughing and irrigation. Application of press mud at 40
tons/ ha is reported to reduce the pH of soil from 8.5 to 7.6.
Table Nutrient content of the pressmud, spentwash and biocompost
Sl. No. Pariculars Nitrogen Phosphorus Potassium

1 Pressmud (%) 1.15 - 3.0 0.60 - 3.50 0.30 - 1.80
2 Spent wash (mg/L) 2630 201 222
3 Biocompost (%) 1.2-2.0 1.5-2.0 2.5-3.0
Oil Cakes
The residue left after oil has been extracted from the
oil seeds
About 2 m t of oil cakes is produced in India/year
Quick acting (The N become available in about 7 to 10
days after application)
These can be grouped as
1. Edible oil cake 2 .Non-edible oil cake
1. Suitable for feeding 1. Not Suitable for
the cattle feeding the cattle
2. Some cakes are used 2. Exclusively used as
as organic manure Organic manure
Average Nutrient Content of COM
Material N (%) P2O5 (%) K2O (%)
Non-edible cakes
Castor cake 5.5 – 5.8 1.8 – 1.9 1.0 – 1.1

Neem cake 5.2 – 5.3 1.0 – 1.1 1.4– 1.5
Karanja cake 3.9 – 4.0 0.9 – 1.0 1.3 – 1.4
Mahua cake 2.5 – 2.6 0.8 – 0.9 1.8 – 1.9
•Mahua cake contain relatively low N and is very

slowly nitrifies
•Because it contain a toxic substance called Saponins
•Hence it should applied 2 months in advance
Material N (%) P2O5 (%) K2O (%)
Edible cakes
Groundnut cake 7.0 – 7.2 1.5 – 1.6 1.3 – 1.4

(decorticated)
Cotton seed cake 6.4 – 6.5 2.8 – 2.9 2.1 – 2.2

(decorticated)
Blood Meal
Dried blood or blood meal is by-product of slaughter house
Quick acting manure and is effective on all crops
Is prepared by adding 1 % Lime to the blood (for coagulate)
and thereafter heating to 80 °C
Fish manure
•Non-edible fish carcasses of fish used to prepare in dry
powder form
•The residue after fish oil extraction can also be used as
manure
Wood ash : Wood ash, cattle dung ash etc are the
indigenous source of K
Guano
The word guano means dung in Spanish
It is mainly constituted of the dropping of sea
birds and also small amounts of dead bodies of
birds or dead fishes
The deposits of guano have been located in
Islands and main lands near river
Horn and hoof meal
This manures prepared by horns and hoofs obtained from
dead animals. Hoofs and horns are boiled in bone digester
and are powdered after drying. Hoof meal is better than horn
meal.
Animal origin
Fish Meal 4 – 10 3–9 0.3 – 1.5
Blood Meal 10 - 12 1 – 1.5 <1
Guano 7 – 16 8 -12 1 -3
(4-6) (20 -25)
Fertilizers
Fertilizers are usually an industrial manufactured

inorganic material having definite chemical
composition, with higher analytical value and capable
of supplying plant nutrients in available forms.
Fertilizers
Fertilizers are materials (solid, liquid or gas)
containing one or more chemical compounds or
the organic or inorganic nature
These occur either as a natural deposit or are
synthesized in a chemical factory.
These are graded as concentrated plant foods
On application these material dissolve fully or
sparingly in the soil-water and release the
nutrients in the ionic form
Some fertilizer after application to soil undergo
biochemical transformation before releasing the
nutrients in plant available form
Comparison between Manures and Fertilizers
Manures Fertilizers
1. Organic in nature 1. Inorganic in nature (Except urea
and CaCN2)
2. Mostly synthesized in Industries
2. Prepared from plant and animal
residue or obtained as plant or
animal by-products
3. No definite chemical composition 3. Definite chemical composition
4. Low in plant nutrient 4. High in plant nutrients
5. Supply almost all the plant 5. Supply only one or two specific
nutrients nutrients
6. Have residual effect for succeeding 6. No residual effect
crops
7. Improve soil condition 7. No such effect on soil properties
8. Does not produce acidity or 8. Leave acidic or alkaline residue
alkalinity in the soil
9. Slow acting with high OM 9. Very quick acting with low OM
Classification of fertilizers
Fertilizers
Straight
fertilizers is a Compound or Mixed fertilizer or
single complex fertilizers Mixture - are
compound -is also single prepared by mixing
containing compound but two or more
one primary contains two or fertilizers. Such
(N or P or K) more nutrients of mixtures can be
nutrient only which at least two prepared by mixing
primary nutrients two or more
are in chemically straight fertilizers
combined form or one or more
N- Fertilizers straight fertilizers
with one or more
P-Fertilizers complex fertilizers
K-Fertilizers
complete Incomplete
Nitrogenous fertilizer
• Elemental Nitrogen, recognized by Rutherford in 1772 as a
colourless, odorless and inert gas, is the main constituent of air
(approximately 79 percent by volume).
• Hence one might naturally expect that plants may not have any
deficiency for this nutrient element and that there may be large
deposits of mineral compounds of N on the surface of the earth.
• But actually this is not so. Though in the air over an acre of land
there is a N supply of over 35,000 tons (an abundant supply) the
plants, except the legumes, are incapable of utilizing this
elemental N for their growth.
• Most of important mineral deposits are the Chile salt peter
(NaNO3), or Chilean niter and Niter (KNO3) or Bengal salt peter.
Sources of nitrogen
1. Mineral deposits
a) Chile saltpeter (NaNO3): Chile, Peru, Bolivia, California and
Nevada.
b) Niter (KNO3) or Bengal saltpeter: Spain, Egypt, Persia, India
and U.S.A.
2. Addition through rain water

A small amount of about 25 - 30 kg ha-1 year-1 is added
to the soil during thunderstorms in these process discharges of
atmospheric electricity produce nitrous oxide and rain carries
this to the soil as nitric acid where it is quickly converted into
nitrates.
3. Soil organic matter

This is the main sources of nitrogen in the soil and the
nitrogen content of any soil will depend upon the quality and
quantity of organic matter of that soil.
Sources of nitrogen
4. Nitrogen fixing organisms
The free living, non-symbiotic (Azatobactor and Clostridium) and
symbiotic (Rhizobium) bacteria are found to fix considerable amounts of the
elemental nitrogen in a combined form. For example the non- symbiotic
bacteria are found to fix 5 -15 kg N ha-1 year-1, while the symbiotic
organisms fix about 300-350 kg N ha-1 year-1.
5. Industrial source
The nitrogen is obtained from the industries in a combined form from
the following processes.
a) Direct oxidation/ arc process
b) Cynamide process
c) Synthetic ammonia process
For the commercial manufacture of the various nitrogenous

fertilizers, the elemental nitrogen has to be converted into either as ammonia
(NH3) or nitric acid (HNO3) which may serve as the basic material for the
synthesis of other materials.
Classification of N fertilizers
N - Fertilizers
Based on forms
Nitrate form Ammonium form Both NH4 and NO3 Amide or cyanamide
(NO3 – N ) (NH4 – N) (NH4-N & NO3-N) -NH2 or – CN2
E. g. E.g. E.g. E.g.

NaNO3 (NH4)2 SO4 NH4NO3 CO(NH2)2
Ca(NO3)2 NH4Cl CaNH4NO3 CaCN2
KNO3 NH3 (NH4)2SO2NO3
Classification of N fertilizers
N - Fertilizers
Based on whether they leave acidic or basic residue
Acidic N-fert Neutral N-Fert Basic N-Fert
E.g. E.g. E.g.

(NH4)2 So4 CaNH4NO3 NaNO3
NH4Cl
NH3
CO(NH2)2
N fertilizers
Sl. No. Name of the N fertilizer N content (%) Form of N
1. Sodium Nitrate (NaNO3) 16.0 Nitrate

2. Calcium Nitrate (Ca(NO3) 2) Nitrate
3. Potassium Nitrate (KNO3) 12.5-13.5 Nitrate
4. Ammonium Sulphate (NH4)2 SO4 20.6 -21 NH4
5. Ammonium Chloride (NH4 Cl) 25-26.0 NH4
6. Ammonium Nitrate (NH4NO3) 33 - 35 NH4 – 16.5
NO3 – 16.5
7. Ammonium Sulphate Nitrate 25.6 NH4 – 19.5
(NH4)2SO2NO3 NO3 – 6.6
8. Calcium Ammonium Nitrate 26 NH4 – 13
(NH4)2SO2NO3 NO3 – 13
9. Urea (CO (NH2)2) 46.0 Amide
10. Calcium cyanamide (CaCN2) 20.6 Amide
Synthetic Nitrogenous Fertilizers
For the commercial manufacture of the various N
fertilizers, the elemental N has to be converted into a
combined form either as NH3 or HNO3 which may serve as
the basic material for the synthesis of other materials.
There are three main processes of synthetic fixation of N,
1. Direct oxidation process (Arc process): The final
product is dilute HNO3.
2. Calcium cynamide process: Final product is CaCN2.
3. Synthetic ammonia or Haber –Bosch process: Final
product is anhydrous or aqueous NH3.
I. Arc Process
This method was demonstrated by Cavendish in 1766
on a laboratory scale.
This is the most simple process of synthetic N fixation
and it was first to be commercially utilized.
Commercial venture was established by Bradley and
Lovejoy in USA during 1902-1904
The basic reaction of this process involved is the union
of N and O by means of an electric arc, the process
being similar to that which is known to take place
between N and O in the atmosphere due to lightening
discharge of electric storms ( nearly 100 m tonnes of
the atmospheric N fixed).
Arc Process
It involves a reaction between N2 and O2 in an
electric arc field at a temp of 3500°C.
This is accomplished by blowing air through a
flaming electric arc, When about 2% of air
combines to yield nitric oxide, which is allowed to
combine with O2 and water to yield HNO3
• N2 + O2 _____ 2 NO
• 2NO + O2 ------ 2NO2
• 3NO2 + H2O ------ 2HNO3 + NO.
But this process requires high amount of electric power and high
capital cost. It requires about 5 times as much electricity to fix a ton
of N as is required by the cyanamide process. But this method is
found to be suitable for countries like Scandinavia and Norway where
the electricity is very cheap.
II. Cynamide process
• This process was developed in Germany by
Adolph Frank and Nicodem Caro in 1898.
• The first step or stage involving burning of
limestone in a vertical furnace or kiln at about
1300°C where the limestone decomposes to
CaO.
1300° C
CaCO3 CaO + CO2
II. Cynamide process
• Calcium carbide is next produced by heating
the lime with coal or coke in an electric
furnace
Ca O + 3C Ca C2 + CO
• Pure N (obtained by fractional distillation of
liquefied air) is then reacted with CaC2 at
about 1000°C to obtain
CaC2 + N2 CaCN2 +C
III. Direct or synthetic ammonia process
• This was developed between 1900 and 1910 by Haber,
Nernst, Bosch and others.
• The main principle of this method is when 3 moles of H
and one mole of N are brought into contact with a
suitable catalytic surface at elevated temperature and
pressure, ammonia is formed.
• High pressure and temperature are necessary, because
at high temperature and pressure alone the reaction is
irreversible.
Catalyst-Fe3O4
High temperature Promoter- Mo/Al/K/CaO
(400 -1200 °C )
• 3H2 + N2 2NH3 The conversion of two reactants
High pressure 200 – to NH3 is usually 17 – 28 %
1000 atm
Natural Steam Air Steam reforming process
gas CH4 H2O N4O
Reforming reaction 2CH4+H2O+N4O 2N2 +5H2+CO
CO +Steam (Shift reaction) CO +H2O CO2 +H2
CO2 removal CO2 absorbed in alkaline medium
Final CO2 removal

CO2 +4H2 CH4 +2H2O
CO +3H2 CH4 +H2O
Compr
essor Recycle of unconverted N and
H mixture
150-350
Ammonia
atm
converter
7CH4+10H2O+8N2+2O2 16 NH3+ 7 CO2

Ammonia
Sources of N and H
Sources of N
1.Air
2.Air gas or producer gas
Feed stock for H

1. Natural gas
2. Naphtha
3. LPG (liquefied Petroleum gas) –Mainly butane (C4H10) and
propane (C3H8)
4.LNG (Liquefied natural gas)
5. Fuel oil
6. Coal
Natural gas
• Natural gas is obtained from two sources
1.Oil wells -Assam
2.Decomposition of OM
• Natural gas from oil wells is used as a H source
accounts over 70%
• This is a mixture of several gases
Composition of Natural gas-feed stock
Composition % by volume
Methane CH4 93.5
N2 2
Argon 0.4
CO2 0.01
H2S < 5 ppm
Hydrocarbon
Ethane C2H6 33
Propane C3H8 0.9
Butane C4H10 0.2
Pentane C5H12 0.01
Naphtha
• Naphtha is a one of the by-product of petroleum
industry. Obtained by fractional distillation of
petroleum. The following fractions are obtained
at different ranges of temp
Fractions Temp. range° C
Gasoline 40- 200 Elements Amount
Naptha 200 -250 C 84.6 %
Kerosene oil 250 - 300 H 15.7 %
Gas oil 300 -350 S 368 ppm
Residual oil – Lubricating oil, Vaseline, Grease, Paraffin etc
Reactor for Ammonia Synthesis
Figure A : Kellogg reactor - 2nd generation Figure B : Topsoe’s reactor 3rd generation
Uses of Ammonia
1. Agricultural and fertilizer industry (production of other fertilizers)
– Production of ammonium phosphate, (NH4)3PO4
– Production of ammonium nitrate, NH4NO3
– Production of ammonium sulphate, (NH4)2SO4
– source of protein in livestock feeds for cattle, sheep and goats
2. Nitric Acid Production – used in making explosives such as

Trinitrotoluene (TNT)
3. Ammonia-soda industry – uses ammonia for producing soda ash
4. Petroleum industry uses ammonia to
– neutralize acid constituents of crude oil
– protect equipment from corrosion
5. Rubber industry – prevent premature coagulation by stabilizing
natural rubber
6. Pulp and paper industry – for pulping wood
7. Textile industry – manufacture of synthetic fibers such as nylon and
rayon.
8. Plastics industry – manufacture of phenolics and polyurethanes
Fertilizers synthesized from ammonia
+ NH3
NH4NO3 35-36 % N
HNO3 + Na2CO3
NaNO3 16% N
+ Rock phosphate Nitro phosphate
+O2
12 -27 % N; 20 – 35 % P2O5
+ H2SO4
(NH4)2SO4 20 -21 % N
NH3 + H3PO4 Ammonium phosphates

11 -12 % N; 46 – 55 % P2O5
Ammonium polyphosphate Liquid

0 - 11% N; 34 - 37% P2O5
Urea 46 % N
Nitrogen solutions 27 -32 % N
NH4OH 20 -25% N
I. Nitrate fertilisers
1.Nitrate fertilizers are readily soluble in water
2.These are generally used as good top dressing materials.
3.Nitrate fertilizers are physiologically alkaline fertilizer,
4.Nitrate fertilizers are best used in acid soils.
5.Nitrate fertilizers are easily leached from the soil because of
less adsorption.
1) Sodium nitrate (NaNO3) 16.0 % N

It is obtained as a natural product (caliche) in Chile
and manufactured from synthetic ammonia. The important
impurities of natural product caliche are common salt
(NaCl), Glauber’s salt (Na2SO4), gypsum, iodates, borates.
The natural product (caliche) is processed by two methods i)
Shank’s method and ii) Guggenheim’s process.
Preparation of sodium nitrate
The gaseous nitrogen obtained from coal gas is combined with

hydrogen to form ammonia. The ammonia formed is oxidized
to nitrogen oxide in the presence of catalyst. The nitrogen
oxide are then absorbed in a solution of sodium carbonate.
The resulting solution is sodium nitrate. It is evaporated and
the solid material is crystallized.
4NH3 + 5O2 4NO + 6H2O

( 2NO + O2 2NO2 ) x 2
4NO2 + 2H2O 4HNO3
4NH3 + 7O2 + 2H2O 4HNO3 + 6H2O
Na2CO3 + 2HNO3 2NaNO3 + H2O + CO2
General characteristics
1.It is readily soluble in water and good for top dressing

material.
2.It contains 27% Na, it has a favourable influence of
potassium economy.
3.Field crops benefited by sodium application are sugar beet,
cotton.
4.It may damage the structure of the soil by reducing
flocculation.
5.It is a basic fertilizer, 100 kg of sodium nitrate reduces the
acidity equivalent to 29 kg of calcium sulphate.
6.Natural sodium nitrate contains traces of micro nutrient, viz.,
Mn, B, Cu, Zn.
2) Calcium nitrate [Ca(NO3)2] 15.5 % N
Calcium nitrate is also called Norgessal peter (Norwegian

saltpeter). It is also called as nitrate of lime. It is a first
synthetic nitrogenous fertilizer. Its manufacture and use in
India is limited.
1) Calcium nitrate is prepared by reacting limestone with

nitric acid. The 80 % of total products is solid in which 40 % is
calcium nitrate, 20 % ammonium nitrate is added to increase
the nitrogen content to 15.5 %. By centrifugation methods
granules are made of the mixture.
CaCO3 + 2HNO3 Ca(NO3)2 + H2O + CO2 + energy

2) Calcium nitrate [Ca(NO3)2] 15.5 % N
2) Calcium nitrate is also a byproduct of the Odda process for
the extraction of calcium phosphate. When rock phosphate is
treated with nitric acid and calcium nitrate is formed. Calcium
nitrate is separated by acidulation.
Ca3(PO4)2 + 6HNO3 2H3PO4 + 3Ca(NO3)2
General characteristics of Calcium nitrate

1.The calcium nitrate is highly hygroscopic in nature.
2.The drilling quality of the calcium nitrate depends upon
relative humidity of the atmosphere, (RH < 40 %), if more than
60 % RH, the fertilizer is fully liquefied.
3.It contains 15.5 % N, 16 % water soluble Ca and 7 % Mg.
4.Due to the presence of calcium in the fertilizer it is a good
fertilizer for acid soils.
The equivalent alkalinity produced by the calcium nitrate is 21
kg gypsum per 100 kg of fertilizer.
3) Potassium nitrate (KNO3) (13.9 % N)
Potassium nitrate is also called as nitrate of potash,
saltpetre and nitre. It is derived from Latin sal petræ means
stone salt. Potassium nitrate is a natural occurring mineral
source of nitrogen. The major sources of potassium nitrate
were the deposits crystallizing from cave walls and the draining
of decomposing organic material.
When used by itself as a fertilizer, it has 13.9 % and 38.7 %

of nitrogen and potassium, respectively. Its most important
usage historically has been as a component of gunpowder.
II. Ammoniacal/ Ammonium fertilisers
1.Ammonium fertilizers are readily soluble in water
2.Ammonium fertilizers are not hygroscopic
3.Ammonium fertilizers are acidic fertilizer
4.Ammonium fertilizers are best suited for neutral soils.
5.Ammonium fertilizers are retained by the soil colloids.
6.Ammonium fertilizers are less readily available to the plant
than nitrate forms
7.These are generally used as for basal application to crops.
8.Rice and sugarcane prefers ammonium fertilizer
Sulphuric acid
Most of the fertilizer industries are based on elemental
sulphur except for Hindustan Copper Ltd., Khetri and
Hindustan Zinc Ltd., Udaipur which are based on flue gases
from copper and zinc smelters respectively. Sulphuric acid
produced is based on iron pyrite and similar plant of larger
capacity is under construction by Sindri of FCI. The fertilizer
industries are the greatest consumer of sulphuric acid for
acidulation of rock phosphate and for the manufacture of
ammonium sulphate.
The elemental sulphur is burnt to sulphur dioxide and
pyrites are roasted to oxidize the sulphide content to sulphur
dioxide. Sulphur dioxide after catalytic conversion to sulphur
trioxide is absorbed in water to give sulphuric acid.
S + O2 SO2
2SO2 + O2 2SO3
SO3 + H2O H2SO4
i) Chamber/ tower process
The oldest process is the chamber process, so called
because the reactions which produce sulphur trioxide and
sulphuric acid take place within a lead chamber. The
conversion to sulphur trioxide and then to sulphuric acid in the
chamber is made possible by the use of nitrogen oxides as
oxygen carrying catalysts. The need to attain greater output of
acid resulted in the development of the so called tower process
in which packed towers are substituted for the lead chamber.
ii) Contact process

In this process, sulphur dioxide is converted to sulphur
trioxide by the use of a metal or metal oxide catalyst. The more
common catalysts are platinum, iron oxide and vanadium pent
oxide, although newer plants use the latter almost exclusively.
Sulphur trioxide is passed to a tower where it is absorbed in
recycling conc. sulphuric acid.
Ammonium sulphate
(NH4)2SO4 is one of the important fertilizers produced in India. It
contains about 21% N and 24% S and has been traditionally
been very popular in various parts of the country.
Production capacity
The total installed capacity in the country is about one million
tones of (NH4)2SO4 corresponding to about 2,00,000 t P a of N.
Raw materials / sources

The raw materials required to produce (NH4)2SO4 are
- H2SO4 for its recovery from coke oven plants.
- NH3 and H2SO4 for neutralization process.
- Gypsum (natural or by product from H3PO4 plants) and NH3
for process using gypsum route.
Ammonia Liquor
Manufacturing
Steam
Reactor or
Saturator
H2SO4
Slaked lime + ammonia liquor
Heat
Method of manufacture
1. Recovery from coke-ovens
The production of Amm. sulphate was started during 1933 at Tata
Iron and Steel Co.ltd, Jamshedpur
The coke-oven gas (obtained when coal is heated to make coke)
contains about 1% NH3 by volume.
The NH3 is recovered by cooling and bubbling it through water.
Thus the ammonia is absorbed by water to form ammonia liquor.
The ammonia liquor is distilled with slaked lime to set free the
ammonia from ammonium carbonate.
The liberated ammonia is passed into saturators containing weak
H2SO4.
The ammonia reacts with H2SO4 to yield (NH4)2SO4
crystals formed in the saturator are recovered, centrifuged,
washed and dried.
2NH3 + H2SO4 (NH4)2SO4
2. Direct neutralization
• The production of Amm. sulphate by this process
was started in 1941 Mysore chemicals and
Fertilizers Ltd, Belagula
• Gaseous ammonia is directly neutralized with
H2SO4 to produce (NH4)2SO4.
• 2NH3 + H2SO4 (NH4)2SO4
• The neutralizer reactor and the crystallizer are
interconnected so that the heat released during
neutralization is used to evaporate water in the
slurry. The crystallizer is designed to produce
uniformly sized crystals.
3. Gypsum process
• The production was started in 1947 by FACT,
Alwaye
• NH3 gas is absorbed in water and then converted
to (NH4)2 CO3 by absorbing CO2. The (NH4)2CO3 is
reacted with gypsum (CaSO4, 2 H2O) to produce
(NH4)2SO4 and CaCO3.
• Ca SO4 2H2O + (NH4)2CO3 (NH4)2 SO4 +
CaCO3 + 2H2O
• CaCO3 is removed by filtration (NH4)2SO4 solution
is evaporated, crystallized, centrifuged and dried.
NH3 CO2 at 5 atm
Gypsum suspended
in water
Filtration CaCO3 precipitate is

separated
Evaporation of
(NH4)2SO4
Crystals of (NH4)2SO4
4. Byproduct from caprolactum plants
Ammonium sulphate was obtained as a by
product during 1974 in GSFC, Baroda
(NH4)2SO4 solution is formed during the
manufacture of caprolactum (the starting
material for Nylon- 6).
The solution is concentrated, and (NH4)2SO4 is
recovered by crystallization, centrifuging and
drying.
Specification as per FCO
- Moisture % by weight. Max 1.0
- NH4 – N % by weight Min 20.6
- Free acidity as H2SO4 % by weight max 0.025
- Arsenic (As As2 O3) % by weight max 0.01
Properties
It is white (sometimes tints of blue, brown, gray, yellow may be
found due to impurities), soluble in water and nearly non-
hygroscopic, crystalline compound and it is an acidic fertilizer (110 kg
of calcium carbonate)
Handling storage and packing

Does not normally pose any problem in handling and storage.
However, it generally contains some powdered material which causes
caking especially under high humidity.
Due to its susceptibility to caking and slight acidity (NH4)2SO4 is normally
bagged in polyethylene lined gunny bags or high density polyethylene
(HDPE) woven sacks.
Ammonium chloride (NH4Cl) 26% N
This is sometimes called muriate of ammonia. It is
commercially prepared by combining ammonia with
hydrochloric acid and the resultant product, ammonium
chloride is found to have very good physical condition. This
fertilizer is also obtained as a by-product of the Solvay’s
process of making sodium carbonate.
The commercial sample is a white, crystalline salt
containing 26 % N in the ammoniacal form. The fertilizer is
suitable for many crops except for those, which are sensitive
to high chlorine content. This is physiologically acidic fertilizer.
Preparation
1) Sodium chloride is treated with ammonia and carbon
dioxide to form ammonium chloride and sodium bicarbonate.
The resulting ammonium chloride is then separated.
NaCl + CO2 + NH3 + H2O NH4Cl + NaHCO3
2) Ammonium chloride is also obtained as a byproduct of soda ash
(Na2CO3) and manufactured as Solvay’s process. It is prepared by
reacting calcium chloride with ammonium carbonate.
2NH3 + H2O + CO2 (NH4)2CO3

(NH4)2CO3 + CaCl2 2NH4Cl + CaCO3
3) Ammonium chloride is obtained by double decomposition between

ammonium sulphate and sodium chloride at 130oC.
(NH4)2SO4 + 2NaCl 2NH4Cl + Na2SO4
4) Ammonium chloride is produced by reaction between ammonia

and hydrochloric acid.
2NH3 + 2HCl 2NH4Cl
Properties
1.It is more acidic compare to ammonium sulphate, 100 kg of
ammonium chloride produces acidity which requires 128 kg of
CaCO3 of neutralise.
2.It contains chlorine, as such it acts as decalcifying fertilizer.
3.Though this fertilizer has not been used extensively as
straight fertilizer, it is preferred in preparing many fertilizer
mixtures because of its good physical properties.
Ammonium chloride is extensively used in Japan for rice,

compared to ammonium sulphate, but in India for industrial
purpose.
Ammonium sulphate under reduced condition, it may produce

H2S, which may cause Achioki disease in rice.
III. Ammonium and nitrate fertilisers
1.These fertilizers contain both ammonium and nitrate forms

2.These fertilizers are readily soluble in water
3. These fertilizers are hygroscopic (AN is highly hygroscopic,
ASN and CAN slightly hygroscopic)
4.These are generally used as good basal and top dressing of
crops.
5.These fertilizers are physiologically acidic fertilizers, except
CAN which is neutral fertilizer
6.Nitrate nitrogen form is readily available to the plants for
rapid growth and the ammonium nitrogen resists leaching loss
and provides a steady source of nitrogen.
NITRIC ACID MANUFACTURE
• About 75% of the HNO3 produced is consumed in the
fertilizer manufacture, while about 15% of the production
goes into the manufacture of explosives. The remainder is
used in a wide variety of outlets, the more important ones
being synthetic fibers, dyes and plastics.
Production capacity
• HNO3 in produced in about 50 factories in India. Out of
these, 18 factors are producing above 100 t p a.
Raw materials
NH3 and air are required for the manufacture of HNO3
Manufacture
• HNO3 is produced by NH3 oxidation process.
• The liquid NH3 is evaporated, superheated and sent with
compressed air to the converter, containing platinum –
rhodium catalyst, where NH3 is converted to nitric oxide,
which is then converted to nitrogen dioxide in oxidation
vessel with the help of secondary air.
• 4NH3 + 5O2 4NO + 6 H2O ---1
• 2NO + O2 2NO2 ----2
• In the process, water absorbs nitrogen dioxide to from
HNO3 while running in counter flow to the raising nitrogen
dioxide in absorption column.
• 3NO2 + H2O 2HNO3 + NO-------3
• 2NO + O2 2 NO2 -------4
• Reactions 3 and 4 repeat through the absorber
Ammonium Nitrate
• Raw materials – Nitric acid and Ammonia
• This is mainly manufactured by passing NH3 gas into
HNO3 and then isolating the product in a solid form
suitable for use as fertilizer. The equipment should be
stainless steel or other special alloys.
• HNO3 + NH3 NH4 NO3 + Heat
• NH4 NO3 produced in neutralization tower. Where NH3
gas is introduced near the bottom of the tower, while
air is added at a higher point to cool the solution and
carry off the water vapour. The solution containing
about 80% of NH4 NO3 is withdrawn and converted to
crystals or pellets as the case may be.
Properties
• Pure NH4 NO3 is a white crystalline salt having
33% of N, one half of which is in the NH4 form
and the other half in the NO3 form. It is readily
soluble in water and it is acidic fertilizer and
highly explosive
• It is highly hygroscopic and cakes up very soon.
• But, when the crystal is coated with about 5% of
a conditioning agent like clay etc, it is found to
have good physical properties.
• The acidity of product is found to be equivalent
to 59 lb of CaCO3 for every 100 lb of NH4 NO3.
Ammonium sulphate nitrate (ASN) (NH4)3SO4NO3
It is also known as Leuna salt petre or sulphonitrate. It is
a double salt and combination of ammonium sulphate (62.5 %)
and ammonium nitrate (37.5 %) and has a nitrogen content of
26 %. It is acidic in nature. Application of 100 kg of ASN makes
the soil acidity requires 93 kg of CaCO3 to neutralize.
FCO Specifications of ASN are

1. Moist % by weight, maximum = 1.0
2. Total ammonia and nitrate nitrogen% by weight, Min = 26.0
3. Amount N% by weight Min = 19.25
4. Free acidity (as HNO3) % by weight maximum = 0.15
Calcium ammonium nitrate (CAN) CaCO3.NH4NO3
Manufactured during 1961 at NFL, Nangal
This is prepared by mixing NH4 NO3 with either precipitated
CaCO3 or ground limestone or ground dolomitic limestone.
The purpose of adding CaCO3 to NH4NO3 is
1. To reduce the explosive nature of NH4 NO3
2. To bring the action of the fertilizer to a neutral condition
so as not to leave acidic or basic residue in the soil .
3. To improve the physical condition of the fertilizer.
4. To increase the Ca content in the fertilizer.
The fertilizer is in the granular form free from dust and is
completely non-hygroscopic. It contains 25% of N, half of is
NO3 form and the other half is in the NH4 form. Grade
containing 26% N is also manufactured .
It is grey or light brown in colour, partly soluble, amorphous
and neutral fertilizer
Pulverized lime stone or
Con. NH4NO3
CaCO3
4 6
Reaction
Granulated
Dried
Cooled
Coated with soapstone
CAN
CAN (25 % N) SPECIFICATION
• Moisture per cent by weight, maximum 1.00
• Total ammoniacal and nitrate nitrogen per cent
by weight, minimum 25.0
• Ammoniacal nitrogen per cent by weight,
minimum 12.5
• Calcium nitrate per cent by weight, maximum 0.5
• Particle size –[Not less than] 80 per cent of
the material shall pass through 4 mm IS sieve
and be retained on 1 mm IS sieve. Not more
than 10 per cent shall be below 1 mm IS
sieve
IV. Amide fertilisers
1. These are synthetic organic fertilisers (urea and calcium

cyanamide).
2.Amide fertilizers are readily soluble in water
3.Amide fertilizers are hygroscopic
4.Urea is a acidic fertilizer where as calcium cyanamide is a
basic fertilizer
5.Amide fertilizers are not directly available to the plant as such
but quickly converted to ammonium nitrogen form and then to
nitrate due to the action of microorganisms in about a week.
6.Leaching loss is very less because amide is converted to
ammonium form, it is retained by the soil colloids and slowly
released and nitrified to nitrate.
7.These are generally used as for basal and top dressing to
crops.
Urea
• Urea was first identified in 1773 after
isolation in crystalline form from urine.
• It was synthesized in the laboratory in 1828 by
Wohler from ammonia and cyanuric acid
NH3 + HCNO CO(NH2)2
• Manufactured in India during 1959 at FCI Ltd.
Sindri
Manufacturing – Method I
• Urea is manufactured by reacting pure NH3 with pure CO2
under high temp (175 – 210 °C) and pressure (170 – 400
atm)
2NH3 + CO2 NH2CO2NH4
NH2CO2NH4 CO(NH2)2 + H2O
Amm.Carbomate
• Ammonia reacts with carbon dioxide to form ammonium
carbomate.
• A Substantial fraction of ammonium carbomate dehydrates
to yield urea
• Unchanged NH3, CO2, NH2CONH4 called off gases are
removed to get urea
Manufacturing – Method II
• The CO2 and NH3 are compressed and heated as
they enter the converter (190 -270 atm pressure
and 180 -190 °C temp) where urea is formed. A
large excess of NH3 is used in order to increase
the conversion rate.
• The unreacted NH3 and CO2 are removed by
means of an evaporator still and are then
recycled.
• The urea solution is pumped to the crystallizer
where cooling and crystallization take place.
• The urea crystals are centrifuged and dried.
• 2NH3 +2CO2 CO(NH2)2 + (NH4)2CO3
• (NH4)2CO3 CO(NH2)2 + H2O
CO2 + NH3 RECYCLED
CO2
Compressor Still
Crystallizer
Convertor
High pressure
Liquid Centrifuge
NH3
Conditioning
agent
Mixer drier
UREA
FLOW CHART FOR UREA MANUFACTURE

Properties of Urea
• Commercial urea is relatively pure, white and
crystalline, having 42 to 46% N in the amide
form.
• Water soluble
• It is hygroscopic and acidic fertilizer
• It produces an equivalent acidity of 80 kg
Urea (granular) specification
• Moisture, per cent by weight, maximum 1.00
• Total nitrogen, per rent by weight (on dry
basis), minimum 46.00
• Biuret per cent by weight, maximum 1.5
• Particle size -—[Not less than] 90 per cent of
the material shall pass through 4 mm IS sieve
and be retained on 2 mm IS sieve. Not more
than 5 per cent shall be below 2 mm IS sieve."
Biuret Content
• During concentration and evaporating of urea to prepare either
crystalline or prilled urea biuret is formed
• When urea is heated to temp above 170°C biuret is formed by
elimination of one molecule of NH3 from two molecules of urea
O O
• H – N –C – N – H + H – N –C – N – H >170° C
H H H NH2 CO NH CO NH2 + NH3

H Biuret
• The permissible max. content of biuret is 1.5%.

• Biuret is toxic to plant particularly when it is applied as foliar
spray
V. Slow release N fertilisers
The basic concept of slow release fertilizers is that they
release their nutrient contents at more gradual rates that
permit maximum uptake and utilization of the nutrient while
minimizing losses due to leaching, volatilization or excessive
turf growth. They represent a relatively small segment of the
total fertilizer industry (3 - 4 %), but their use is growing faster
than soluble (quick-release) materials. The nitrogen fertilizers
are relatively cheap materials and are remanufactured with
the addition of high valued products for fertilizer availability to
match the gradual and continual plant nutrient needs, also
minimizing sudden leaching of excess fertilizer. The basic
strategy is to either make the nitrogen insoluble or trap it with
some sort of barrier.
Types of slow release N fertilisers
Slow release fertilizers are broadly divided into uncoated

and coated products.
1. Uncoated products rely on inherent physical
characteristics, such as low solubility, for their slow release.
2. Coated products mostly consist of quick-release nitrogen
sources surrounded by a barrier that prevents the nitrogen
from releasing rapidly into the environment.
1. Uncoated controlled-release fertilizers
The non-coated materials of limited solubility, can be
manufactured in a smaller particle size than coated products,
which makes them good choices for use. The uncoated
products are homogenous, hence, release at a rate that is not
dependent on any coating.
i. Ureaformaldehyde
Ureaformaldehyde (UF) reaction products are having

been first produced in 1936 and commercialized in 1955.
Ureaform fertilizers are manufactured by the reaction of
formaldehyde, CH2O, with urea, CO(NH2)2, to produce
compounds polymer-chain molecules of varying lengths, such
as
a) methylene diurea [ NH2C(=O)NH-CH2-NHC(=O)NH2 ]

b) dimethylene triurea [ NH2C(=O)NH-CH2-NHC(=O)NH-
CH2-NHC(=O)NH2 ]
a) Ureaform is sparingly soluble, and contains at least 35 %
total N, with atleast 60 % of the total N as cold-water-insoluble N
(CWIN). Ureaform is composed largely of longer-chained molecules
of UF polymers. The unreacted urea N content in UF is usually less
than 15 % of the total N.
b) Methylene ureas are a class of sparingly soluble products

that evolved during the 1960s and 1970s. These products
predominantly contain intermediate-chain-length polymers. The
total N content of these polymers is 39 - 40 %, with between 25 and
60 % of the N present as CWIN. The unreacted urea N content
generally is in the range of 15 - 30 % of the total N.
Ureaform solutions are clear water solutions. They contain only

very low molecular weight, water-soluble UF reaction products, plus
unreacted urea. They contain a maximum of 55 % unreacted urea
with the remainder as one or more of methylolureas, methylolurea
ethers, methylene diurea (MDU), di methylene triurea (DMTU) or
triazone.
ii. Isobutylidene diurea (IBDU)
The reaction of urea with isobutyraldehyde forms a single
type of molecule. Urea with isobutyraldehyde,
(CH2)2CHCHO, instead of with formaldehyde, yields
isobutylidene diurea [ NH2C(=O)NH-CH(CH (CH2)2)-
NHC(=O)NH2 ]. IBDU is a white crystalline solid available in
fine (0.5 - 1.0 mm), coarse (0.7 - 2.5 mm) and chunk (2.0 -
3.0 mm) particle sizes. The product contains a minimum of
30 % N with 90 % of the N in water-insoluble form. The
typical commercialized product contains about 31 % N.
2. Coated fertilizers
Fertilizer granules when coated with any suitable material will
release nitrogen at slow rate. Coated products have several
advantages. Some coated products offer a relatively inexpensive
means to exploit slow-release characteristics. They also may offer
desirable release characteristics in certain conditions.
i. Sulfur-coated fertilizers
Sulfur-coated urea (SCU) technology was developed in the
1960’s and 1970’s by the National Fertilizer Development Center.
Sulfur was chosen as the principle coating material because of its
low cost and its value as a secondary nutrient. Urea granules are
uniformly coated with a layer of sulphur. About 5 % coal tar oil is
mixed with urea to kill any organism that might break down the
coating. The compositions of SCU are urea (80 – 85 %), 30-40 % N,
sulphur (13 – 16 %) and conditioner (2 – 3 %), wax (2 %).
Depending on the coating weight, nitrogen application rate and
environmental conditions, SCUs can effectively provide N for 6 - 16
weeks of applications.
ii. Lac coated urea (LCU)
The resin required for coating is prepared by mixing one
part of matter Shallac with 2 part of resin at 260°C and allowed
for 30 minutes to complete reaction. This is cooled, solidified
and powdered. Urea granules are uniformly smeared with
linseed oil at 50 ± 2°C followed by the addition of resin
powders. The resin melts and gives coating over urea
granules coal tar and soap stone are also added finally the
granules are coated with paraffin wax to seal the fine cracks.
The compositions of LCU are urea (73.7 %), resin (16.2 %),
linseed oil (3.3 %), soapstone (2.9 %), wax (3.6 %) and coal tar
(0.3%).
iii. Neem coated urea (NCU)

Urea (100 kg) is mixed with solution of 1 kg of coal tar in
2 litres of kerosene, 20 kg of powdered neem cake is added in
a drum and the contents were thoroughly mixed.
iv. Gypsum coated urea (GCU)
Urea (100 kg) is mixed with 20 kg of gypsum. Urea is
coated with gypsum of ensure slow release properties and
present losses with the added secondary nutrients calcium,
sulphur.
v. Urea super granules (USG)

For controlling the release of nitrogen is to increases the
size of the granule to such and extend that it affects its
solubility. It is called as urea briquettes or super granules.
3. Nitrification inhibitor
The materials that are used to inhibit the activities of
micro organism that are responsible for dentrification process.
Ammonium and amide forms of nitrogen gets oxidized to
nitrate form by biochemical oxidation. The nitrate can get
denitrified into nitrogen (N2) and nitrous oxide (N2O) due to
low redox potential and get lost into atmosphere. One of the
measures taken, therefore, to avoid denitrification is to control
the production of nitrates. This can be achieved by using
nitrogen inhibitors. Some of the nitrification inhibitors are:
a) Nitrapyrin [2- chloro -6 (trichloro methyl) pyridine] (N

serve)
It is toxic to Nitrosomonas which oxidizes ammonium
ion to nitrate. It is applied @ 0.2 – 2 % of N (0.5 kg/ha)
effective for 22 days only.
b) 2 - amino – 4 chloro – 6 (methyl) pyridine [AM]
It is toxic to Nitrosomonas bacteria when applied @ 4 –
10 ppm by mixing with the fertilizer. It is also used as coating
material for solid fertilizers using oil as a binder. The effect is
only 40 days.
c) Dicyano diamide (DCD)

It is applied @ 5 – 24 % on N basis to inhibit nitrification.
In winter its effectiveness may go up to 5 months. Higher
concentration is toxic to plants.
d) Etridiazol [5 ethoxy - 3- (trichloromethyl) – 1,2,4

thiadiazole] (Dwell)
Etridiazol was equally effective in reducing nitrification of
ammonium N in soils up to 160 days following application when
compared to nontreated fertilizers.
4. Urease inhibitors
The inhibition of conversion of urea into either ammonium
carbonate and/ or ammonium is mediated by urease enzyme.
There are three categories
i) By blocking essential sulpha hedral groups at active sites of

the enzymes.
Ex. Metal ions (Cu, Hg, Ag) and organic compounds (quinones,
benzoquionone, dihydric phenols)
ii) Structural analogous of urea compete for the same site of

enzyme.
Ex. Thiourea
iii) The compounds that reacts with nickel in the urease

molecule.
Ex. Hydrooxamic acid, caprylohydroamic acid, phenyl
phosphrodiaamidate (PPD).
When ammonium sulphate is
added to soil, it dissociate to yield
ammonium and sulphate ions
(NH4)2SO4 2 NH4+ + SO4-2
N2
NH3
Adsorption NH
4
Plant uptake Clay
NH4
Uptake
Leaching
Volatilization
NH4 + HCO3 NH3+CO2+ H2O
Nitrification
Nitrosomonas
(O) -2H (O)
NH4 HONH2 ½ HONNOH NO2 + H + energy
Hydroxylamine Hyponitrite Nitrite
Nitrobacter
(O)
NO2 NO3 + Energy
NITRIFICATION
H2SO4
(NH4)2SO4 2NH4 + SO4
2NH4 + 3O2 2NO2 +2H2O + 4H
2NO2 +O2 2NO3
HNO3
(NH4)2SO4 +4O2 2HNO3 + H2SO4 + 2 H2O
Calculation of Calcium carbonate equivalent
1. Consider the following reaction, which show the loss of Ca
(NH4)2SO4 2NH4+ +SO42-
+
NH4 Clay Ca Clay
NH4
Thus one molecule of AS yield 1 atoms of Ca that can be lost by

leaching
2. Consider the following reaction, which show the loss of Ca high
in CaCO3
(NH4)2SO4 + 4O2 H2SO4 + 2HNO3 + 2H2O
CaSO4 + CO2+H2O
+ +
CaCO3 CaCO3 Ca(NO3)2
+CO2 + H2O
Thus one molecule of AS yield 2 atoms of Ca that can be lost by

leaching
Thus one molecule of AS causes a loss of 1 atom of Ca by cation
exchange reaction and 2 atoms of Ca by reaction of CaCO3
1 molecule of (NH4)2SO4 = (1+2)/ 2 or 1.5 atoms of Ca
132 kg of (NH4)2SO4 = 1.5 x40 kg of Ca
100 kg of (NH4)2SO4 = (60/132) x 100kg of Ca

100 kg of (NH4)2SO4 = 45.5 kg of Ca
Molecular wt of CaCO3= 100 kg

40 kg Ca is present in 100 kg of CaCO3
45.5 kg Ca is present in (100/40) x 45.5 = 113.7 kg of CaCO3
Therefore to compensate the loss of Ca 113.7 kg of pure CaCO3

is needed and it is approximated as 110 kg
•A long-range effect of all ammonium based nitrogen
fertilizers is to lower soil pH.
•Anhydrous ammonia, urea, diammonium phosphate,
and nitrogen solutions, when first applied, greatly but
temporarily increase soil pH in the zone of application.
•Ammonia is released and can “burn” germinating seeds
or seedling roots in the area of fertilizer placement.
• In the eventual conversion of NH4+ to NO3-, however, an
acid residue is formed.
•The residual acidity from the common N sources is
given in Table.
Equivalent acidity
Fertilizer (lb of calcium carbonate
equivalent/100 lb of fertilizer)
Anhydrous ammonia—NH3 148

Urea—NH2-CO-NH2 84
Ammonium nitrate—NH4NO3 63
Ammonium sulfate—(NH4)2SO4 113 (110)
Diammonium phosphate (DAP)—
74
(NH4)2HPO4
As a rule of thumb, 6 pounds of limestone are required for each pound of
nitrogen applied as ammonium sulfate, and 3 pounds of limestone are required
for each pound of nitrogen applied as anhydrous ammonia, urea, ammonium
nitrate, or nitrogen solution.
To neutralize the soil acidity produced by 100 kg of AS, 110
kg of pure CaCO3 is needed
Fate of urea
The nitrogen in urea is completely water-soluble.
Upon application, urea nitrogen changes rapidly to NH4-N.
Urea nitrogen therefore is readily available to plants on
application to the soil.
Urea presents another problem, in that when it is surface-
applied, significant quantities of nitrogen as ammonia may
be lost through volatilization. Losses are accelerated by
warm moist soils, high pH, and surface organic matter.
Losses are higher on low cation exchange capacity (CEC) or
sandy soils than on soils with a high CEC, a heavy clay
content, or a high organic matter content. Thus, urea or
nitrogen solutions (which are approximately 50 percent
urea) should be incorporated into the soil by mechanical
mixing or by water movement
Fate of urea
•The nitrogen in urea is completely water-

soluble.
•Upon application, urea nitrogen changes
rapidly to NH4-N. Urea nitrogen therefore is
readily available to plants on application to the
soil.
•Urea presents another problem, in that when it
is surface-applied, significant quantities of
nitrogen as ammonia may be lost through
volatilization.
Fate of Urea
Upon application to soil, urea is acted on by the
enzyme urease, which hydrolyzes it to unstable
ammonium carbomate, which decomposes to
yield ammonia
urease
CO(NH2)2 +H2O H2NCOONH4 2NH3 + CO2
CO(NH2) N2
NH3
Hydrolysis
Volatilization
NH4
Plant uptake Clay
NH4
Uptake
Leaching
Reactions of urea in soils
1. CO(NH2)2 + 2H2O Urease (NH4)2CO3
2. CO(NH2)2 + H+ + 2H2O Urease 2NH4+ + HCO3-

NH4+ + H2O NH3 + H3O+
3. (NH4)2CO3 + 2H2O 2NH4OH + H2O + CO2

2NH4+ + 5O2 2NO3 + 4H2O
4. (NH4)2CO3 + 3O2 2HNO2 + 3H2O + CO2

2HNO2 + 2O2 2HNO3
NITRIFICATION
(NH2)2CO + 2H2O (NH4)2CO3
(NH4)2CO3 2NH4 + CO3
2NH4 + 3O2 2NO2 +2H2O + 4H
H2CO3
2NO2 +O2 2NO3
HNO3
(NH2)2CO +4O2 2HNO3 + H2CO3+ 2 H2O
1. Consider the following reaction, which show the loss of Ca
(NH2)2CO + 2H2O 2NH4+ + CO32-
+
NH4 Clay Ca Clay
NH4
Thus one molecule of urea yield 1 atoms of Ca that can be lost by

leaching
2. Consider the following reaction, which show the loss of Ca high
in CaCO3
(NH2)2CO + 4O2 H2CO3 + 2HNO3 + 2H2O
CO2+H2O
+
CaCO3 Ca(NO3)2
+CO2 + H2O
Thus one molecule of urea yield 1 atoms of Ca that can be lost by

leaching
Thus one molecule of urea causes a loss of 1 atom of Ca by cation
exchange reaction of CaCO3
1 molecule of (NH2)2CO = 1/2 atoms of Ca
60 kg of (NH2)2CO = 0.5 x 40 kg of Ca
100 kg of (NH2)2CO = (20/60) x 100 kg of Ca

100 kg of (NH2)2CO = 33.3 kg of Ca
Molecular wt of CaCO3= 100 kg

40 kg Ca is present in 100 kg of CaCO3
33.3 kg Ca is present in (100/40) x 33.3 = 83.25 kg of CaCO3
Therefore to compensate the loss of Ca 83.25 kg of pure CaCO3

is needed and it is approximated as 84 kg
•A long-range effect of all ammonium based nitrogen
fertilizers is to lower soil pH.
•Anhydrous ammonia, urea, diammonium phosphate,
and nitrogen solutions, when first applied, greatly but
temporarily increase soil pH in the zone of application.
•Ammonia is released and can “burn” germinating seeds
or seedling roots in the area of fertilizer placement.
• In the eventual conversion of NH4+ to NO3-, however, an
acid residue is formed.
•The residual acidity from the common N sources is
given in Table.
Phosphate fertilizers
In 1842, John B. Lawes patented a process by which
rock phosphate was acidulated with sulphuric acid to
produce Super phosphate
He estabalished the commercial production plant in
the year 1843
J. B. Lawes was called father of fertilizer industry
In India the first fertilizer was produced in 1906 and it
was SSP by EID-Parry (India) Ltd, at Ranipet.
Phosphorous
It was discovered in 1669 by Hemming Brandt
Phos – light, phor – to bear (glows)
(i.e., yellow light in the dark upon heating)
It occurs naturally as mineral deposits consisting mainly of
Ca3(PO4)2 ‘apatite’
These natural deposits serve as the basic raw material for the
synthesis of all other phosphatic fertilizers
Apatite occur in igneous, metamorphic and sedimentary rock
formations. Sedimentary deposits are the most important ones
yielding large proportion of commercial phophate rocks at
present
For the conversion of P to P2O5 : % P x 2.29
For the conversion of P2O5 to P : % P2O5 x 0.44
In fertilizer the phosphorus content is commonly expressed in
oxide form as P2O5
Rock phosphate
The phosphate mineral in lithosphere is found to occur
as tricalcium phosphate Ca3(PO4)2 in combination with
either CaCO3, CaF2, Ca(OH)2 or CaCl2.
mineral called ‘apatite’ and its massive form is
sometimes called as ‘Phosphorite’.
The apatite is of igneous origin found as a constituent f
granites, gneisses and basalt.
There are five important forms of apatite that are found
to occur and they are called according to the other
components contained in the molecules.
Apatite
General formula (Ca3(PO4)2)3 Ca x or Ca10 (PO4)6
where x = CO3, Cl2, F2, SO4 or (OH)2.
1. Carbonato apatite [Ca3 (PO4)2]3 CaCO3
2. Fluor apatite [Ca3 (PO4)2]3 CaFa2
3. Chlor apatite [Ca3 (PO4)2]3 CaCl2
4. Hydroxy apatite [Ca3 (PO4)2]3 Ca(OH)2
5. Sulphate apatite [Ca3 (PO4)2]3 CaSO4
Of all the above five apatite fluoro apatite is the most
commonly occurring one.
Deposits of apatite of economic importance have been found
in every continent and in many island of the world (US-
Florida, Canada, Mexico, Brazil, Russia, Tunisia, Morocco,
China, Israel, Syria, India etc .
In India, the phosphate deposits are found in Trichy district of
Tamil Nadu, Udaipur of Rajasthan and Singhbum of Bihar.
(P2O5 is around 32%)
Apatite
Apatite is a member of the Apatite group, a group of
isomorphous hexagonal minerals. Apatite may be regarded as a
single mineral, but is usually divided into three more minerals:
Fluorapatite, Chlorapatite, and Hydroxylapatite. Since it is
hard to distinguish between these minerals, and since they
may partially replace each other, a distinction between them is
rarely made, and they are simply called "Apatite". However,
most Apatite is Fluorapatite, the most common member.
Apatite is named from the Greek word apate, which means

"deceit", since Apatite has a similar appearance to so many
minerals.
Apatite
Colorless, white, yellow, brown, red, pink, purple, blue,
green. Some specimens are multicoloured
Apatite is the most common phosphate mineral, and is
the main source of the phosphorus required by plants.
The bones and teeth of most animals, including humans,
are of the same material as Apatite.
Classification of phosphatic fertilizers
Based on source or manufacture
Phosphatic materials
Natural Treated or processed Industrial Synthetic

phosphates phosphates byproducts Phosphates
E.g. E.g.
1. Bones E.g. E. g.
1. Super phosphate
2. RP 1. Basic slag 1. Amm. phosphate
2. Bone ash
3. Bone super
Classification of phosphatic fertilizers
Based on the solubility of the phosphate
Phosphatic Fertilizer
Water soluble Citric acid soluble Insoluble or

Phosphates or phosphate or tricalcium phosphate
Monocalcium phosphate Dicalcium phsophate
E.g. E. g.
E.g.
1. Superphosphate (16 % 1.Rock phosphate
1. Basic slag (14-18 % P2O5)
P2O5) (30 - 40 % P2O5)
2.Dicalcium phosphate
2.Conc. SP (48 % P2O5) 2. Raw bone meal
(34-38 % P2O5)
3.Amm. Phosphate (20 % (20-25 % P2O5)
3.Rhenania phosphate (23-
P2O5)
26 % P2O5)
Water-soluble P: The P fertilizer is dissolved in distilled
water and filtered and the P content in the filtrate
represents the fraction of water soluble P
Citrate-soluble P: Is the amount (or fraction) of P
extracted by 1 N ammonium citrate from the residue
remained after WSP is extracted
The residue from the leaching process is added to solution
of neutral 1 N ammonium citrate. It is extracted for a
prescribed period of time by shaking, and the suspension is
filtered. The P content of the filtrate is determined and the
amount present, expressed as a percentage of the total
weight of the sample is termed the Citrate soluble P
Citrate –insoluble P: The fraction of P present in the
residue remaining from the water and citrate extractions
Process used in the manufacture of various
phosphate fertilizers.
Orthophosphoric Acid
This is an important intermediate product and to a less
extent an end product in Phosphate fertilizer industry
(nearly 90 %)
Two types of processes are used for the production of
phosphoric acid
1. Furnace Processes –White or furnace acid
2. Wet Processes – Green or wet process acid, used
largely in the fertilizer industries.
Furnace process – White or furnace acid
The P-mineral and silica are fused with the help of an
arc produced with carbon or graphite electrodes. The
carbon in coke reduces the phosphate to elemental
form and recovered
Ca10(PO4)6F2 +15C + 6SiO2
1.5P4+15CO+3(3CaO.2SiO2) +CaF2
When P is heated in an abundant supply of O2, it
burns and forms P2O5 which, when dissolved in water
forms metaphosphoric acid
4P + 5O2 2P2O5
P2O5 + H2O 2HPO3
When this meta phosphoric acid is heated with water,
it forms orthophosphoric acid which is commonly
called as phosphoric acid
HPO3 +H2O H3PO4
Wet Process
OP acid is manufactured by treating RP with
H2SO4
Ca10(PO4)6 F2 + 10 H2SO4+20H2O
10CaSO4.2H2O +6H3PO4+2HF
Wet process phosphoric acid is the source of P
used in the manufacturing of TSP, Ammonium
phosphate, nitrophosphate and liquid fertilizers
Orthophsophoric acid
H3PO4 has 3 replaceable H+ atoms, Hence it forms 3
classes of salts replacing one or two or all the three
hydrogen atoms.
2H3PO4 + Ca(OH)2 Ca(H2PO4)2+ 2H2O monocalcium phosphate

2H3PO4 + 2Ca(OH)2 2CaHPO4 + 4H2O dicalcium phosphate
2H3PO4 + 3Ca(OH)2 Ca3(PO4)2+ 6H2O tricalcium phosphate
1. Monocalcium phosphate – Ca(H2PO4)2 – WS

2. Dicalcium phosphate – Ca2(HPO4)2 or CaHPO4-CAS
3. Tricalcium phosphate- Ca3(PO4)2 – Soluble in strong acid
Single superphosphate
It is also called ordinary superphosphate or super
phosphate
It contains 16 % P2O5 (% P = ?)
P is present as monocalcium phosphate
Raw material required for manufacturing are
1) Rock phosphate and 2) H2SO4
Manufacturing - by Den process
1. Batch process
2. Continuous process
(Ca3(PO4)2)3 CaF2+7 H2SO4 3Ca(H2PO4)2 +
7CaSO4 + 2HF
Rock
Phosphate H2SO4 Batch Process
•Required quantities of
pulverized RP (4 mesh size)
and H2SO4 are mixed for
one minute in a pan mixer.
Mixer •The mixed material is
dropped in to a den and
kept for 6 – 36 hours.
•The
The water vapour, CO2
and HF formed during
reactions are escaped or
recovered.
Den •The remaining material is
removed to curing piles
where it is stored for
several weeks (2-10 weeks
• The material is dried,
Curing excavated, pulverized and
pile bagged
RP H2SO4 Continuous Process
•Measured quantities of RP and H2SO4 are
continuously mixed in a mixer for about 2-3
min.
•The mixture is then dumped to one end of
the slant conveyer in a den.
Mixer •After complete filling, the material is allowed
to solidify in the den
•The solidified mixture is slowly moved to the
rotary cutter and product is powdered.
Den •The
The powdered product is transferred to
curing pile for curing and then bagged
Slant conveyer
Rotary
Cutter Curing pile
Properties
• Composition
1. Monocalcium phosphate monohydrate – 26.6 %
Ca(H2PO4)2 . H2O
2. Dicalcium phsophate dihydrate - 2.2 %
CaHPO4 .2H2O 4.6 %
3. TCP Ca3(PO4)2 - 2.2 %
4. Gypsum CaSO4.2H2O - 50%
5. Water - 6%
6. Free phosphoric acid - 0.3%
• Odour- Acidic odour due to presence of H3PO4
• Colour- Grey
• Hygroscopocity –slightly hygroscopic
• Nutrient content- 16 % P2O5: 20 % Ca and 12 % S
• It is neutral fertilizer
Superphosphate specification
• Free phosphoric acid (as P205) per cent by
weight, maximum 4.0
• Water soluble phosphates (as P2O5) per cent
by weight, min 16.0
• Sulphur (as S),percent by weight ,min. 11.0
Triple superphosphate or
concentrated superphosphate (46 % P2O5)
• TSP is produced by reacting phosphate rock
with phosphoric acid
• Ca10(PO4)6F2 +14H3PO4+ 10 H2O
10Ca(H2PO4)2.H2O+ 2HF
• Manufactured by batch or continuous process
Ca3(PO4)2.CaX + 10 H2SO4 6 H3PO4 + 10 CaSO4 + H2X

Ca3(PO4)2.CaX + 14 H3PO4 10 Ca(H3PO4)2 + H2X
Properties
• Composition: Essentially monocalcium phosphate,
also contain di and tri calcium phosphate and free
H3PO4
• Odour: Acidic odour
• Phosphorus content: 18.9-22.4 % P (44-52 % P2O5) of
which 95-98% water soluble
• Other element Sulphur-1.6 % and Ca-14 %
• Is an acidic fertilizer
• Solubility : water soluble fertilizer
Specification
• Moisture, per cent by weight, maximum = 12
• Free phosphoric acid (as P2O5) per cent by weight, maximum = 3
• Total phosphorous (as P2O5), per cent by weight, minimum =46
• Water soluble phosphates (as P2O5), per cent by weight min.= 42.5
Rock phosphate
• Is a good source of Phosphorus, Calcium and other trace
minerals.
• RP is mined from natural deposits.
• RP will not leach out of the soil, and will remain until taken up by
the plant's roots.
• Is insoluble in soils with a pH above 7 and releases Phosphorus
very slow and can last up to five years.
• It contains over 30% total Phosphorus with 3% available and 48%
calcium
Rock phosphate
The recommendation of rock phosphates to neutral and
alkaline soils:
1) Mixture of rock phosphate with organic matter

2) Rock phosphate solubilising bio-fertiliser
3) Mixture of rock phosphate with pyrite
4) Artificially acidulated rock phosphate
Table Composition of the rock phosphate
Constituents Amount (%) Constituents Amount (ppm)
1 Phosphorus (P2O5) 20 – 24 6 Potassium (K2O) 1000 – 5000
2 Calcium (CaO) 37 – 45 7 Zinc (Zn) 100 – 150
3 Silica (SiO2) 5 – 10 8 Chromium (Cr) 40 – 60
4 Fluorine (F) 1–3 9 Molybdenum (Mo) 5 – 75
5 Sulphur (S) 0.5 – 1.0 10 Copper (Cu) 10 – 50
RP; Rajasthan State Mines and minerals limited
• It is mostly Carbonate Rock Phosphate.

• The major activity of RSMML is the mining of Rock
phosphate ore. It operates one of the largest and
fully mechanised mines in the country at
Jhamarkotra, 26 Km. from Udaipur and Kanpur
Group of Mines located 15 Km. from Udaipur is
upcoming as a second Rock phosphate complex in
Rajasthan.
• Producing RP with different grades for different kind
of uses
RP products
• 31.5% P2O5 Rock Phosphate (SSP)
(SSP Manufacturing Units)
• 31.5% P2O5 Rock Phosphate (Non SSP)
(For Non SSP Manufacturing Units)
• 34% P2O5 Rock Phosphate (DAP)
(DAP/ Nitrophosphate Manufacturing Units)
• 31.54 % P2O5 Beneficiated Rock Phosphate
(SSP & DCP Manufacturing Units)
• 18-20% P2O5 Rock Phosphate (RAJPHOS)
(Fertilizer for direct application in acidic soils)
• 30-31% P2O5 Rock Phosphate (Stones)
(Elemental Phosphorus Manufacturing Units)
• 18-20% P2O5 Rock Phosphate (RAJPHOS)
(Fertilizer for direct application in acidic soils)
Specification of RP
• Particle size – minimum 90 % of the material
shall pass through 0.15 mm IS sieve and the
balance 10 % of material shall pass through
0.25 mm IS sieve
• Total phosphate (as P2O5), per cent by weight,
minimum = 18
3. Polyphosphates
Polyphosphates differ slightly from more common

orthophosphate fertilizers. Nearly all of the liquid fertilizers
containing phosphorus are of the polyphosphate type.
Polyphosphates are composed of a series of orthophosphate
molecules connected by the process of dehydration. The
commercial ammonium polyphosphates are usually a mixture
of orthophosphate and polyphosphate. With prolonged
storage, polyphosphates will hydrolyze to orthophosphates.
The solutions of ammonium polyphosphate most commonly
made are 10-34-0 and 11-37-0. The most common dry
polyphosphate is 13-52-0.
O O O O
II + II II II + H2O
OH –P-OH OH –P-OH OH –P -O - P-OH
II II II II
OH OH OH OH
(orthophosphoric (orthophosphoric (pyrophosphoric
acid) acid) acid)
O O O O
II II + 3NH3 II II
OH –P -O - P-OH H4N-O –P -O - P-O-NH4
II II II II
OH OH OH O-NH4
(pyrophosphoric acid) (triammonium pyrophosphate)
4. Meta phosphates
i) Calcium meta phosphate
Phosphorus in burnt in a furnace where hot and gaseous
combustion products pass through the lump rock phosphate is
packed in the upper part of the furnace. The rock phosphate
and hot vapour are chemically combined to form calcium meta
phosphate which contains 62 – 64 % citrate soluble phosphate.
High grade phosphatic fertilizer is used for soil application and
for mixed fertilizer.
Ca10(PO4)6F2 + 7 P2O5 + H2O +10 O2 10 Ca(PO4)2 + 2 HF
Total phosphate (P2O5) - 63.0%

Calcium oxide (CaO) - 26.6%
Sesquioxide - 3.8%
Silica - 6.4 %
Fluorine - 0.2%
4. Meta phosphates
ii) Potassium meta phosphate
It is prepared in the same manner by substituting with
muriate of potash instead of rock phosphate. It contains 60 %
P2O5 of which 57 - 60 % citrate soluble, 35 % K2O.
10 KCl + 5 P2O5 + 5 H2O +5 O2 10 KPO4 + 10 HCl
KCl + H3PO4 KPO3 + HCl + H2O
iii) Ammonium metaphosphate (NH4PO3)

The product is a mixture of ammonium metaphosphate,
metaphosphoric acid and ammonium salt of metaphospheric
acid. It contains 17% N, 80% P2O5. This is found to be superior
to nitrophosphate.
2P2O5 + 4 NH3 2PN (OH)2 + 2 NH4PO3
2P2O5 + 6 NH3 2PNO3 HNH4 + 2 NH4PO3
Rhenanina phosphate (Silicophosphate)
This is also called as artificial basic slag manufactured by
calcining or sintering mixture of PR with an alkali usually
Na2CO3 and Silica.
2[Ca3(PO4)2]3 CaF2 + 6 Na2CO3 + 5 SiO2 6(Na2O.2CaOP2O5

+ (CaOSiO2) + SiF4 + 6 CO2
The PR and SiO2 are ground together to pass through 180

mesh sieve, mixed with proper amount of Na2CO3 and then
10% of water is added to the charge. The moistened charge is
fed continuously into the kiln, heated from 1100 to 1200°C and
allowed to stand for 2 hrs. Water is sprayed continuously on the
charge coming out of the kiln. The product is ground and used.
It contains 28 % P2O5, 42 % CaO, 10.5 % SiO2, 12 % Na2O, 4.5
% R2O3 and 1.5 % F. It is found to be suitable for a variety of
soil
Dicalcium phosphate
This is also prepared from PR and H2SO4
[Ca3(PO4)2]3 CaF2 + 4 H2SO4 6 CaHPO4 + 4CaSO4 + 2 HF
[Ca3(PO4)2]3 CaF2 + 4 H2SO4 10 Ca H PO4 + 2 HF
In this process actually a small quantity of either H2SO4 or

H3PO4 is required to produce an equivalent amount of phosphate
when compared to manufacture of ordinary or concentrated super
phosphate.
Usually in the industry, PR is treated with an acid to produce
MCP and this is further neutralized or reacted with either lime or NH3
to get DCP.
[Ca3(PO4)2]3 CaF2 + 14 HCl 3 Ca(H2PO4)2 + 7CaCl2 + 2 HF
3 Ca (H2PO4)2 + 7CaCl2 + 2 HF + CaO 6 CaHPO4 + 7 CaCl2 +
4 H2O + CaF2
3 Ca (H3PO4)2 + 7CaCl2 + 2 HF + 8 NH3 6 CaHPO4 + 3CaCl2 +
CaF2 + 8 NH4Cl.
The phosphate content various from 30 to 32 % and it is mainly in
the citric acid soluble from.
5. Basic slag
It is a by-product from the steel industry. During the
steel manufacture, the phosphorus in the iron ore is removed
to get a high quality steel as the steel containing more than 2
% P which is brittle. The basic slag is obtained by the various
processes of steel manufacture.
i) Thomas and Gilchrist method

The method was introduced as a modification to the old
Bessemer process in 1877. In this, molten iron containing the
various impurities like calcium, silica, sulphur and phosphorus
is introduced into a limed converter with air blast
arrangements. At a particular temperature, lime melts and
combines with the acid forming impurities and the resulting
product, which are lighter, rise to the surface of the molten
mass. The floating solids are poured off as slag, cooled,
powdered and marketed. This is containing 17 or 20 % P2O5.
ii) Open Hearth method (Modern method)
Here the impurities are oxidized by means of the iron ore
(iron oxide) itself. Iron ore and lime are heated in an open heater and
molten iron is then added. This carries not more than 15 % P2O5
and not less than 8 % P2O5.
The flux which is added to remove acidic impurities produces

basic slag. The basic slag is a heavy dark powder and is alkaline to
litmus. The availability of phosphorus is found to increase with the
fineness of the product as well as with silica content and decrease
as the fluoride content increase. The phosphate is found to be
present in a double silicate form with lime [(CaO)5 P2O5 SiO2] but
some consider it as tetra calcium phosphate (Ca4P2O5) and still
others consider it is a basic silicon oxy apatite. It is more useful for
acid soils.
Constituents Amount (%) Constituents Amount (%)
1 Phosphate (P2O5) 12 – 20 3 Silica (SiO2) 5 – 16
2 Lime (CaO) 40 – 50 4 Sesquioxides (R2O3) 12 – 16
6. Bone meal
Bone meal is both phosphatic manure and fertilizer. It is
a cheap source of phosphorus but it is slowly available to crop.
It is obtained in the two forms:
i) Raw bone meal/ untreated bone meal

It is prepared by drying and crushing of bones after
collection from the slaughter houses without any treatment
which is used as manure. It contains 2 - 4 % organic N and 20
- 25 % P2O5 (8 % citrate soluble).
ii) Steamed bone meal or bone phosphate
Steamed bone meal is a white grayish light weight powder
material. Chemically it is Ca3(PO4)2 and it is commonly referred
as bone phosphate of lime. Generally young bones contain
less phosphorus and more nitrogen than older bones. Young
bones are boiled and steamed at high pressure for removing
fats that are used for manufacturing of getatin sticks. The
bones are then ground for easy handling and distribution.
Particle size of steamed bone meal should be less than 2.24
mm is considered suitable for fertilizer.
The steamed bone meals contain 1 – 2 % N and 25 – 30 %

P2O5 (16 % citrate soluble). During application it should be
mixed with saw dust, because it is light weight material. Bone
meal is produced in India is 30,000 - 35,000 MT/ year. After
removal of gelatin, finer materials are steamed and exported
chiefly for feeding live stocks.
Fate of SSP
• The SSP granule when added to soil start absorbing moisture
from the soil
• In the moistened granule, H3PO4 and CaHPO4.2H2O are formed
Ca(H2PO4)2.H2O + H2O CaHPO4.2H2O + H3PO4
• The so formed H3PO4 begins to move out into the soil as more
soil water is being absorbed.
• The H3PO4 laden solution moves into the soil, dissolving and
displacing Fe, Al, and Mn leaving insoluble CaHPO4.2H2O in the
granule
• The Fe, Al and Mn reacts with phosphate to form insoluble
compounds which along with the residue of CaHPO4.2H2O are
the primary reaction products
P-fixation
• In neutral to alkaline soils
Ca(H2PO4)2 + 2CaCO3 Ca3(PO4)2+CO2+H2O
• In acid soils
Al3+ + H3PO4 +H2O Al(OH)2H2PO4
(Al-hydroxy phosphate)
Potash fertilizers
Potassium Fertilizers
• Like phosphates, potassium fertilizers are
obtained from deposits found at great depth
below the earth’s surface.
• Like phosphates, too, the potassium ores must be
beneficiated to produce high grade K fertilizers
• But unlike RP, Potassium salts (ore) do not require
treatment with heat or strong acids to render the
contained K available to plants, for they are water
soluble.
Potassium
• The Chinese were the pioneers among the various farmers who
used K for agricultural purposes.
• The mineral deposits were not discovered and used as
fertilizers till the eighteenth century.
• Potash is the trade name for K containing fertilizers, was
derived from pot ashes.
• The first product to be used as K manure was the wood ash (4
to 21 % K) and the practice of using wood ash existed for
centuries.
• In olden days, the wood ash was obtained by burning wood in
pot and the resultant ash was leached in mud pots to get the
salt mixture containing Cl, SO4 and CO3 of K, Ca and Mg. (Pot +
ash = Potash).
• The potassium content in K fertilizers is expressed in oxide form
% K = % K2O x 0.83 and % of K2O = % K x 1.2)
Source of potassium
• The following are the main sources of K.
1. Mineral deposits
2. Industrial by-products and
3. Synthetic K salts
Classification of K Fertilizers
K Fertilizer and manure
Based on source
Natural Processed Synthetic
1. Potassic 1. Muriate of 1. KNO3

minerals potash 2. KH2PO4
2. Wood ash 2. Sulphate
3. Sea weed of Potash
Potassium Containing Minerals
• Potassium is present in IR, SR and MR

• but commercial recovery is mainly restricted to
two types of sedimentary deposits,
1. deeply buried marine evaporite deposits at
depths typically ranging from 400 metres (m) to
greater than 1000 m below the surface,
2. surface brine deposits associated with saline
water bodies such as the Dead Sea, the Great
Salt Lake and China’s Qarhan Lake
World Production and Reserves
• Worldwide potash resources are
estimated at 250 billion tonnes (Bt)
(K2O equivalent) with an economic
and sub economic reserve base
reported at 18 Bt and economically
extractable reserves at 8.3 Bt
(Jasinski 2009).
Natural sources : Potassic minerals
There are as many as 50 minerals that are found to contain K but all
of them are not economically important. The K containing minerals
are roughly classified into
1. Minerals highly soluble in water occurring in brines or salt deposit
Sylvinite - KCl (Sylvite) ,
Carnallite _ KCl. MgCl2. 6 H2O
Langbeinite - K2SO4. MgSO4
Kainite - KCl. MgSO4. 3 H2O
2. Minerals less soluble in water.
Polyhalite - K2SO4. MgSO4. 2 CaSO4 . 2 H2O
3. Minerals insoluble in water
Glauconite - KFeSi2O6. 2 H2O
Feldspars - orthoclase - KAlSi3O8
Micas - Muscovite and biotite.
Natural sources : Potassic minerals
The following are commercially used for the manufacture
of potassic fertilizers.
1. Sylvinite – KCl.NaCl – contains approx 28 % K2O
2. Carnallite - KCl. MgCl2. 6 H2O - contains 17% K2O
3. Kainite - KCl. MgSO4. 3H2O - contains 18.9% K2O
4. Langbeinite - K2SO4. 2 MgSO4 – contains 22.6% K2O
5. Polyhalite - K2SO4. MgSO4. 2CaSO4. 2H2O – contains
15.5% K2O
Muriate of potash (KCl)
It is found that at least 90% of the potassic fertilizers
consumed is in the form of muriate of potash
KCl is commercially manufactured using any one of the
minerals;
1. Sylvinite or sylvite and 2. Carnallite
• There are two main steps involved in the manufacture

of this fertilizer.
1. Mining of the K mineral
2. Separation of the main ingredient and purifying
(Benificiation)
Mining
Potash ores in solid beds at depths no greater than
1400 m below the earth’s surface are extracted mainly
by conventional mechanized underground mining
methods.
1. room and pillar,
2. long-wall,
3. cut and fill, and
4. open stope techniques are commonly used.
Solution mining is employed when underground
extraction is no longer feasible because of depth to
deposits and/or when water inflow problems interfere
with conventional underground mining.
Solar evaporation of brines that naturally contain
potassium is the third method of obtaining potash ore.
Room and pillar method Mining
After a mine shaft is sunk to a point slightly
below the level of the ore body a large tunnel is
driven on both sides of the shaft. At right angles
to this tunnel the ore is mined in larger rooms
about 25 to 50 feet wide and 300 feet long.
The ore is brought over to the surface by
electrically operating elevators and machineries.
Arriving on surface, the potash has an average K2O
content near 23%. Unwanted components must be
separated to ensure minimum product standards
(i.e., > 60%K O) and various particle size categories
are met.
Refining of Potassium ore

Recovery of KCl from sylvinite ore is made by the
1. Mineral flotation process or
2. Solution of KCl, followed by recrystallization
The potash ore is a mixture of approximately
38 % KCl (sylvite) and 60 % NaCl (halite), with an
insoluble fraction, up to 2 % composed mainly of clay
minerals and sulphate .
Arriving on surface, the potash has an average

K2O content near 23 %. Unwanted components must
be separated to ensure minimum product standards
(i.e., > 60 %K2O) and various particle size categories
are met.
Floatation method
Principle:
1. Floatation is a metallurgical process
2. In this process which small quantities of special regents are
added to the pulp to coat or film some of the minerals
selectively with respect to other minerals present.
3. When the reagent added pulp is agitated in a mechanical cell
in such a manner that air is drawn into the pulp to create a
frothing action or condition,
4. the finely divided air bubbles attach themselves to the reagent
filmed particles and float them to the surface of the cell,
5. The froth rich with the selected mineral may be skimmed off.
(1) Sulphonated aliphatic alcohols of KCl and

(2) 20% of mono-n-octadecyl- amines neutralized with acetic acid and a
0.5% solution of this is found to be very effective to NaCl that is
present in sylvinite.
Floatation method
1. First, after grinding and passing through the screen, the
desired sized sylvinite mineral is dissolved in water to get a
pulp
2. The reagent is added to the pulp. [Reagents are (1)
Sulphonated aliphatic alcohols of KCl and (2) 20% of mono-
n-octadecyl- amines neutralized with acetic acid and a 0.5%
solution of this is used]
3. The reagent will form a coating or film round the NaCl
molecules
4. This reagent added pulp is allowed to pass through a series
of floatation cells in which air is introduced at the bottom in
such a manner so as to form a small bubble froth that
attaches to NaCl.
5. The froth rich with the selected mineral may be skimmed
off
Flotation
1. The ore is ground to separate the crystals and disperse
the clay slime
2. The ground ore is suspended and agitated in saturated
NaCl-KCl brine.
3. The slurry is deslimed to remove the clay (Clay content
increase the requirement for the flotation reagents)
4. The deslimed slurry is conditioned with aliphatic amine
acetate salts to film the KCl particles selectively. The NaCl
particles are not filmed
(1) Sulphonated aliphatic alcohols of KCl and

(2) 20% of mono-n-octadecyl- amines neutralized with acetic acid
and a 0.5% solution of this is found to be very effective to NaCl
that is present in sylvinite.
Flotation Contd…
5. The conditioned slurry then passed to rougher
flotation cells into which air is drawn by
agitation. The air bubbles attach to the filmed
KCl particles and float them to the surface. The
froth is mechanically skimmed off and passed
in to cleaner flotation cells for further
purification
6. The froth and brine are centrifuged and the KCl
is dried in rotary driers.
7. The dried KCl is moved to the screening area
for sizing into four products-granular, coarse,
standard and special standard
Purification
• This involves the following process:
1. Grinding
2. Lixiviation or converting the ore into solution
form
3. Crystallization
4. Separation, drying etc.
1. Grinding
The potassic ore, after mining and bringing
over to the factory site, is ground to fine size and
screened to get only the ore of required size.
2. Solutioning
1. The ore is dissolved in hot water
2. NaCl solution (brine) is added for obtaining a mixture
of KCl + NaCl.
3. The temperature of the mixture is increased by which
more and more of sylvinite will dissolve and the
solubility of NaCl will stop after a stage.
4. This is continued till a saturated solution of KCl is
obtained
3. Crystallization
The saturated solution containing both KCl and NaCl
is suddenly cooled in a vacuum and the KCl separates out
as crystals while NaCl remains in the solution.
The principle involved in the crystallization is the differential
solubility of KCl and NaCl in cold and hot solution.
When KCl is mixed with NaCl it is much more soluble in hot

water than in cold water, whereas NaCl is somewhat more soluble in
cold water than in hot water.
By increasing the temperature, therefore, the solubility of KCl

increases while that of NaCl remains virtually constant.
4. Separation
Crystallized KCl can be separated out by mechanical means
and it is dried, powdered and used.
Solution, followed by recrystallization
• The difference in the temperature-solubility
relationships of KCl and NaCl is the usual basis
of this method of recovery
• The solubility of KCl increases rapidly with a
rise in temp, whereas NaCl solubility varies
slightly over a wide temperature range.
Solution, followed by recrystallization
• Cool brine saturated with both salts is heated
and passed over the ore. KCl plus small
amounts of NaCl are dissolved.
• The saturated solution containing both KCl
and NaCl is suddenly cooled in a vacuum and
the KCl separates out as crystals while NaCl
remains in the solution
.
Properties
Composition: It contains 50 to 52 % K ( or 60 to 63 % K2O)
and 35 to 47 % Cl. It is usually 95 % KCl
Form: The commercial product is either granular or

powdery
Colour: pink or white or red or brown colour.
Solubility: Readily soluble in water
It is a neutral fertilizer
Specification
• Water soluble potash content (as K20) per cent by
weight, minimum 6O.0
• Sodium as NaCI per cent by weight (on dry basis)
maximum 3.5
• Particle size -—Not less than 65 cent of the material
shall pass through 1.7 mm IS sieve and be retained
on 0.25 mm IS sieve.
SOP (Sulphate of Potash)
• SOP is a white salt which contains 41.5 to 44.2
K (50 to 53.2 K2O), in water soluble form
Manufacturing
Decantation or Langbeinite Process
The raw materials required are the mineral langbeinite
and KCl
K2SO4. 2Mg SO4 + 4 KCl 3K2 SO4 + 2MgCl2.
The ppt of Potassium sulphate is separated from

solution by decantation
Trona Process
• Burkite (Na2CO3.2Na2SO4) is reacted with
potassium chloride to form glaserite
(Na2SO4.3K2SO4) and reacted with KCl brine to
give potassium sulphate
Glaserite Process
Commercial production of SOP by a two stage
process
First Step
• Sodium sluphate and KCl react to form glaserite
• 4Na2SO4 +6KCl Na2SO4.3K2SO4+6NaCl
Second step
• Glaserite is then reacted with KCl to form K2SO4
• Na2SO4.3K2SO4 + 2 KCl 4K2SO4 +2NaCl
Mannheim process
• Sulphuric acid reacts with potassium chloride
to yield potassium sulphate
• H2SO4+2KCl K2SO4 +2HCl
Hargreaves Process
• Sulphur dioxide from a sulphur burner is
mixed with water vapour and air and passed
over heated beds of potassium chloride to
yield potassium sulphate and HCl
SOP-specification
• Moisture per cent by weight, maximum1.5
• Potash content (as K2O) per cent by weight,
minimum 50.00
• Total chlorides (as CI) per cent by weight, (on
dry basis) maximum 2.5
• Sodium as NaCI per cent by weight, (on dry
basis) maximum 2.0
• Sulphur (as S),percent by weight ,min.17.5
Fate of MOP and SOP
1. Plant uptake It is necessary ?
2. Adsorption on It is customary ?
exchange surface
3. Fixation It is Tradition ?
4. Leaching and It is Ritual ?
erosion loss
Complex fertilizers
Complex fertilisers
Complex fertilizers contain more than one of the primary plant
nutrients produced by a process of chemical reaction. It is
obtained by mechanical blending of two or more straight
fertilizer. Each granule contains specified proportion of nutrient.
Some of nutrients like sulphur and micronutrients can easily be
incorporated if required.
Types of complex fertilisers

The complex fertilizers are divided into two types.
•Incomplete fertilizer: The fertilizer with contains two plant
nutrients obtained by manual mixing of two or more straight
fertilizer.
•Complete fertilizer: A fertilizer material containing all the
three plant nutrients.
Characteristics of complex fertilizers
•Complex fertilizers are granulated ones and maintain uniform
grain size, good physical condition during storage, handling
and application
•The complex fertilizers are high analysis fertilizers, transport
and application cost is less in comparison to straight fertilisers
•The nutrients in the complex fertilizers are water soluble form
•They are not hygroscopic fertilizers and do not form cakes
•Cost per unit nutrients are high but the cost per unit fertilisers
is cheaper
•The complex fertilizers are prepared to suit a group of crops
and soils.
Advantages of complex fertilizers
•The possibility of adulteration is generally less.
•Each granule is homogenous in nutrient content.
•Being granular, the drilling of fertilizer is easy.
•They are cheaper than straight or mixed fertilizers.
•Phosphorus availability is not affected.
Disadvantages of complex fertilizers

•The complex fertilizers may not always supply balanced
nutrients to the crops.
•The ratios of the nutrients in the complex fertilizers are fixed
and the farmers may have to supplement with straight
fertilizers.
1. Ammonium phosphate
a) Monoammonium phosphate (MAP)/ b) diammonium
phosphate (DAP)
Ammonium phosphates are formed by reacting high grade
phosphoric acid (40 – 42 % P2O5) with ammonia (89 %) at a
pH of 5.6 under controlled conditions. The resulting solution
contains both nitrogen and phosphorus. The liquid is turned
into a granular product in the granulator. The granular product
is dried and screened. If the product is too small or too large
is recycled to the granulator.
NH3 + H3PO4 NH4H-2PO4 (MAP)

2NH3 + H3PO4 (NH4)2HPO4 (DAP)
DAP (18-46-0)
• Most popular, widely used incomplete
complex fertilizer.
• This can be used as such or in the preparation
of mixtures
Manufacturing of DAP
• Granular DAP is commonly 2 NH3 H3PO4
produced by a slurry process in
which wet process phosphoric
acid of about 40% P2O5 is Pre-neutralizer
allowed to react with ammonia
in either a single step or two Ammonification and
stages such that the mole ratio granulation
of NH3:PO4 in the final product
is maintained around 2:1
• 2NH3 + H3PO4 Drying, cooling
(NH4)2HPO4 and bagging
Properties of DAP
• It is a whitish-grey granular fertilizer
• Non-hygroscopic
• Possesses excellent physical properties
• It is an acidic fertilizer
• It contains 18% N (all in ammoniacal form),
46% total P2O5 and 42.5 % water soluble P2O5
DAP (18-46-0) Specification
• Total nitrogen per cent by weight, minimum 18.0
• Ammoniacal nitrogen form per cent by weight, minimum 15.5
• Total nitrogen in the form of urea per cent by weight, maximum 2.5
• Neutral ammonium citrate soluble phosphates (as P205) per cent by
weight, minimum 46.0
• Water soluble phosphates (as P205) per cent by weight,
minimum 41.0
• Particle size -–[ not less than]90 per cent of the material shall pass
through 4 mm IS sieve and be retained on 1 mm IS sieve. Not more
than 5 per cent shall be below than 1 mm size.
When DAP is applied as plant food, it temporarily
increases the soil pH, but over a long term the treated
ground becomes more acidic than before upon nitrification of
the ammonium. It is incompatible with alkaline chemicals
because its ammonium ion is more likely to convert to
ammonia in a high-pH environment.
FCO specification MAP DAP

1 Moisture % by weight (max) 1 1
2 Total N % weight (min) 11 18
3 Total P2O5 % weight (min) 52 46
4 Water soluble P2O5 % weight (min) 44.2 41.6
c) Ammonium phosphate nitrate
It is essentially a mixture of ammonium nitrate and
ammonium phosphate. It is prepared by direct neutralization of
phosphoric acid (54 % P2O5), nitric acid (60 %) and ammonia
to produce the product of 26 : 26 : 0.
d) Ammonium phosphate sulphate

It is prepared by direct neutralization of sulphuric acid,
phosphoric acid and ammonia. It contains mainly ammonium
sulphate (60 %) and ammonium phosphate (40 %) with a 16
% nitrogen and 20 % P2O5 in 16 : 20 : 0 grade, 20 % nitrogen
and 20 % P2O5 in 20: 20 : 0 grade some urea is added to
increases the nitrogen content.
H2SO4 + H3PO4 + 3NH3 (NH4)3H2PO4SO4
FCO specification 16: 20 20: 20 : 0

:0
1 Moisture % by weight (max) 1 1
2 Total N % weight (min) 16 18

3 Total P2O5 % weight (min) 20 20
4 Water soluble P2O5 % weight (min) 19.5 17

e) Urea ammonium phosphates (UAP)
It is manufactured by using urea, ammonia and
phosphoric acid. The urea and phosphoric acid in the required
proportions are reacted in the pre neutralizes. The resulting
ammonium phosphate slurry is pumped into the granulator.
The nitrogen content is increased by adding more ammonia
and solid urea.
FCO specification 28: 28 20 : 20 24 : 24
1 Moisture % by weight (max) 1 1 1
2 NH4 - N % weight (min) 9 6.4 7.5
3 N in the form of urea % weight 15.5 13.5 16.5
(min)
4 Total N % weight (min) 28 20 24
5 Total P2O5 % weight (min) 28 20 24
6 Water soluble P2O5 % weight (min) 25.2 18 20.4
2. Nitrophosphates
The nitrophosphates are prepared by from the following
of processes, which are commercially important.
1) Rock phosphate with nitric acid
It is produced by acidulation of rock phosphate with nitric
acid in a series of reactions. This reactant mass contains
calcium nitrate and phosphoric acid. To this reacted mass is
added high concentrated water soluble phosphate and the
reaction mass is ammoniated in a series of reactors to provide
nitrogen balance. At every stage pH and temperature are
maintained.
Ca10(PO4)6F2 + 20 HNO3 6 H3PO4 + 10 Ca(NO3)2 + 2 HF
6 H3PO4 + 10 Ca(NO3)2 + 2 HF + 14 NH4NO3 + 3 Ca(NO3)2 +

7 (NH4)2H2PO4 6 Ca(H2PO4)2 + H3PO4 + CaF2
14 NH4NO3 + 3 Ca(NO3)2 + H3PO4 20 NH4NO3 + 4 NH4H2PO4 +

6 Ca(H2PO4)2 + CaF2 + 10 NH3 9 CaHPO-4 + CaF2
Ca10(PO4)6F2 + 20 HNO3 + 20NH4NO3 + 4NH4H2PO4 +
7(NH4)2HPO4 + 10 NH3 9CaHPO-4 + CaF2
2) Rock phosphate with mixtures of acid
i) Phosphoro nitric nitrophosphate: Rock phosphate is treated with nitric
acid and sufficient quantity of phosphoric acid to adjust the molecular ratio
– 4 in rock
phosphate. As such the product of reaction is treated with liquid ammonia
to form dicalcium phosphate, monoammonium phosphate and ammonium
nitrate. The amount of water soluble phosphorus in this mixture is
controlled by altering the ratio of nitric acid and phosphoric acid. The total
nutrient content of nitrophosphate manufactured by this process ranges
from 39 – 47 %.
Ca10(PO4)6F2 + 16HNO3 + 6H3PO4 + 2Ca(H2PO4)2 + 10Ca(NO3)2 + 2

4H3PO4 HF
6H3PO4 + 2Ca(H2PO4)2 + 16NH4NO3 + NH4H2PO4 +

10Ca(NO3)2 + 2HF + 17NH3 9CaHPO-4 + CaF2
Ca10(PO4)6F2 + 16HNO3 + 16NH4NO3 + NH4H2PO4 +

4H3PO4 + 17NH3 9CaHPO-4 + CaF2
ii) Sulpho nitric nitrophosphate: Rock phosphate is treated
with mixtures of nitric acid and sulphuric acid. As such the
product of reaction is treated with liquid ammonia to form
dicalcium phosphate, monoammonium phosphate and
ammonium nitrate. The total nutrient content of
nitrophosphate manufactured by this process ranges from 26
– 33 %.
Ca10(PO4)6F2 + 12HNO3 + 6H3PO4 + 6Ca(NO3)2 + 2CaSO4 + 2
4H2SO4 HF
6H3PO4 + 6Ca(NO3)2 + 2CaSO4 + 12NH4NO3 + NH4H2PO4 +

2 HF + 13NH3 5CaHPO-4 4CaSO4 + CaF2
Ca10(PO4)6F2 + 12HNO3 + 12NH4NO3 + NH4H2PO4 +

4H2SO4 + 17NH3 5CaHPO-4 4CaSO4 + CaF2
The advantages of sulpho nitric nitrophosphate methods
are no investment of phosphoric acid plant, compared to
super phosphate only half of the sulphuric acid is required
FCO specification 20 : 20: 0 18 : 18: 15 : 15: 15
9
1 Moist % by weight (max) 1.5 1.5 1.5
2 Total N % weight (min) 20 18 15
3 Total P2O5 % weight (min) 20 18 15
4 Water soluble P2O5 % weight 5.4 4.9 4.0

(min)
5 Water soluble K2O % weight 9 15
(min)
6 Calcium nitrate Traces traces
7 Particle size: Shall be such that 90 % of the
material will be b/w 4 mm and 1
mm IS sieve.
Complete complex fertilisers
Complete complex fertilizers are efficient products but
trends in using them during past thirty years are increased for
its agricultural efficiency or sustainability.
NPK Total Neutral ammonium Water soluble Water soluble
fertilizers Nitrogen citrate soluble phosphate potash (K2O)
(N) phosphate (P2O5)
15-15-15 15.0 15.0 4.0 15.0
10-26-26 10.0 26.0 22.1 26.0
12-32-16 12.0 32.0 27.2 16.0
22-22-11 22.0 22.0 18.7 11.0
14-35-14 14.0 35.0 29.0 14.0
17-17-17 17.0 17.0 14.5 17.0
14-28-14 14.0 28.0 23.8 14.0
19-19-19 19.0 19.0 16.2 19.0
17-17-17 17.0 17.0 13.6 17.0
20-10-10 20.0 10.0 8.5 10.0
Mixed fertilizers
Terms commonly used
• Fertilizer:
The substance which is used for the supply of plant nutrients
or
Any substance containing one or more recognized plant nutrient(s) which is
used for its plant nutrient content. Unprocessed animal and vegetable
manures, lime, limestone, wood ashes, and other products are exempt from
this definition.
• Fertilizer material or Fertilizer carrier
Is a fertilizer which either
1. Contains important quantities of no more than one of the primary plant
nutrients: N, P2O5 and K2O or
2. Has 85% or more of its plant nutrient content present in the form of a single
chemical compound or
3. Is derived from a plant or animal residue or by-product or natural mineral
deposit which has been processed in such a way that its content of plant
nutrients has not been materially changed except by purification and
concentration.
Terms commonly used
• Mixed fertilizer :
Mixed fertilizers are physical mixtures of fertilizer materials, containing two or
more major plant nutrients.
Prepared thoroughly mixing the ingredients, either mechanically or manually.
• Complete fertilizer :
A single fertilizer material containing the entire three major plant nutrients viz,
N, P and K
• Fertilizer grade :
It refers to the guaranteed minimum percentage of nitrogen (N), phosphate
(P2O5) and potash (K2O) contained in the mixed fertilizer.
Thus, 100 kg of a mixture of a grade 12-6-6 will contain a minimum of 12 kg
N, 6 kg P2O5 and 6 kg K2O.
The numbers representing the grade are separated by hyphens (-) and
always stated in the order of N, P2O5 and K2O
Terms commonly used
• Fertilizer formula :
Is an expression of the quantity and analysis of the materials in
a mixed fertilizer.
• Fertilizer ratio :
FR refers to the relative percentages of N, P2O5 and K2O in the
mixture ( a 6-24-24 grade has a 1-4-4 ratio).
• Acidic fertilizer :Fertilizer capable of increasing the acidity of
the soil by continued applications.
• Basic fertilizer :Fertilizers which increase the pH and the soil
on continued use by leaving a basic residue in the soil.
• Neutral fertilizer :Materials which are neither increasing nor
decreasing the pH of the soil
Terms commonly used
• Conditioners:
These are materials which are added to fertilizer
mixtures during their preparation for reducing
hygrocopicity and improve their physical conditions.
E .g.- tobacco stems, peat, groundnut shell and paddy
husk.
• Filler :
It is called as the ‘make-weight’ material added to
the fertilizer mixtures. Filler materials are inert
materials like sand, saw dust etc, are added to make
up the difference between weight of ingredients
added to supply the plant nutrients in a tonne and
the final weight viz., 1,000 kg.
Terms commonly used
• Dry bulk blending:
Is the process of mechanically mixing solid fertilizer materials.
• A Bulk Fertilizer:
Is a fertilizer distributed in a nonpackaged form.
• Clear liquid fertilizer:
Is the one in which the N-P-K and other materials are completely
dissolved.
• Suspension fertilizer :
Is one in which some of the fertilizer materials are suspended as
fine particles..
• Fluid fertilizer : Is a Clear or suspension liquid fertilizer
• Speciality fertilizer : Is a fertilizer distributed for non form use
Types of fertilizer mixtures
• Open formula fertilizer mixtures
The formula of each fertilizer mixture in terms
of kinds and quantities of the ingredients
mixed are disclosed by the manufacturers.
• Closed formula fertilizer mixtures
The ingredients or straight fertilizers used in
the mixture are not disclosed
Preparation of mixed fertilizers
The preparation of fertilizer mixtures usually involves the weighing and
proportioning of ingredients that are used, sieving and sizing of the
various ingredients, mixing the different materials and packing.
Materials used
1. Suppliers of plant nutrients
N sources : AS, Urea, CAN, CaCN2, NaNO3, Oil cakes
P sources : Super phosphate, Bone meal
K sources : MOP, SOP
2. Conditioners: low grade organic materials are usually added @ of 100
kg/t (tobacco stems, peat, groundnut shell and paddy husk)
3. Neutralizers of residual acidity : a basic material such as dolomite
limestone is added to counteract the acidity
4. Filler: is the make-weight material added to fertilizer mixture (sand,
soil, ground coal, ashes)
Guide for Mixing Fertilizer
Fertilizer compatibility chart
Guide for mixing
• To determine the amount of individual fertilizer
in a mixture, the quantity is calculated as
follows.
(Percentage of plant nutrient desired x (Weight of final mixture)
in the mixture)
Quantity =
(The Percentage of the plant nutrient in the straight fertilizer)
RxT
• A=
P
• R = Percentage in the mixture
• T = Final weight of the mixture
• P = Percentage in the straight fertilizer.
To prepare a mixture of 10: 5: 10 using (NH4)2SO4, (20% N), Super
phosphate (16% P2O5) and muriate of potash (60% K2O), the
following quantities will be required per tonne (1,000 kg)
RxT
A=
P
10 x 1000
1. Ammonium sulphate = = 500 Kg.
20
5 x 1000
2. Super phosphate = = 312.5 Kg.
16
10 x 1000
3. Muriate of potash = = 166.5 Kg.
60 _______________
Total = 979.0 Kg .
Filler = 1000 – 979 = 21 Kg.
If the total calculated weight exceeds the final weight, a mixture of
that ratio can not be prepared.
Points to be considered while preparing mixed fertilizers
1. Fertilizers containing ammonia are not mixed

directly with the basic fertilizers (e.g. RP, limestone,
basic slag, CaCN2) as reaction will take place
resulting in the loss of gaseous NH3.
2. The water – soluble phosphates are not mixed with
those materials which contain free lime (e.g) lime
stone, CaCN2) as there will be reaction towards the
reversing of water – soluble phosphate to water –
insoluble phosphates.
3. Hygroscopic fertilizers are not included as they will
facilitate caking up.
4. The acidic fertilizers are likely to produce some free
acids which may damage the container or packing
materials.
Advantages
• All the three major plant nutrients are made
available in one and the same material.
• There is saving of time and labour.
• The residual effects will not be there.
The fertilizer mixtures are usually prepared taking
into account the acidic or alkaline nature of the
ingredients, and other chemical reactions. Hence,
some of the residual effects like acidity will not be
there.
• Usually mixed fertilizer are prepared to suit a
group of crops and soils.
Disadvantages
• Specific needs of crops and deficiency of
individual nutrient elements cannot be satisfied
by using mixed fertilizers as efficiently as in the
case of straight fertilizers.
• The use of mixed fertilizer in such cases of
specific needs will be a waste as other nutrients
are also added to the soil.
• Unit cost of the various nutrients contained in the
mixed fertilizer will always be higher when
compared to the unity cost of nutrients contained
in the straight fertilizers.
Unit value
• The unit value of a fertilizer or manure is the cost
of that quantity of material capable of supplying
one per cent of the plant food ingredient.
• The cost per unit is arrived at by dividing the cost
per 100 kg by the percentage of nutrient
contained in it.
• For example, if the cost of a 100 kg of ammonium
sulphate is Rs.300/- then the unit value is 300/20
= Rs.15/-. From the unit value it is possible to
evaluate the relative value of any fertilizer or
mixture.
Changes that occur while manufacturing of mixed fertilizer
I. Physical changes
The following are the most important physical changes that will take place during
or after the mixing of fertilizers.
1. Hygroscopicity
It is a property of any substance which absorbs water from air and gets
converted to semi- solid or liquid condition. Fertilizer like calcium nitrate, ammonium
nitrate, sodium nitrate and urea are capable of absorbing moisture from air and
become hygroscopic. In such cases handling will be very difficult for such mixtures.
2. Caking up
Moisture present in some of the ingredients is responsible for caking up.
Moisture dissolves some of the easily soluble ingredients and forms a saturated
solution. This saturated solution on evaporation gives out crystals which together
forming larger lumps. The caking up can be prevented by the use of certain kind of
materials called as ‘conditioners’. The commonly used conditioners are groundnut
hulls, lime, clay etc. The granulation aims at preparation of uniform sized particles
with reasonable stability which presents caking up.
3. Segregation
This relates to separation of different sized particles individually. When
ingredients of different sizes and densities are included there will be the tendency for
the segregation (sorting out to different sizes) to take place.
II. Chemical changes
The chemical changes are found to be influenced by temperature,
moisture content and particle size of the ingradients.
1. Double decomposition
The reaction is between two compounds without a common ion in the
presence of moisture. New compounds are formed which may have different
physical and chemical properties.
Ca(H2PO4)2 + (NH4)2SO4 CaSO4 + 2 NH4H2PO4

NH4NO3 + KCl NH4Cl + KNO3
(NH4)2SO4 + 2 KCl 2 NH4Cl + K2SO4
2. Neutralization
This reaction takes place when free acids present in some of the fertilizers
are neutralized by alkalis or Ca containing salts included in the mixture.
H3PO4 + NH3 NH4H2PO4
2 H3PO4 + CaCO3 Ca(H2PO4)2 + H2CO3
3. Hydration
The process of tying up of water by the anhydrous form of salts is called
hydration. Some of the fertilizers are found to have this property.
CaSO4 + 2 H2O CaSO4.2H2O
CaHPO4 + 2 H2O CaHPO4.2 H2O
4. Decomposition
Under certain conditions of moisture and temperature, there will
be break down in the composition of molecules forming new compounds.
CO(NH-2)2 + H2O 2 NH3 + CO2

(NH-4)2HPO4 NH4H2PO4 + NH3
SOIL AMENDMENT
• Any substance other than fertilizers, such as
lime, sulphur, gypsum, sawdust, used to alter
the chemical or physical properties of a soil,
generally to make it more productive.
Liming materials
• Soil acidity is commonly decreased by adding
carbonates, oxides or hydroxides of calcium
and magnesium, compounds that are referred
to as agricultural lime.
Carbonate forms
• There are number of sources of carbonate of lime,
including marl, oyster shells, basic slag and
precipitated carbonates, but ground limestone is
the most common and is by far the most widely
used of all liming materials.
• The 2 important minerals includes in limestones
are calcite and dolomite
• The Ca and Mg content varies between 75 to 99 %
• Calcitic Lime stone- CaCO3 equiv -95 %
• Dolomitic Lime stone- CaCO3 equiv – (35 to 65%)
Oxide form
• Commercial oxide of lime is normally referred to as
burned lime, quicklime or often simply as the oxide.
• It is produced by heating limestone in large commercial
kilns in which reactions such as the following take place
• CaCO3 CaO + CO2
• CaMg(CO3)2 CaO + MgO + 2CO2
• It is more costly than limestone
• It is more caustic than limestone and consequently is
difficult to handle.
• It reacts much more rapidly with the soil than LS
• The CaCO3 equiv 182.5 %
Hydroxide form
• The hydroxide form of lime is commonly referred
to as hydrated lime, since it is produced by
adding water to burned lime
• CaO+MgO+ 2H2O Ca(OH)2 + Mg(OH)2
• It is more caustic than burned lime.
• It is available in the market as white powder
• It is used where a rapid rate of reaction is desired
and/ or where a high soil pH is necessary.
• The CaCO3 equiv – 140.5 %
Reaction of lime in soil
2CaCO3 + 2 H2CO3 2Ca(HCO3)2
Al Ca
Colloid + 2Ca2+ Colloid + Al3+ + H+ + 4HCO3
H Ca
Al3+ + 3H2O Al(OH)3 + 3 H+
4H+ + 4HCO3 4H2O + 4CO2

Amendments for Sodic soils and
/or saline-sodic soils
• Gypsum (CaSO4.2H2O)
• Elemental sulphur
• Sulphuric acid
• Iron pyrite
Reaction of gypsum in sodic or saline sodic
soil
GR(t/ acre foot soil) = (Nax) X 1.72

Where Nax = Exch. Na(meq/100g)
Soil colloid Na + CaSO4 2H2O Soil colloid Ca + Na2SO4
(If necessary provide drainage)

Calcium sources
Material Formula Ca (%) Relative neutralizing
value*
Calcitic limestone CaCO3 32 95-100
Dolomitic CaMg(CO3)2 29 50-70
limestone
Basic slag 22 None
Gypsum CaSO4.2H2O 22 15-85
Hydrated lime Ca(OH)2 46 150-175
Burned lime CaO 60
Magnesium sources
Material Formula Mg (%)
Dolomitic limestone CaMg(CO3)2 3-12
Magnesia MgO 55-60
Basic slag 3
Magnesium sulphate MgSO4.7H2O 9-20
Potassium-magnesium sulphate K2SO4.MgSO4 11
Sulphur sources
Material Chemical formula S (%)
Ammonium sulphate (NH4)2SO4 24
Ammonium thiosulphate (NH4)S2O3 5H2O 26
Ammonium polysulphide (NH4)2Sx 40-50
Potassium sulphate K2SO4 18
Potassium-magnesium K2SO42MgSO4 22
sulphate
Elemental sulphur S >85
Gypsum CaSO42H2O 12-18
Magnesium sulphate MgSO47H2O 14
Micronutrient sources
Sl. No. Name Formula Element/ Contents
Forms (%)
1. Zinc sulphate* ZnSO4.7H2O Zn 21.0 (15)
2. Zinc sulphate ZnSO4.H2O Zn 33.0
monohydrate
3. Chelated Zn Zn-EDTA Zn 12.0
4. Mangnese sulphate* MnSO4 Mn 30.5 (17)
5. Ammonium (NH4)5Mo7O244H2O Mo 52.0
molybdate
6. Borax Na2B4O7.5H2O B 10.5
(soil application)
7. Solubor Na2B4O7.5H2O + B 19.0
(foilar spray) Na2B10O16.10H2O
8. Ferrous sulphate* FeSO4.7H2O Fe 19.5 (19)
9. Chelated Fe Fe-EDTA Fe 12.0
10. Copper sulphate* CuSO4.5H2O Cu 24.0 (13)
Definition
The percentage of the added fertilizer that is
actually used by plants is the measure of
fertilizer efficiency.
It may be
30 to 70 per cent of added N
10-30 per cent of added P
50 to 80 per cent of added K
Factors affecting fertilizer efficiency
Plant root systems
Fertilizer-water interactions
Fertilizer management techniques
Plant root systems
Certain plants grow well on a given soil while other plants do not
– Some plants are better nutrient scavengers than others
e.g. Dicotyledons, especially legumes, feed strongly on divalent
cations like Ca+2, whereas grasses feed better on monovalent
cations like K.
How well plant absorb fertilizers (i.e. nutrient)
depends upon
1. Root distribution-
Smaller the root system (shallow and/or few in number), the
more dependent the plant is on fertilization.
2. Plant growth rates and size-
small and slow growing plants have low total demands.
Fertilizer-water Interaction
Plant response to fertilizer is dependent upon soil
moisture
Nutrient uptake depends upon the flow of water to the
plant roots
Growth of roots into new soil volumes
Less mobile nutrients, such as Zn and P depend upon
diffusion and root extension to be absorbed
Nutrient uptake increases as water content increases to
near field capacity.
Fertilizer management techniques
Avoid single large fertilizer additions
Especially N and K and if recommendation is >50 kg /ha on sandy soils
Reduce ammonia volatilization losses
by avoiding surface broadcast application of urea and ammonia solutions on moist
calcareous soil
Fertilizers are immediately incorporated by tillage or watered into the soil.
Reduce denitrification losses by
avoiding heavy nitrate fertilizer additions on poorly drained soils, such as rice paddies
and poorly drained clayey soils in wet climates
Use ammonium form and prevent cycles of aerated – nonaerated condition.
Band water-soluble phosphorus fertilizers:
Broadcast and incorporate low solubility materials.
On soils of very low available P, banding is often less productive than broadcast mixing.
On high P fixing soils banding is most efficient.
Use a small amount of (10 to 20 kg/ha) of starter fertilizer with seed,
if fertilizer is not band applied at planting.
Avoid larger salt damaging amounts of N and K fertilizers near seed or roots
Test soils frequently, some fields every year, and follow the recommendations.
However, Soil analysis is no panacea
Measuring nutrient use efficiency
Agronomic indices for assessment of nutrient use
efficiency
RE = Apparent crop recovery efficiency of applied
nutrient (kg increase in N uptake per kg N
applied)
RE=(U – Uo)/F
F – amount of (fertilizer) nutrient applied (kg/ha)

U – total plant nutrient uptake in aboveground biomass at maturity
(kg/ha) in a plot that received fertilizer
Uo – total nutrient uptake in aboveground biomass at maturity (kg/ha)
in a plot that received no fertilizer
PE = Physiological efficiency of applied N (kg yield
increase per kg increase in N uptake from fertilizer)
PE=(Y– Yo)/(U– Uo)
Y – crop yield with applied nutrients (kg/ha)

Yo – crop yield (kg/ha) in a control treatment with no N
U – total plant nutrient uptake in aboveground biomass at
maturity (kg/ha) in a plot that received fertilizer
Uo – total nutrient uptake in aboveground biomass at
maturity (kg/ha) in a plot that received no fertilizer
IE = Internal utilization efficiency of a
nutrient (kg yield per kg nutrient uptake)
IE=Y/U
U – total plant nutrient uptake in aboveground biomass at
maturity (kg/ha) in a plot that received fertilizer
AE = Agronomic efficiency of applied
Nutrient (kg yield increase per kg nutrient applied)
AE=(Y – Yo)/F or
AE=RE x PE
PFP = Partial factor productivity of applied
nutrient (kg harvested product per kg nutrient
applied)
PFP=Y/F or
PFP=(Yo/F) + AE

right product,
right rate,
right time and
right place.
These are the underpinning principles of fertilizer BMPs.

Right product:
Match the fertilizer source and product to crop
need and soil properties.
e. g.
1. Selection of S containing fertilizer material if the soil
S status is low
2. Avoid using water soluble P fertilizer in acid soil
3. Use SOP for potato, tobacco
4. Use ammonical form for paddy
Right rate:
Match the amount of fertilizer applied to the crop
needs.
Too much fertilizer leads to leaching and other losses to the
environment
too little results in lower yields and crop quality and less
residue to protect and build the soil.
Realistic yield goals, soil testing, omission plots, crop

nutrient budgets, tissue testing, plant analysis, applicator
calibration, variable rate technology, determine the right
rate of fertilizer to apply.
Right time:
Make nutrients available when the crop needs
them.
Nutrients are used most efficiently when their
availability is synchronized with crop demand.
Application timing (pre-plant or split applications),
controlled release technologies, stabilizers, inhibitors
and product choice are examples of BMPs that
influence the timing of nutrient availability.
Right place:
Place and keep nutrients where crops can use
them.
Application method is critical for efficient
fertilizer use.
Crop, cropping system and soil properties dictate
the most appropriate method of application, but
incorporation is usually the best option to keep
nutrients in place and increase their efficiency.
Fertilizer BMPs should help ensure that fertilizer
uptake and removal by target crops is optimized and
fertilizer loss to the environment is minimized.
Fertilizer BMPs should increase nutrient use

efficiency, but maximum use efficiency is not the
primary objective. The goal is to use fertilizers
efficiently and effectively in providing adequate
nutrition for crops.
Table 1. Indices of nutrient use efficiency, their calculation
using the difference method, and their interpretation
Index Calculation Interpretation N in cereals

Apparent crop RE=(U – Uo)/F • RE depends on the 0.3–0.5 kg/kg;
recovery congruence between 0.5–0.8 kg/kg
efficiency (RE) plant demand and in well-managed
of applied nutrient release from systems, at low
nutrient (kg fertilizer. levels of N use,
increase in N • RE is affected by the or at low soil N
uptake per kg N application method supply
applied) (amount, timing,
placement, N form) and
factors that determine
the size of the crop
nutrient sink (genotype,
climate, plant density,
abiotic/ biotic stresses).
Introduction
Fertiliser is the key input for sustainable agriculture.
In the Post Green Revolution period, more than 50% of
additional food grains production has been contributed by
the fertiliser alone.
To ensure adequate availability of right quality of fertilizers
at reasonable price to the farmers in the country, the
‘Fertiliser’ was declared as an Essential Commodity in
March, 1957 and the Fertiliser Control Order (FCO) was
promulgated by the Central Government under section 3 of
the Essential Commodities Act (ECA), 1955 to regulate the
trade, price, quality and distribution of Fertilisers in the
Country.
The amendments are issued from time to time- latest was in
2003
No.11-3/83-STU
Government of India
Ministry of Agriculture and Rural Development
(Department of Agriculture and Cooperation)
New Delhi, dated 25th September 1985
THE FERTILISER (CONTROL) ORDER 1985
The FERTILIZER (CONTROL) ORDER-1985 of the
Essential Commodities Act (ECA), provides for:
Compulsory registration of fertilizer makers, importers and sellers.
Specifications for all fertilizers produced, imported or sold in India.
A set of regulations on the manufacture of fertilizer mixtures.
Packing and labelling of fertilizer bags.
Appointment of enforcement agencies and creation of quality control
laboratories.
Banning of the manufacture or import and sale of non-standard,
spurious or adulterated fertilizers.
The order also provides for cancellation of authorization
letter/registration certificates of dealers and mixture manufacturers.
Offenders under ECA may also face imprisonment from 3 months to 7
years and/or a fine. The FCO offence has been declared as cognisable
and nonbailable.
ORDER
G.S.R. 758 (E). In exercise of the powers conferred
by section 3 of the Essential Commodities Act,
1955 (10 of 1955), the Central Government hereby
makes the following Order, namely
1. Short title and commencement

1.This Order may be called the Fertiliser (Control) Order, 1985.
2.It shall come into force on the date of its publication in the
Official Gazette.
2. Definition
In this Order, unless the context otherwise requires:
a. "Act" means the Essential Commodities Act, 1955 (10 of
1955).
b. "certificate of source" means a certificate given by a State
Government, Commodity Board, manufacturer, + importer,
pool handling agency or --as the case may be, wholesale
dealer indicating therein the source from which fertiliser for
purpose of sale is obtained.
c. "Commodity Board" means the Coffee Board constituted
under section 4 of the Coffee Act, 1942 (7 of 1942) or the
Rubber Board constituted under section 4 of the Rubber Act,
1947 (24 of 1947), or the Tea Board constituted under section
4 of the Tea Act, 1953 (29 of .1953), or as the case may be, the
Cardamom Board constituted under section 4 of the
Cardamom Act, 1965 (42 of 1965).
d. "compound or complex fertiliser" means a fertiliser
containing two or more nutrients during the
production of which chemical reaction takes place
f. "dealer" means a person carrying on the business of
selling fertilisers whether wholesale or retail or
industrial use* and includes a manufacturer,
+Importer, and a pool handling agency carrying on
such business and the agents of such person,
manufacturer, +importer or pool handling
agency.
h. "fertiliser" means any substance used or intended to
be used as a fertiliser of the soil and/or crop and
specified in Part A of Schedule I and includes a
mixture of fertiliser and special mixture of
ferti1isers.
j. "grade" means the nutrient element contents in
the fertiliser expressed in percentage
k. "granulated mixture" means a mixture of
fertilisers made by intimately mixing two or more
fertilisers with or without inert material, and
granulating them together, without involving any
chemical reaction.
l. “importer" means a person who imports fertiliser
in accordance with the Export and Import Policy of
the Central Government, as amended from time to
time.
m. "inspector" means an Inspector of Fertilisers
appointed under clause 27.
u. "prescribed standard" means:-
i. in relation to a fertiliser included in column 1 of
Part A of Schedule-I, the standard set out in the
corresponding entry in column 2, subject to the
limits of permissible variation as specified in Part B
of that Schedule; and
x. "retail dealer" means a dealer who sells fertilisers to
farmers or plantations for **agricultural use such as
for fertilisation of soil and increasing productivity
of crops.
aa. "wholesale dealer" means a dealer who sells
fertilisers otherwise than in retail-for agricultural
use such as for fertilisation of soil and increasing
productivity of crops.
II Price control
3. Fixation of prices of fertilisers
1. The Central Government may, with a view to regulating equitable
distribution of fertilisers and making fertilisers available at fair prices,
by notification in the Official Gazette, fix the maximum prices or rates
at which any fertiliser may be sold by a dealer, manufacturer, +importer
or a pool handling agency.
2. The Central Government may having regard to the local conditions of

any area, the period of storage of fertilisers and other relevant
circumstances, fix different prices or rates for fertilisers having different
periods of storage or for different areas or for different classes of
consumers.
3. No dealer, manufacturer +importer or pool handling agency shall sell or

offer for sale any fertiliser at a price exceeding the maximum price or
rate fixed under this clause.
4. Display of stock position and price list of fertilisers
Every dealer, who makes or offers to make a retail sale of any fertilisers,
shall prominently display in his place of business:-
III. CONTROL ON DISTRIBUTION OF FERTILISERS
BY MANUFACTURER/ IMPORTER
6. Allocation of fertilisers to various States
The Central Government may, with a view to securing
equitable distribution and availability of fertilisers to
the farmers in time, by notification in the Official
Gazette, direct any manufacturer/importer to sell the
fertilisers produced by him in such quantities and In
such State or States and within such period as may be
specified in the said notification
IV. AUTHORISATION OR REGISTRATION OF DEALERS”
7. Registration of Industrial dealers and authorization of other dealers
No person shall sell, offer for sale or carry on the business of selling of fertilizer
at any place as wholesale dealer or retail dealer except under and in accordance
with clause8: Provided that a State Government may, if it considers it necessary
or expedient, by notification in the Official Gazette, exempt from the provisions
of this clause any person selling fertilizer to farmers in such areas and subject to
such conditions as may be specified in that notification.”
8. Application for intimation or registration
Every person intending to sell or offer for sale or carrying on the business of
selling of fertilizer as Industrial Dealer shall obtain a certificate of registration
from the controller by making an application in Form A together with the fee
prescribed under clause 36 and a Certificate of source in Form O.
9. Grant or refusal of certificate of registration
The Controller, shall grant a certificate of registration in Form 'B’ within thirty
days of the receipt of application to any person who applies for it under clause 8;
Provided that no certificate of registration shall be granted to a person: -
a. if his previous certificate of registration is under suspension;
10. Period of validity of certificate of registration
and letter of authorization
Every certificate of registration granted under clause 9
and every authorization letter issued under clause 8
shall, unless renewed, suspended or cancelled, be valid
for a period of three years from the date of its issue.
V. MANUFACTURE OF MIXTURES OF Fertilisers
VI. RESTRICTIONS ON MANUFACTURE/ IMPORT, SALE, ETC.
OF FERTlLISER
19. Restriction on manufacture/import, sale and
distribution of fertilisers
• No person shall himself or by any other person on his
behalf: manufacture/import for sale, sell, offer for sale,
stock or exhibit for sale or distribute any fertlliser which Is
not of prescribed standard;
VII. ENFORCEMENT AUTHORITIES
26. Appointment of registering authority The State
Government may, by notification in the Official Gazette,
appoint such number of persons, as it thinks necessary, to
be registering authorities for the purpose of this Order [
$]for industrial dealers, and may, in any such notification
define the limits of local area within which each such
registering authority shall exercise his jurisdiction.
26A. Notified Authority- The State Government may, by

notification in the Official Gazette, appoint such number
of persons, as it thinks necessary, to be Notified Authorities
for the purpose of this Order and define the local limits
within which each such Notified Authority shall exercise
his jurisdiction.
27. Appointment of inspectors
The State Government, or the Central Government may, by
notification in the Official Gazette appoint such number of
persons, as it thinks necessary, to be inspectors of fertilisers
for the purpose of this Order, and may, in any such
notification, define the limits of local area within which each
such inspector shall exercise his jurisdictions.
27A. Qualifications for appointment of fertiliser Inspectors
No person shall be eligible for appointment as Fertiliser
Inspector under this Order unless he possesses the following
qualifications, namely:-
Graduate In agriculture or science with chemistry as one of the
subjects, from a recognised university; and
Training or experience in the quality control of fertilisers and
working in the State or Central Government Department of
Agriculture.
28. Powers of Inspectors
An inspector may, with a view to securing compliance
with this Order:-
require any manufacturer, +importer, pool handling
agency, wholesale dealer or retail dealer to give any
information in his possession with respect to the
manufacture, storage and disposal of any fertilizer
manufactured or, in any manner handled by him
draw samples of any fertiliser in accordance with the
procedure of drawal of samples laid down in Schedule
II. Provided that the inspector shall prepare the
sampling details in duplicate In Form J, and hand over
one copy of the same to the dealer or his representative
from whom the sample has been drawn;
28. Powers of Inspectors ..... contd
enter upon and search any premises where any

fertiliser is manufactured/ Imported or stored or
exhibited for sale, if he has reason to believe that any
fertiliser has been or is being manufactured/imported,
sold, offered for sale, stored, exhibited for sale or
distributed contrary to the provisions of this Order;
seize or detain any fertiliser in respect of which he has
reason to believe that a contravention of this Order has
been or is being or is [attempted] to be committed;
VIII. ANALYSIS OF SAMPLES
29. Laboratory for analysis
A fertiliser sample, drawn by an inspector, shall be
analyzed in accordance with the instructions
contained in Schedule II in the -Central Fertiliser
Quality Control and Training Institute, **Faridabad or
Regional Fertiliser Control Laboratories at Bombay,
Madras or Kalyani (Calcutta) or in any other laboratory
notified for this purpose by the State Government
[with the prior approval of the Central Government.
IX. MISCELLANEOUS
31 Suspension, Cancellation Or Debarment
SCHEDULE I
[See Clause 2(h) & (q)]
PART-A
SPECIFICATIONS OF FERTILISERS*
SCHEDULE II
(See clause 28 (1) (b) and 29)
PART A
PROCEDURE FOR DRAWAL OF SAMPLES OF
FERTILIZERS
PART B
METHOD OF ANALYSIS OF FERTILIZERS
Fertilizer quality control as per FCO
The CENTRAL FERTILISER QUALITY CONTROL AND
TRAINING INSTITUTE (CFQCTI) is the main body that is
involved in fertilizer quality testing. It is located in the city
of Faridabad in Haryana with three Regional Fertilizer
Control Laboratories (RFCL) situated in Navi Mumbai,
Chennai and Kalyani. The main objectives of CFQCTI are:
Undertaking inspection and analysis of imported and
indigenous fertilizers
Standardization and development of method of analysis
Training of fertilizer enforcement officers and analysts.
Acting as a referee laboratory
Providing technical guidance to the Central and State
governments on Fertilizer Quality Control Laboratories.
Currently there are around 67 Fertilizer Quality
Control Laboratories in the country.
Every year, they analyse around 1,25,205 samples.
Most samples are checked for adulteration and use of
spurious products.
States usually have one or more labs; however,
Arunachal Pradesh, Sikkim, Manipur, Tripura,
Meghalaya, Delhi, Goa and all Union Territories with
the exception of Pondicherry do not have any
laboratory and use central services.
PROCEDURE FOR DRAWAL OF SAMPLES OF FERTILIZERS
1. General requirement of sampling
In drawing samples, the following measures and
precautions should be observed.
(a) Samples shall not be taken at a place exposed to
rain/sun;
(b) The sampling instruments shall be clean and dry
when used;
(c) The material being sampled, the sampling
instrument and the bags of samples should be free
from any adventitious contaminations;
(d) To draw a representative sample, the contents of each bag
selected for sampling should be mixed as thoroughly as
possible by suitable means;
(e) The sample should be kept in suitable, clean dry and air
tight glass or screwed hard polythene bottle of about 400
gm capacity or in a thick gauged polythene bag. This
should be put in a cloth bag which may be sealed with the
Inspector's seal after putting inside the detailed
description as specified in Form "J" Identifiable details
may also be put on the cloth bag like sample No./Code
No. or any other details which enables its identification;
(f) Each sample bag should be sealed air tight after filling and
marked with details of sample, type and brand of
fertilizer, name of dealer/manufacturer/importer and the
name of Inspector who has collected sample.
2. Sampling from bagged material
(i) Scale of sampling
(a) Lot (for manufacturers/importers)
All bags in a single consignment of the material of the same grade and
type drawn from a single batch of the manufacturer/importer shall
constitute a lot. If a consignment is declared to consist of different
batches of manufacturer/import, all the bags of each batch shall
constitute a separate lot. In the case of a consignment drawn from a
continuous process,2000 bags (or 100 tones) of the material shall
constitute a lot.
(b) Lot (for dealers)
The lot is an identifiable quantity of same grade and type of fertilizer
stored at an identifiable place subject to a maximum limit of 100 tones.
The lot shall be identified by the inspector based on visible appearance
of bags, their packing and storage conditions. The stock of less than 100
tones with a dealer may also constitute one or more lots, if the material
(fertilizer) of different sources and brand is available in such quantities.
(c) Selection of bags for sampling
The number of bags to be chosen from a lot shall depend upon the size of the
lot as given in the table below.
Lot size (No. of bags) No. of bags to be selected
(N) for sampling (n)
Less than 10 1
10-100 2
100-200 3
200-400 4
400-600 5
600-800 6
800-1000 7
1000-1300 8
1300-1600 9
1600-2000 10
All the bags of a lot should be arranged in a systematic manner. Start counting from any
bag randomly, go on counting as 1,2,3,- up to r and so on, r being equal to the integral of
N/n. Thus every rth bag counted shall be withdrawn and all bags shall constitute the
sample bags from where the sample is to be drawn for preparing a composite sample
(ii) Sampling from big godowns/high stackings.
If the procedure given in Para 2(i) (c) is not possible
to be adopted, the sample should be drawn from the
randomly selected fertilizer bags from different
layers, from top and from all open side in a zig
fashion.
(iii) Sampling from small godowns

All the fertilizer bags of the same grade and type of
each manufacturer though received on different dates
shall be segregated and properly stacked. All bags of
same grade and type of fertilizer manufactured by a
particular manufacturing unit may be considered as
one lot based on their physical conditions and the
sample shall be drawn as per procedure laid in Para
2(i) (c) and 4.

(iv) Sampling from damaged stock
(a) In case of torn or lumpy bags, damaged
fertilizer bags or sweepings, the stock should be
arranged according to identifiable lots. From each
lot the number of bags shall be selected as per
procedure 2(i)(c). If the bags allow the use of
sampling probe conveniently, the samples should
be drawn by sampling probe.
(b) In case it is not possible to use the sampling

probe, the bags may be opened and fertilizer
material mixed together uniformly by hammering
the big lumps or putting pressure, if required and
then samples drawn by using suitable sample
device.
3. Sampling probe
(i) An appropriate sampling instrument to be used by the
Inspectors for collection of a representative sample is called
sampling probe. The probe may comprise of a slotted single tube
with soil cone tip made of stainless steel or brass. The length of
the probe may be approximately 60 to 65 cms and the diameter
of the tube may be approximately 1.5 cm and the slot width 1.2
to 1.3 cms. The probe may be use if the physical condition of the
fertilizers and the packing material permits it use.
(ii) In case of High Density Polyethylene packing and also

when the fertilizer material is not in free flowing condition, the
use of sampling probe may not be possible. In such a case,
selected bags for drawing samples may be opened and the
fertilizers may be taken out of the bags and spread on a clean
surface and samples drawn with the help of a suitable Sampling
device which may be made of stainless steel or brass cup.
4. Drawal of samples from bags.
(i) Drawal of sample and preparation of composite samples. Draw, with an
appropriate sampling instrument, (sampling probe) small portions of the
material from the selected bags as per procedure in para 2(i) (b) 2(ii)
2(iii)and 2 (iv) (a). The sampling probe shall be inserted in the bag from one
corner to another diagonally and when filled with fertilizer, the probe is
withdrawn and fertilizer is emptied in a container/or on polythene sheet/or
on a clean hard surface and made into one composite sample.
(i) If the bags do not permit the use of sampling probe, empty the
contents of the bags on a level, clean and hard surface and draw a
composite sample by the process of quartering as described under para 3
(ii) or 5.+(iii) In case of chelated micro-nutrients and mixtures of micro-
nutrients, the three identical containers of the batch, grade, type and
manufacturer, shall be selected which shall constitute the composite
samples, provided it is not possible to draw a composite sample of the size
given under para 4A (iii)."
"4A. Weight of one sample
One sample of fertilizer shall have the approximate weight, as specified
below:-
(i) For straight micro-nutrient fertilizers- 100gms.
(ii) For chelated micro-nutrient fertilizers and 50gms or mixtures of
micro-nutrients the maximum packing size of similar quantity
(iii) For other fertilizer and mixtures of fertilizers 400 gms."
5. Preparation of composite sample

If the composite sample collected from the different selected bags is
large than required weight, its size shall be reduced by method of
quartering as detailed below:-
Spread the composite sample on a level, clean, hard surface, flatten it
out and divide it into four equal parts. Remove any diagonally opposite
parts. Mix the tow remaining parts together to form a cone, flatten out
the cone and repeat the operation of quartering till a composite sample
of required weight is obtained.
6. Preparation of test sample and reference sample
(i) The composite sample obtained above shall be spread out on a clean, hard
surface and divided into three approximately equal proportions + each of the
weight as specified in Para 4A. Each of these samples shall constitute the test
sample.
(ii) Each test sample shall be immediately transferred to a suitable container as
defined under para 1(e). The slip with detailed description may be put inside the
sample bag. Each bag shall also be properly labeled as mentioned in Para 1(f)
(iii) Each test sample container shall then be sealed with the seals of the
inspector. If possible, seal of the manufacturer/importer/dealer or purchaser as
the case may be, may also be affixed.
(iv) One sample so sealed shall be sent to the Incharge of the Laboratory notified
by the State Government under clause 29 or Central Fertilizer Quality Control and
Training institute, Faridabad * or Regional Fertilizer Control Laboratories at
Bombay, Madras or Kalyani (Calcutta) for analysis and the second give to the
manufacturer or importer or dealer or the purchaser as the case may be. The
third sample shall constitute the reference sample and shall be sent by the
inspector to his next higher authority for keeping in safe custody for production in
court, if required.
(ii) Sampling procedure
(a) Drawal of samples from the ship of bulk fertilizers
A. Sampling from conveyor belt.
When the material is unloaded from the ships transported to
temporary/storage godowns through conveyor belts, the sample
can be drawn by passing the sampling cup through the entire
stream of material as the material drops from a transfer belt or
spout. The long slot in the top of sampling cup should be
perpendicular to the falling stream. pass the cup through the
complete stream at a uniform speed, so that the cup will collect
approximately equal amounts in each pass but will never
overflow.
A minimum of 10 equally timed and speed stream must be
taken during the transfer operation. However, the stream
samples are not applicable unless uniform continuous flow of
fertilizer is maintained for more than 3 minutes while lot is
being sampled.
(b) Drawal of samples from bulk carriers-trucks etc. The sample can be drawn
as per vertical probing procedure of Association of Official Analytical
Chemists. The sampling probe should be about 4 1/2' to 5' length. Draw 10
Vertical cuts from the following locations relative to the entire top of the
conveyance. The 10 vertical cores are combined into a composite sample.
7 4 8
3 1 2 5
10 6 9
PART B
METHOD OF ANALYSIS OF FERTILIZERS
1. Preparation of sample for analysis in the laboratory

(i) Procedure
(a) Reduce gross sample to quantity sufficient for analysis or grind not < 250
Gm of reduced sample without previous sieving.
(b) For fertilizer materials and moist fertilizer mixtures, that form a paste on
putting pressure, grind in porcelain pestle and mortar to pass sieve with 1mm
circular openings or No. 20 standard sieve.
(c) For dry mixtures that tend to segregate, grind in a porcelain pestle and
mortar to pass No. 40 standard sieve.
(d) Grind as rapidly as possible to a avoid loss or gain of moisture during
operation.
(e) Mix thoroughly and store in tightly stoppered bottles.
Agrochemicals
Dr.T.H.Hanumantharaju
Associate Professor
Definition of a Pesticide
US EPA - any substance or mixture
of substances intended for
preventing, destroying, repelling, or
mitigating any pest. The term pest
means any harmful, destructive, or
troublesome animals, plants, or
microorganisms.
Pesticides
A chemical, physical or biological
agent that destroys or controls pest
organisms
• Common: insecticides, herbicides,
fungicides
• Approximately 500,000 tons applied in
the U.S. each year
• Public health: disease prevention
(malaria, typhus, yellow fever) and
increased agricultural production
Pesticides
DDT Story
• Saved lives through prevention of
malaria, DDT kills mosquito’s
• Banned later as a result of
bioaccumulation in the food chain
• DDT was found in marine sediments,
wildlife, and human lipids
• Caused thinning of eggshells in birds
Pesticides
Many hazardous waste sites have
been created as a result of pesticide
use
Abandoned pesticide manufacturing plants
Mixing and loading areas, surface and GW
contamination
Pesticide Nomenclature
• Common and Trade names used most
often
The farm chemicals handbook
The following is an introduction to different
Pesticides
Pesticides
Insecticides
• Natural products were used for
centuries (nicotine, rotenone)
• Until the “first generation”
Metals – lead arsenate and methylarsenate
• Second Generation
Synthetic organic insecticides
• Organochlorine compounds, DDT 1939
• Organophosphorus ester insecticides,
Pesticides
Insecticides
• Second generation continued
Thousands created from 1940-
1940-1970
Now they are banned
More than 400 insect species have
developed resistance
• Third generation
Natural products and pheremones
Use of these with 2nd generation is called
integrated pest management
Pesticides
Organochlorine Insecticides
• Chlorinated aliphatic and aromatic
compounds
May contain O and S
Highly lipophilic (fat loving
Disrupt the Na+ and K+ balance of cellular
membranes and neurological pathways
Though banned in the U.S. and Europe, still
found in the environment
Degrading slowly in U.S., still manufactured
here and sold overseas
Pesticides
Common organochlorine insecticides
include:
• DDT, methoxychlor, lindane, aldrin,
dieldrin, and endosulfan
Organophosphorus esters
• Nonselective, broad spectrum
insecticides that inhibit acetyl
cholinesterase, an important enzyme for
neurological function
History of Pesticides
Sulfur used as a fumigant by the Chinese
before 1000 B.C. and as a fungicide in the
1800s in Europe against powdery mildew
on fruit; Sulfur containing compounds are
still used in CA today.
The Chinese applied moderate amounts of

arsenic--containing compounds as
arsenic
insecticides in the 16th century. In the
1800s arsenic trioxide was used as a weed
killer.
History (Continued)
The 1930s ushered in the era of modern
synthetic chemistry.
By the beginning of WWII there were a

number of synthetic pesticides.
Pesticides
It is important to appreciate
• despite the modern day development of
second-- and third
second third-- generation
derivatives of the early chemical
pesticides, all pesticides are inherently
toxic to some living organism, otherwise
they would be of no practical use.
• There is no such thing as a completely
safe pesticide.
Human Problems
Target species and nontarget species can
be affected.
On a world wide basis, intoxications due to
pesticides are estimated to be 3 million
cases of acute, severe poisoning annually
with an equal number of unreported
cases, and some 220,000 deaths.
In CA, ~ 25,000 cases of pesticide-
pesticide-
related illness occur annually among
agricultural workers. National ~ 80,000
cases per year.
Pesticide Regulation
Studies related to environmental impact
on birds, mammals, aquatic organisms,
plants, soils, environmental persistence,
and bioaccumulation are required.
The average development cost for a new

pesticide is on the order of 30 - 50 million
$.
Insecticides
All of the chemical insecticides in use
today are neurotoxicants and they
act by poisoning the nervous system
of target (also non-
non-target)
organisms.
Classes of Insecticides:
• Organochlorine Insecticides
• Organophosphate/Carbamate
Insecticides
• Pyrethroid Insecticides
Organochlorine Insecticides
The organochlorine (chlorinated
hydrocarbon) insecticides are a diverse
group of agents belonging to the following
chemical classes:
• dichlorodiphenylethanes
• chlorinated cyclodienes
• chlorinated benzenes
• chlorinated cyclohexanes
Organochlorines (Continued)
These agents were used extensively from
the mid 1940s to the mid 1960s in all
aspects of agriculture and forestry,
building and structural protection, and in
human situations to control a wide variety
of insect pests.
Properties which made them good
insecticides:
• low volatility
• chemical stability
• lipid solubility
• slow rate of biotransformation and
degradation
These properties also led to their demise
because of their persistence in the
environment, bioaccumulation, and
biomagnification through the food chains.
Studies in wildlife species and laboratory
animals have demonstrated potent
estrogenic and enzyme-
enzyme-inducing
properties, which interfere with fertility
and reproduction.
• In birds, the interference is related to steroid
metabolism and the inability of the bird to
mobilize sufficient calcium to produce a strong
eggshell. Eggshell cracking allows bacteria
into the egg, which kills the embryo.
• Reproduction in fish is affected by the
bioconcentrations of these agents in the
yolk--sac of fry.
yolk
• The o,p'
o,p'--isomer of DDT has been shown
to compete with estradiol for binding
with the estrogen receptor in rat uterine
cells.
Typical Mechanism of Action
For DDT Type Pesticides:
• periodic sequences of persistent tremoring
and/or convulsive seizures suggestive of
repetitive discharges in neurons.
• these tremors, seizures can be initiated by
tactile and auditory stimuli, indicating that the
sensory nervous system appears to be much
more responsive to stimuli.
Chlorinated Cyclodiene-
Cyclodiene-, Benzene
Benzene-- and
Cyclohexane-- type Insecticides
Cyclohexane
These insecticides act in the CNS.
• (1) Mimic the action of the chemical
picrotoxin, a nerve excitant and
antagonist of the neurotransmitter
GABA found in the CNS.
GABA induces the uptake of chloride ions by
neurons.
• The blockage of this uptake results in
only partial repolarization of the neuron
and a state of uncontrolled excitation.
(Continued)
• (2) Inhibitors of Na/K ATPase and
Ca/Mg ATPase that is essential for the
transport of Ca++ across membranes.
The inhibition of Ca/Mg ATPase located in
synaptic terminals of neurons results in an
accumulation of intracellular free Ca++
which stimulates neurotransmitter release,
depolarization of adjacent neurons, and
propagation of stimuli throughout the CNS.
Metabolism of Compounds
Very slow rate for DDT due to complex
aromatic ring structure and chlorination.
Half--life is 335 days in cattle.
Half
DDT broken down to DDE both

nonenzymatically and by cytochrome P450
reductive dechlorination. All metabolites
are highly lipophilic.
Metabolism (Continued)
Biotransformation is also slow for
cyclodiene--type insecticides.
cyclodiene
Aldrin and Heptachlor are converted by

cytochrome P450 oxidation reactions to
dieldrin and heptachlor epoxide without a
change in lipid solubility or toxicity.
Why Prolonged Repolarization
(1) DDT affects the permeability of the
nerve cell membrane to K+ ions reducing
K+ transport across the membrane.
(2) DDT alters the Na+ channels, they
open normally but are closed (inactivated)
slowly.
(3) DDT inhibits neuronal ATPase activity
particularly Na/K ATPase and Ca ATPase
which play a role in repolarization of the
neuron.
Why (Continued)
All of these factors reduce the rate at
which repolarization occurs and
increase the sensitivity of the
neurons to small stimuli that would
not elicit a response in a fully
repolarized neuron.
Pyrethroid Insecticides
This is the newest class of insecticides, a
group of chemicals that entered the
marketplace in 1980 but by 1982
accounted for approx. 30% of worldwide
insecticide use.
These synthetic chemicals are similar to
the insecticides extracted from pyrethrum
or chrysanthemum flowers.
Pyrethroids (Continued)
Type I pyrethroids affect Na+ channels in
nerve membranes (both sensory and
motor) and gives long afterpotential
similar to DDT.
Type II pyrethroids cause persistent
depolarization and prolonged repetitive
firing of sensory receptors and muscle
fibers.
Both types also inhibit Ca/Mg ATPase
resulting in increased intracellular Ca++
levels and increased neurotransmitter
release.
Organochlorine Pesticides
Background Information
7 Common Characteristics
5 Major Groups of OC’s
Background
DDT’s success stimulated the
production of several OC pesticides
Successful eradicators
Severe toxic effects
Currently in the U.S. and Europe
OC’s are not a major pesticide, but
they are in developing countries and
tropical regions
Cost--benefit
Cost
7 Common Characteristics
1. Atomic structure
2. Lipid solubility
3. Persistence
4. Bioaccumulation
5. Toxicity
6. Physiological Response
7. Interactions
1. Atomic Structure
Characterized by the presence of
carbon, chlorine, and hydrogen
(sometimes oxygen)
Cyclic carbon chains (benzene ring)
Atomic Structure
2. Lipid Solubility
High lipid solubility (non-
(non-polar)
High log Kow
Stored in lipids/fat
• Fasting can cause reentry into
circulation
The concentration in biota has
decreased since the banning of
several OC’s
3. Persistence
Persistence is based on the half lives
in the organism and in the
environment
Stable compounds
Physical and biological influences
• Environmental
• Organism
Persistence Cont.
Dependent on the compound…
• Aldrin is rapidly metabolized
• Endrin and dicofol have short half lives
in an organism and in the environment
• DDT, it’s metabolites and dieldrin are
extremely persistent
4. Bioaccumulation
Accumulation of pesticides through
absorption through skin, gills, or food
Bioconcentration and
biomagnification
Aquatic organisms vs. terrestrial
organisms
5. Toxicity
Biochemical lesions
Neuroactive agents
Ingestion, inhalation and dermal
absorption
Mortality
• Lethal brain and liver residues indicate
biochemical lesions
Influences on toxicity
Toxicity Cont.
DDT
• Acts on CNS by interfering with ion movement
through neuronal membranes
• 4 mechanisms
Na2+ and K+
ATP
Ca 2+ inhibition
Ca2+Mg2+
• Maintain depolarization, which leads to
hypersensitive neurons
• Persistent tremoring, seizures or convulsions
Toxicity Cont.
Cyclodienes
• Alter the neurotransmitter gamma
gamma--
aminobutyric acid (GABA)
• Inhibit Na2+, K+, and Ca2+Mg2+ channels
HCH
• Block chloride ion
• Alter Ca2+ levels
6. Physiological Response
Induced enzyme activity
• Species variations
Persistence and excretion
Endocrine disruptors
7. Interactions
Synergism, potentiation,
antagonism, or additive toxic effects
• Antagonistic: Japanese quail were
treated with chlordane and later with
parathion
• Synergism: Aldrin increases the storage
of DDT
• Additive effects are most common for
industrial chemicals and pesticides
5 major groups of OC’s
1. Dichlorodiphenylethane
• DDT, dicofol, and methoxychlor
2. Cyclohexane
• Hexachlorocyclohexane (HCH)
3. Chlorinated cyclodiene
• Aldrin, dieldrin, and endrin
4. Toxaphene
5. Mirex and chlordecone
DDT, DDD, and DDE
(Dichlorodiphenylethane)
Paul Muller (1939)
Subsequent discovery of large-
large-scale
mortality of birds, insects, and
invertebrates
Determination lethal brain residues
DDE
DDT, DDD, and DDE Cont.
Adverse affects on wildlife
• Avian populations
Brown pelicans
Peregrine falcons
Osprey and bald eagles
• Fish and bats
DDT, DDD, and DDE Cont.
DDD sprayed 3 times on Clear Lake,
which lead to bioaccumulation data
Resistance to DDT
DDT was banned in 1972
DDT has estrogenic activity
Aldrin/Dieldrin (cyclodiene)
Very toxic
Aldrin is quickly transformed into Dieldrin
• Aldrin/Dieldrin spraying in 1960 and 1961 for
Japanese beetles
• Whistling ducks, snow geese, and others
• Gray bats in Missouri
The combined effects of DDE and Dieldrin
Aldrin/Dieldrin were banned in 1974
Endrin (cyclodiene)
Short half life, but very acutely toxic

• Brown pelican
• Voles, birds, and quail
Metabolic pathways
• 12
12--Ketoendrin is more toxic than endrin
Endrin was banned in 1979
Hexachlorocyclohexane (HCH)
(Cyclohexane)
Lindane (gamma isomer)
Persistent or easily eliminated?
Veterinary and human medicine
Some isomers were voluntarily
canceled by the primary
manufacturer in 1978; lindane is still
in use
Dicofol (dichlorodiphenylethane)
Produced from DDT

Persistence or Elimination?
• Adverse affects on wildlife
• Ecotoxicological studies
Dicofol products that contain >1% of
DDT ceased in 1989, products with
<1% are still in use
Methoxychlor
(dichlorodiphenylethane)
Replaced DDT in treating Dutch elm
disease
Rapidly broken down
Estrogenic activity
Still in use
Organophosphate / Carbamate
Pesticides
~ 200 different organophosphate

insecticides
~ 25 different carbamate insecticides
These two types of insecticides are

considered together because they have a
similar mechanism of action.
(Continued)
Organophosphorus insecticides were first
synthesized in 1937 by German chemists
as potential chemical warfare agents.
• Sarin is an organophosphate compound that
was used against Kurdish people in northern
Iraq in 1988.
The first carbamates were synthesized in

the 1930s as fungicides.
Mechanism of Action
Both organophosphate and carbamate
insecticides act by inhibiting the action of
acetylcholinesterase (AchEase) at the
synapse between two neurons or between
a motor neuron and a muscle.
• AChEase is the enzyme responsible for the
breakdown of the neurotransmitter
acetylcholine (ACh).
• Organophosphate compounds are irreversible
inhibitors of AChEase while carbamate
compounds are reversible inhibitors of
AChEase.
Mechanism (Continued)
The reaction between an organophosphate
and the active site on AChEase (a serine
hydroxyl group) results in the formation of
an intermediate that undergoes partial
hydroylsis with the loss of the "Z" group,
leaving a stable, phosphorylated,
permanently inhibited enzyme.
Signs and symptoms are prolonged and
persistent. Without intervention, the
toxicity will persist until sufficient amounts
of "new" AChEase are synthesized in 20 to
30 days.
Carbamate compounds attach to the
serine hydroxyl group, the "X" group
is removed by hydrolysis forming a
carbamylated enzyme, and then
decarbamylation occurs regenerating
free, active AChEase.
• Carbamate pesticides are really just
poor substrates for AChEase.
Metabolism
Both types of insecticides undergo
extensive metabolism in all forms of life.
The routes and rates are highly species
specific. Both phase I and phase II
mechanisms are involved.
• One reaction, oxidative desulphuration, results
in a significant increase in toxicity. In
parathion, methyl parathion and malathion,
the presence of the P = S reduces the AChEase
inhibiting properties of the compound.
There is a characteristic prolongation of
the falling phase of the action potential.
The nerve membrane remains in a
partially depolarized state and is
extremely sensitive to complete
depolarization again by very small stimuli.
Pesticides
Organophosphorus esters
• Discovered in 1854, use didn’t start until the
1970’s when the organochlorines were banned
Very low half-
half-life, persist for days or weeks, not
years like organochlorines
Acutely toxic however
3 drops of parathion applied to the skin will kill the
average adult
• Common names
Parathion most widely used, Methyl Parathion,
Malathion, and Diazinon
Pesticides
Insecticides
• Carbamate Esters
N-methyl carbamates modeled after the
natural product physostigmine, a neurotoxic
alkaloid
First developed in 1954, by 1985 25
carbamates had been developed
Derivatives of carbamic acid, which is so
unstable that it does not exist
HO-C-NH2
O
Pesticides
Insecticides
• Carbamate Esters
However, replacing the H attached to the
oxygen with an alkyl group and one H
attached to the amino group with a methyl
Creates a stable molecule
Carbamates also interfere with acetyl
cholinesterase
Common names include: carbaryl,
carbofuran, and aldicarb
Pesticides
Herbicides
• Agents that destroy vascular plants and
are employed mainly as weed killers
Most widely used class of pesticides
Last in the environment from a few days to
over a year
Degradation rates are a function of the
herbicide structure and the environmental
conditions
Pesticides
Herbicides
• Kill through a variety of mechanisms
Interference with DNA replication
Mimicking growth hormones
120 different compounds
20 families
Review of five families
Pesticides
Herbicide families
1. Acid Amides – alachlor,
alachlor, propanil
propanil,,
Exact mechanism of kill unknown, appears to
interrupt protein synthesis and nucleic acid
replication
2. Aliphatics – Glyphosate (Roundup), Methyl
Bromide
Interference with amino acid synthesis
3. Phenoxy Herbicides – 2,4
2,4--D, 2,4,5-
2,4,5-T and
Silvex
Phenyl ethers with an oxygen link to the benzene
ring
27,000 tons of 2,4-
2,4-D used per year in U.S.
Agent Orange used in Vietnam was 50:50 mixture
of 2,4-
2,4-D and 2,4,5-
2,4,5-T
Mimics auxins – growth regulators produced by
plants
Pesticides
Herbicides
4. Substituted Ureas
Urea – a bound form of N excreted by animals
Common diuron and linuron
5. Trazines
Predominantly N-
N-alkylated derivatives of 2-
2-chloro-
chloro-
4,6--diamino-
4,6 diamino-s-triazine
Most common are atrazine, cyanazine, and senecor
Work by interfering with photosynthesis
Work well because they lose their phytotoxicity
within one growing season and are not very toxic to
humans
Pesticides
Fungicides
• Destroys fungi and molds to prevent the
deterioration of fruit, grain, and
vegetables
• 70% of fungicides used are from
ethylene--bis
ethylene bis--dithiocarbamates (EBDC’s),
captan, and benzimidazoles
• Some contain manganese and zinc
(Mancozeb and EBDC)
Pesticides
Fungicides
• Pentachlorophenol (penta or PCP)
Used to preserve telephone poles and
railroad ties
Also as an insecticide, fungicide, aracacide,
herbicide, disenfectant, etc
Hundreds of Hazardous Waste sites are
contaminated with PCP
PCP is only moderately toxic, but when
degraded dioxins are produced from it and
they are highly toxic and biorefractory
Pesticides
Soil Fumigants
• Used to control a range of pests
• Early fumigants include (HCN) hydrogen
cyanide and carbontetrachloride
• Resulted in GW contamination
Polychlorinated Biphenyls
(PCBs)
PCB’s
• Heat stable oils once used as transformer and
hydraulic fluids
• Non flammable transformer dielectric cooling
oil
• Mineral oil was used but PCB was more stable
• Also used as a plasticizer and lubricant until
banned in 1979
• Basic unit aromatic hydrocarbon biphenyl, 10
possible Cl positions on two rings
• 207 Congeners – compounds formed from the
same process
Polychlorinated Dibenzodioxins
and Dibenzofurans
PCDD’s and PCDF’s
• Not produced for a potential use
• Waste products of production
Trace impurities formed during the
chlorination or combustion of organic
compounds
• Extremely toxic compounds
A low concentration can be found in burning
wood
Aromatic and non-
non-planar
75 possible congeners
Metals and Inorganic Nonmetals
Metal defined as an element that:
1. Conducts electricity
2. Has a high thermal conductivity
3. Has a high density
4. Characterized by malleability and
ductility
Most metals wastes is produced
during electroplating
Arsenic (As)
Has a complex chemistry
Used to make herbicides to control weeds
Used to make glass, growth stimulants for
plants and animals, and fungicides
Used in semiconductor production
Cadmium (Cd)
Found in plastics, household batteries,
electronics, pigments and appliances
Metals finishing
Highly toxic, range of health effects from
hypertension to cancer
Chromium (Cr)
Used in electroplating, leather tanning,
wood preservation, catalysts and
commercial electronics
Lead (Pb)
Used in autobatteries, electronics, plastics and glass
Ubiquitous in the environment after use in gas and
paint
Nickel (Ni)
Used in stainless steel, iron ferrous alloys,
electroplating, catalysts, ceramics, and salt
Mercury (Hg)
Found in three forms, elemental, inorganic, and
organic
Used to make electrical products, dental supplies,
caustic soda, chlorine, instruments ,and paints
Cyanides (CN-)
An inorganic nonmetal anion
HCN CN- + H+ Ka = 7.94 x 10-10
Hydrogen cyanide, highly toxic, acute
poison
HCN produced by mixing ammonia and
methane under controlled conditions
Used in electroplating, stored in ponds,
caused dead wildlife and GW contamination
Asbestos
Generic label attached to fibrous metal
silicates of sodium, magnesium, calcium,
and iron
Asbestos is a commercial label given to six
mineral fibers made from magnesium
silicates
Uses: roofing products, friction products,
asbestos cement pipe, packing, and paper

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Department Soil Science and Agricultural Chemistry

University of Agricultural Sciences, GKVK, Bangalore

1. Degree : B.Sc.(Agri.)/ B.Sc.(AgMaCo)

2. Class : III B.Sc.(Agri.)

4. Course No : SAC 301

5. Course Title : Manures, Fertilisers and Agro-chemicals

6. Credit hours: : 1+1

SAC 301, Manures, Fertilizers and Agro-Chemicals, (1+1)

Class and Section Course Teachers

Scheme of Evaluation Max. Marks

SAC 301 (1+1), Manures, Fertilisers and Agro-chemicals

Dept. of Soil Science and Agricultural Chemistry

This is to certify that Mr./ Ms _____________________________bearing

Date Signature of the Teacher

Sl. Page Remarks

Study of manures and fertilisers

The word manure is originated from French “Mano-euvrer” which refers

Manures/ Organic manures

Classification of manures and fertilizers

ii) Concentrated organic manures

2) Compost: Compost is an organic manure prepared from plant residues and

5) Green manures: Green manuring is the process of growing of a quick

Table 2. Average nutrient contents (%) of sewage and sludge

Table 3. Nutrient contents (%) of oil cakes

Table 4. Nutrient content of some of the concentrated organic manure

ii) Particle size

iv) Granule hardness

v) Moisture content/ hygroscopicity

ii) Artificial manures

2. Nature of the materials present/ presence or absence of carbon in the

ii) Inorganic manures

3. Number of nutrient element present in fertilizer

ii) Complex/ compound manures

4. Physiological property of the fertiliser

ii) Basic fertiliser

iii) Neutral fertiliser

5. Amount of nutrient content in the fertiliser

ii) High analysis fertilizer

Natural Synthesised Plant origin Animal origin Processed

Nitrogenous Phosphatic Potassic Compound Complex Mixed

Ammonium Nitrate Ammonium & Amide Plant origin Animal origin

Natural Treated/ Industrial Synthetic

Natural Processed Synthetic

2) Ammonium chloride (26 % N): It is sometimes called muriate of ammonia.

3) Ammonium nitrate (33 % N): Ammonium nitrate is decreasing in

4) Calcium ammonium nitrate (26 % N): It is produced by granulating

5) Ammonium sulphate nitrate (26 % N): It is a double salt of ammonium

10) Calcium cyanamide (26 % N): It is a calcium compound used as fertiliser,

2) Concentrated superphosphate (46% P2O5): It is also known as triple

3) Monoammonium phosphate (11-48-0): MAP is a dry material being used

4) Diammonium phosphate (18-46-0): DAP is a dry material being used

5) Polyphosphates: Polyphosphates differ slightly from the more common

2) Sulphate of potash (50 % K2O): Potassium sulphate also referred to as

3) Potassium nitrate (44 % K2O): It is also known as nitrate of potash, is being

Determination of nitrogen in organic manures

(NH4)2SO4 + NaOH Na2SO4 + NH3 + H2O

(NH4)3BO4 + H2SO4 (NH4)2SO4 + H3BO4

II. Distillation of the sample

III. Titration of the sample