Manures Fertilizers & Agrochemicals

Author
TNAU

Edited By
 Index
Sn Lecture Page No
1 Manures – types, composition and value - sources 5-7
2 Green manures-Oilcakes-Sewage sludge-Biogas plant slurry-Plant and 8-10
animal refuges
3 Composting of organic wastes – composting technologies 11-17
4 Classification of fertilizers – N, P and K fertilizers 18-21
5 Nitrogenous fertilizers – sources – fundamental processes involved in 22-31
manufacturing procedures for ammonia, sulphuric acid, nitric acid and
phosphoric acid
6 Manufacturing of ammonium sulphate, ammonium nitrate and 32-35
ammonium chloride
7 Manufacturing of urea 36
8 Slow release N fertilizers – chemically modified forms – urea- 37-42
formaldehyde, IBDU, CDU.
9 Controlled release fertilizers and reaction in soil 43-44
nitrification inhibitors – criteria and
advantages
10 P fertilizers – rock phosphate – bone meal – basic slag 45-51
11 Single and triple super phosphates – thermosphosphates – method of 52-54
manufacturing
12 Potassic fertilizers –manufacturing of KCl, K2SO4 and schoenite 55-61
13 Secondary and micronutrient fertilizers- Manufacturing Zinc sulphate, 62-63
and ferrous sulphate
14 Complex fertilizers – manufacturing ammonium phosphates – nitro 64-66
phosphates and NPK complexes
15 Mixed fertilizers – sources – preparations- their compatibility – 67-72
advantages
16 Amendments-calcium sulphate and calcium carbonate 73-74
Midsemester examination 75
17 Biofertilizers- symbiotic and non symbiotic and their advantage 76-92
18 Impact of fertilizers on the environment 93-99
19 Fertilizer control order and Fertilizer storage 100-109
20 Organic chemistry as prelude to agrochemicals- -Diverse type of 110
agrochemicals
21 Pesticides formulations - sprays - emulsion concentrates- water 111-113
miscible liquids-dusts - wettable powders and flowables - manufacture,
characteristics and uses.
22 Pesticide formulation - granules, fumigants and aerosols - Manufacture 114-116
- Characteristics and use. Insecticide classification - Organochlorines -
 Mode of action - lindane, endosulfan - Characteristics and use.
23-24 Organophosphates - characteristics, preparation and use of 117-121
monocrotophos, phosphamidan, and chlorpyriphos. Phorate, phosalone,
dimethoate and quinalphos.
25 Carbamates - characteristics, preparation and use of Carbaryl, 122-125
carbofuran, carbosulfan and aldicarb.
26 Botanicals - characteristics, preparation and use of neem products, 126-128
nicotine and pyrethrum.
27 Characteristics, preparation and use of synthetic pyrethroids – 129-131
Fenvalerate and Cypermethrin.
28 Herbicides - Mode of action -Classification of organic herbicides - 132-139
Characteristics - Use of 2, 4-D. , Butachlor, Glyphosate, Atrazine and
Benthiocarp
29 Fungicides - Classification - Inorganics - characteristics, preparation 140-143
and use of sulfur and copper - Mode of action - Bordeaux mixture and
copper oxychloride
30 Organic fungicides - Mode of action - Dithiocarbamates - 144-147
characteristics, preparation and use of Zineb and maneb.
31 Systematic fungicides - Benomyl, carboxin, oxycarboxin, Metalaxyl, 148-158
Carbendazim, characteristics and use.
32 Insecticide act-Compatibility of pesticides with fertilizers and other 159-170
Agrochemicals.
33 Fate of pesticides in soil and plant. 171-178
34 Plant growth regulators 179-181
Reference 182
Manures Fertilizers & Agrochemicals

01. Manures – types, composition and value – sources

There are many ways of classifying the fertilizers and manures, the classification being
based on one or two properties of the materials.
Nature of source
1.Natural manures
2.Artificial manures
3.Mineral manures
Nutrient content
1.Single manures
2.Compound manures
Nutrient element present
1.Complete manures
2.Incomplete manures
Nature of the materials
1.Organic manures
2.Inorganic manures
3.Indirect manures
Nature of action
1.General manures
2.Special manures
3.Stimulative substances
4.Soil amendments or soil conditioners

Critical consideration of the above-mentioned classification reveals that none of

the classification is satisfactory. Each of the classification is based on only one property
and nay not be suitable to cover wide range of materials.
They are generally classified in to Bulky organic manure and concentrated organic
manures

ORGANIC MANURES
The word manure derived from the French "Manoeuvrer', means to manipulate,
to work, to produce crop. In general manure means excreta of animals. The term bulky
organic manure generally includes those materials of natural origin, organic in
composition having greater volume per unit content of nutrients and being used to
5 AgriMoon.Com
Manures Fertilizers & Agrochemicals

increase the nutrient status of the soils as well as organic matter content of soils. They
are obtained mainly as natural products. The materials included in this group are
farmyard manure, compost, sewage sludge and green manure. Of these FYM, compost
and green manure are the most important and widely used bulky organic manures.
Farm Yard Manure (FYM)

The FYM refers to the refuse from farm animals, mainly sheep, cattle and poultry.
This is one of the oldest manure known and is highly valued for its many of the beneficial
properties that are said to be produced when this manure is added to the soil. It not only
adds the constituents to the soil but also adds organic matter to the soil.

Composition of farm manure

Several factors influence the composition of farm manure and they are the
following
1. Source of manure
2. Feed of the animals
3. Age of the animals
4. Condition of the animals
5. Manner of storage and handling
6. Litter use etc.,
On an average the composition of FYM is usually 0.5 % N, .25 % P2O5 and 0.5 %
K2O.

Methods of collection

Many methods of collecting the cattle manure are in vogue and this include,
1. Use of ordinary cattle shed with kacha floor
2. Use of cattle shed with impermeable floor and provision for collecting urine in
separate urine pit
3. Dry earth system
4. Loose box system
5. Other special methods

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 FYM
1. The heap method

6 AgriMoon.Com
Manures Fertilizers & Agrochemicals

2. The pit method

Various losses during collection and storage of FYM can be prevented or atleast
minimized by adopting the following procedures
1. Better methods of collection
2. Better methods of storage
3. Use of cow dung gas plant
4. Use of chemical preservatives like gypsum, superphosphate etc

Organic Wastes :
Organic wastes are the wastes of biological / animal / agro-industry origin and
can be converted to valuable manure by composting. The various organic wastes can be
classified as follows,

Sources of Organic Wastes

Agriculture Animal Agro-industries Municipal Activities

Husbandry
∗ Crop residues (paddy ∗ Dairy ∗ Sugar Indutry ∗ Household /
straw, sugacane ∗ Goat / Sheep (Pressmud) municipal solid
trash etc) ∗ Poultry ∗ Coir Industry (Ciorpith) waste
∗ Weeds ∗ Piggery ∗ Fruits / vegetables ∗ Market waste
processing industries (Vegetable/ fruit /
∗ Sago Industry flower market)

7 AgriMoon.Com
Manures Fertilizers & Agrochemicals

02. Green manures-Oilcakes-Sewage sludge-Biogas plant slurry-Plant and animal

refuges

GREEN MANURES
Green manure:
Growing the plants in-situ and incorporation in the field.
Green leaf manure
Addition of green or plant tissues obtained from elsewhere viz., trees, herbs, shrubs
pruning andunwanted weeds.
Benefit of Green manure or Green leaf manures
a. Addition of organic matter.
b. Adds Nutrient – Macro, Secondary and micro nutrients.
c. It improves physical condition of soil.
d. Act as a soil amendment to reclamation of problem soils.
e. It act as a cover or catch crop to prevent soil erosion, conserve moisture, prevent
nutrient leaching.
f. Leguminous crops fix the atmospheric – N by the roots and improves N status of the
soil.
Characteristics of Green manure
1. It should have rapid growth and shorter duration so that can be fitted in a crop rotation
2. It should yield abundant biomass and should be succulent to have rapid
decomposition
3. It should have the ability to grow on poor soils.

Nutrient content of agricultural wastes

Agricultural wastes N P2O5 K2O

Sugarcane Begasse 0.25 0.12 0.20

Sugarcane Begasse 1.40 0.45 0.60

compost
Sugarcane Begasse 1 – 1.5 2.0 -
Press mud

8 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Press mud – compost 1.5 1.5 -

Saw dust Traces 0.2 -

0.25
Tobacco waste 0.5 – 1.0 0.8 1.0

Tobacco seed cake 4 – 4.5 7 – 15 5 – 5.5

Tea waste 2.8 – 3.6 03. – 0.4 1–2

Cotton dust 1 – 1.5 - -

Textile waste 1 – 1.5 - -

Nutrient content of Commonly used Concentrated manures

Oil cake N P2O5 K2O

Groundnut cake (Decordicated) 7.8 1.5 – 1.4

1.9
Lin seed cake 5.5 1.4 1.2

Mustard cake 4.5 1.5 1.0

Neem cake 5.2 1.0 1.4

Niger cake 4.8 1.8 1.0

Pungam cake 2.5 1.0 1.0

Safflower (decordicated) 7.8 2.2 2.0

Sesamum 6.2 2.0 1.2

Castor 5.8 1.8 1.0

Coconut 3.2 1.8 1.7

Slaughter House wastes

Wastes N P2O5 K2O

Blood meal 10 – 12 1.2 1.0

Meat meal 10.5 2.5 0.5

Fish meal 4 -10 3–9 0.3 – 1.5

Horn – Hoff meal 13 - -

9 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Leather - waste 7 0.1 0.2

Hair and wool waste 12.3 0.1 0.3

Sewage water 25ppm 5 ppm 15 ppm

Sludge 1.5 – 3.5 0.75 – 4 0.3 – 0.6

Nutrients content of Commonly used Green manures

Green manure N% P2O5% K2O %

Sunhemp 0.5 0.1 0.4
Danicha 1.1 0.2 0.4
Sesbania 0.7 0.1 0.6
Pelli pesera 0.7 0.2 0.4
Cluster bean 0.3 0.1 0.3
Cow pea 0.7 0.2 0.6
Green leaf manure
Kolungi 0.7 0.1 0.4
Calotropis 0.3 0.1 0.6
Pungam 1.2 0.2 0.8
Glyricidia 0.8 0.1 0.7
Puvarasu 0.8 0.2 0.9

Guano - Birds Excreta or bat Dung

Guano 2.6 4.2 0.6

10 AgriMoon.Com
Manures Fertilizers & Agrochemicals

03. Composting of organic wastes – composting technologies

COMPOSTING OF ORGANIC WASTES
Composting is a process of allowing organic materials to decompose more or
less controlled conditions to produce stabilized product that can be used as a manure or
soil amendment. Composting is basically a microbial process, which change the property
of the organic material or mixtures.
Compost is the material resulting from the decomposition of plant residues under
the action of bacteria and fungi. Composting is simply an acceleration of natural process
or organic matter mineralization. The final product is dark brown in colour and resembles
FYM in its properties and appearance.
Essential requirements for composting
A bulky organic manure
A suitable starter
Addition of enough water
Aeration
Main systems of composting
ADCO process (Hutchinson and Richards of England)
Activated compost process (Fowler and Rege)
The Indore process (Howard and Wad)
The Bangalore process (C.N.Acharya)
The coimbatore method
Benefits of composting:
∗ Enables clean environment
∗ Absorbs odors, degrade toxic substances and heavy metals
∗ Avoids un-necessary dumping of wastes
∗ Supply valuable organic manure
Composting technologies
1. Crop residue composting
 Collect the available crop residues and weeds
 Shred them to a size of 2 to 2.5 cm length
 Mix these wastes with green residues (freshly collected), if available
 Form the compost heap ( 4 feet height)
 Add the bio-inoculants (2 kg of bio-mineralizer or 40 kg of cowdung for 1 tonne of
waste)

11 AgriMoon.Com
Manures Fertilizers & Agrochemicals

 Properly aerate the compost either by providing perforated PVC pipes or by

mechanical turning
 Maintain the moisture at 60 % by regular watering
 The compost will mature in 60 days
2. Vermi-composting
Vermicomposting is a process of degradation of organic wastes by earthworms.
The species like Eisenia foetida and Eudrilus eugeniae are effective in converting the
agricultural wastes into compost. The various steps involved in making vermicompost
are as follows
Methods followed:
Heap method
Pit method – aboveground and belowground
Belowground method pit size : 10 X 1 X 0.3 m
Each layer : 6-7cm thick
Sprinkle water once in 8-10 days
Release : 2-2.5 kg worms / pit
Steps:
Collect the predigested wastes and mix cattle dung @ 30 %.
Place it in the pit/container layer by layer
Moist the residues at 60 % moisture
Allow the verms in to the feed material / residues @ 1 kg/ tonne of residue
Protect the pit or container from ants and rats (which are the enemies of
verms)
The residue will be composted in 30 to 40 days
Remove the composted materials layer by layer at a weekly interval so as
To avoid any damage /disturbance to the feeding verms.

Nutritive value of vermicompost

The nutrients content in vermicompost vary depending on the waste materials
that is being used for compost preparation. If the waste materials are heterogeneous
one, there will be wide range of nutrients available in the compost. If the waste materials
are homogenous one, there will be only certain nutrients are available. The common
available nutrients in vermicompost is as follows
Organic carbon = 9.5 – 17.98%
Nitrogen = 0.5 – 1.50%

12 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Phosphorous = 0.1 – 0.30%

Potassium = 0.15 – 0.56%
Sodium = 0.06 – 0.30%
Calcium and Magnesium = 22.67 to 47.60 meq/100g
Copper = 2 – 9.50 mg kg-1
Iron = 2 – 9.30 mg kg-1
Zinc = 5.70 – 11.50 mg kg-1
Sulphur = 128 – 548 mg kg-
3. Coirpith composting
Coirpith is an agricultural waste produced from the coir industry. Approximately
180 grams of coirpith is obtained from the husk of one coconut. Coirpith contains Carbon
: Nitrogen in the ratio of 112:1 and contains 75 per cent lignin which does not permit
natural composting as in other agricultural wastes.
Mushroom Pleurotus has the capacity to degrade part of the lignin present in
coirpith by production of enzymes like cellulases and lactases. The carbon: nitrogen ratio
of coirpith is reduced from 112:1 to 24:1 as a result of composting.
Composting method
Select a shaded place of 5 x 3 m dimension and level it after removing weeds. Spread
100 kg of coirpith uniformly. Spread 100 g of Pleurotus spawn on this and cover with a
second layer of 100 kg of coirpith. On the surface of the second layer, spread one kg of
urea uniformly.
Repeat this sandwiching of one layer of coirpith with spawn followed by another layer of
coirpith with urea up to one metre height.
Sprinkle water to keep the heap moist. Allow the heap to decompose for one month.

Manure conversion
The coirpith is converted into good manure after 30 to 40 days and the lignin content is
reduced from 40 per cent to 30 per cent. The nitrogen content is increased from 0.20 per
cent to 1.06 per cent. Coirpith compost contains macronutrients and micronutrients. It
can absorb water up to eight times its weight. Coirpith, when added to sandy soil at 2 per
cent increases the water holding capacity up to 40 per cent. It can be applied to a wide
variety of crops and can be used to prepare potting mixture and can be applied as
organic manure in kitchen gardens.
4. Composting of crop residues and weeds:

13 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Composting is one of the useful ways for utilizing the some of the weeds and
noncommercial plants like Parthenium, Water hyacinth, lpomoea etc. instead of their
eradication. The plants can be composted using Trichoderma viridi and Pleurotus sajor-
caju as a microbial consortium with supplementation of urea. Select an elevated shady
area of a thatched shed and mark an area of 5x1.5 meter. Cut the composting materials
into 10 – 15 cm size. Spread 100 kg of these materials over the marked area. Sprinkle 1
bottle of microbial consortia over this layer. Again spread another 100 kg of composting
materials over this layer. Spread 1 kg of urea uniformly over this layer. Likewise repeat
these processes of spreading composting materials, then microbial consortia, again
composting materials followed by urea application until a minimum of 1-meter height is
reached. Sprinkle water to attain a moisture level of 50% to 60%. The surface of the
heap is covered with a thin layer of soil. Water should be sprinkled depending upon the
necessity to maintain the moisture around 50%. A turning is given at the end 20 days to
give a thorough mixing of outside material with that of the inside ones. The bio-converted
compost will be ready in about 40 days time.

5. Method of composting the Municipal Solid Wastes

Biodegradable municipal solid waste should be separated and collected for

composting. Five hundred kg of material should be heaped in the compost yard. In that
heaped waste, 1 kg of TNAU microbial consortium should be applied in the form of slurry
to cover the full waste material. This 1 kg microbial consortium can be mixed with 5 litres
of water to make slurry. This slurry is sufficient to cover 0.5 tonne of material Then, 50
kg of cowdung should be mixed with 30 litre of water to form cowdung slurry. This cow
dung slurry should be sprayed over the heap of municipal solid waste Then, 1 kg of urea
should be mixed with solid waste. 60% moisture should be maintained through out the
period of composting. Compost should be turned up once in 15 days to create good
aeration, and for thorough mixing. Because of this practice, a uniform composted
material will be obtained. Solid waste can be composted with in 90 days by this method
with the indication of reduction in the volume, appearance of dark coloured materials and
a small of earthy odour After the completion of composting, compost should be sieved
through normal mesh to separate unwanted and partially composted material
6. Value addition of poultry waste compost

A known quantity of poultry droppings and coir pith @ 4:5 ratio should be mixed
well to attain a C/N ratio of 25:1 to 30:1 which is considered to be the optimum C/N ratio

14 AgriMoon.Com
Manures Fertilizers & Agrochemicals

for compositing. Pleurotus sajor-caju, a lignocellulolytic organism, should be inoculated

into the mix @ 2 packets per tonne of waste in order to speed up the composting
process. The mix should be heaped under the shade. The moisture content of the mix
should be maintained within 40 – 50%. Periodical turning should be given on 21st, 28th
and 35th day of composting. Another two packets of Pleurotus sajor – caju is to be
added when turning is given on the 28th day of composting. A good quality compost will
be obtained in 45 days, which contains 2.08% N, 1.93 % P and 1.41 % K with C/N ratio
of 10-16
7. Enriched Farm Yard Manure (EFYM)/ Reinforced FYM

Phosphorus content in FYM is relatively low and complete utilization of nitrogen

and potassium in the manure is seldom realized. Hence, heavy quantities intended to
supply the needed quantity of phosphorus will result in wastage of nitrogen in most soils.
To overcome this P insufficiency, addition of superphosphate to the manure is
recommended and the process is called reinforcing / enriching and the resultant material
is called “enriched farmyard manure”. The Single Super Phosphate (SSP) can be
sprinkled either in the cattle shed or on the manure heap. Rock phosphate can also be
recommended for this purpose.
Factors affecting the Composting Process:
I. The Type and Composition of the Organic Waste
II. The Availability Of Microorganism
III. Aeration
IV. The C, N and P Ratios
V. Moisture Content
VI. Temperature
VII. pH
VIII. Time
Preparation of Coir Waste Compost Using Yeast Sludge:
Yeast sludge is a waste product by alcohol distilleries @ 2t/day. This
waste contain 6% N, 0.3% P and 0.9% K with other micronutrients, vitamins and growth
promoting substances. The coir waste should be sieved so as to remove all the fibrous
materials. For one tone of coir waste 200 kg of yeast sludge and 10 kg of rock
phosphate should be added and mixed thoroughly. Moisture should be maintained at
60%. After mixing the material should be formed as heap. Within 4-5 days the
temperature of the heap will be raised to 50-60° C. Within 40 to 50 days the coir waste
and yeast sludge will become as mature compost. The matured compost will turn from
15 AgriMoon.Com
Manures Fertilizers & Agrochemicals

brown to black. There will not be any odor. The volume of the compost heap will be
reduced to 1/3. The temperature of the heap will be 25-30°c and it should be constant.
The compost will be very light and fine textured. The compost prepared by this means of
above method contains N-1.09%, P-1.35%, K-1.95% besides copper, manganese, iron
and zinc. This compost doesn’t have any phytotoxicity and used for all agricultural crops.
C. Preparation of sugarcane trash compost using yeast sludge:
sugarcane trash collected from sugarcane field has to be cut into small bits using
chaff cutter or shredder to a size of 1-2cm. for every tone of sugarcane trash 200 kg of
yeast sludge and 10kg of rock phosphate are added and mixed thoroughly. Moisture is
maintained at 60%. the heap is formed to a height of 1-1½ m. within 45-50 days
sugarcane trash compost will be ready for application to crops. The sugarcane trash
compost consists of N-1.2%, P-0.7%, K-1.5% and considerable quantities of
micronutrients. This compost can be applied at the rate of 5t/ha.
d. Japanese method of composting:
Instead of pits in conventional composting system, vats of 18-30’ in
length, 3-4’ in width and 2.5-3.0’ height are made of bamboo stakes of 2.5-3.0’ width. For
growth a non-leaky surface is prepared with broken stone stable or brick and plastered
with cement. About 2 feet space is kept free on one side of the vat to facilitate turning
the residues regularly. Sliced and broken pieces of coconut, shells, leaves, fibrous
materials, tender tree barks or pieces form the bottom 10-15 cm layer. Second layer of
dry leaves, grass residues, groundnut haulms are of 10-15 cm height. Cow dung, urine,
biogas slurry are sprinkled over and this layer of soil and ash is spread over. Nitrogen
rich green leaves of pongamia, albizzia, daincha, sesbania and crop residues forms third
layer of 10-15 cm. Fourth layer of 10-15cm contains organic wastes rich in phosphorous
and potash. Over these 2-3 buckets of cow dung and biogas slurry are sprinkled. Fifth
layer contains paddy or ragi straw that is rich in carbon and provides energy for
microorganisms. Sixth layer contains exclusively of dried and powdered cow dung of 20-
30cm. Over these small quantities of old compost, tank silt and ash are sprinkled. For
rapid degradation Aspergillus, Penicillium, Trichoderma should be inoculated. Pleurotus
and Polyporus should be inoculated for degradation of high lignin contained residues.
Azotobacter and Phosphobacteria can be mixed for enriching the composts.
General Properties Of Commercially Accepted Compost.:
N% >2 Color Brown Black
C: N <20 Odor Earthy
Ash % 10-20 Water Holding Capacity (%) 150-200

16 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Moisture %10-20 CEC (Meq 100 g-1) 75-100

P% 0.15-1.5 Reducing Sugar (%) <35%

17 AgriMoon.Com
Manures Fertilizers & Agrochemicals

04. Classification of fertilizers – N, P and K fertilizers

Classification of fertilizers
Commercial N, both organic and inorganic is desired from a wide variety of
materials which are found to differ very widely in their sources, properties, method of
preparation and their reactions in the soil. Classification based on chemical form seems
to be more satisfactory as indicated below.

Fertilizers and manures

Bulky organic Concentrated Artificial

manures organic fertilizers
(FYM,compost, manures
Green manure) Oil cakes
Guano

Nitrogenous Phosphatic Potassic Compound Mixed

18 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Nitrogenous Fertilizers

Inorganic ammoniates Organic ammoniates

Ammonical Amide-
Ammonical-N Nitrate-N + Nitrate -N Plant origin
N/synthetic

1.Ammonium sulphate 1. Sodium nitrate 1 .Amm.nitrate

2. Ammonium chloride 2. Potassium nitrate 2.Calcium
amm.nitrate
3. Ammonia 1. Urea
2. Calcium
cynamide

1.Oil Cakes
2.Cabbage waste

19 AgriMoon.Com
Manures Fertilizers & Agrochemicals

The nitrogen content of different nitrogenous fertilizers is given below

Sl.No Name of the N Form of N

fertilizer content (%)
1 Sodium nitrate 16.0 Nitrate (NO3)
(NaNO3)
2 Potassium nitrate 12.5-13.5 Nitrate
(KNO3)
3. Ammonium sulphate (NH4)2 20.6 NH4
SO4 (Ammonia)
4. Ammonium chloride (NH4 26.0 NH4
Cl)
5. Ammophos - A 11.0 NH4
6. Ammophos – B 16.0 NH4
7. Ammonium Nitrate (NH4) 33.0 NH4 – 16.5
NO3 – 16.5
8. Ammonium sulphate nitrate 25.6 NH4 – 19.5
NO3 – 6.6
9. Urea (CO (NH2)2) 46.0 Amide
10. Calcium cyan amide 20.6 Amide
(CaCN2)
11. Dried blood 3-14 Protein(organic)
12. Groundnut cake 8.0 Protein(organic)
13. Meat meal 09.0-11. Protein
(organic)
14. Guano 10.0 Protein
(organic)

20 AgriMoon.Com
Manures Fertilizers & Agrochemicals

PHOSPHATIC FERTILIZERS

Natural Treated or processed Industrial byproduct Chemical or

Super phosphate Basic slag synthetic
Ground rock Bone char Ammonium
phosphate phosphate
Bone meal

Bone meal POTASSIC

Natural Synthetic
Potash mineral Processed Pot.nitrate
MOP Pot.phosphate
SOP

21 AgriMoon.Com
Manures Fertilizers & Agrochemicals

05. Nitrogenous fertilizers – sources – fundamental processes involved in

manufacturing procedures for ammonia, sulphuric acid, nitric acid and
phosphoric acid

NITROGENOUS FERTILIZERS
Elemental Nitrogen, recognized by Rutherford in 1772 as a colorless, odorless
and inert gas, in the main constituent of air (approximately F9 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 80. 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 in capable of utilizing this elemental N for their growth. Most of important
mineral deposits are the Chile saltpeter (NaNo3), or Chilean niter and Niter (K NO3) or
Bengal saltpeter.

Sources of N
1. Mineral deposits: Chile saltpeter (NaNO3) in Northern Chile, Peru, Bolivia,California
and Nevada.
Niter (KNO3) or Bengal saltpeter: present in Spain, Egypt, Persia, India and U.S.A.
and ammonium sulphate in various “volcanic regions of the world”.
2. Addition through rain-water
A small amount of about 10 to 12 kg of N per year per acre 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 HNO3 where it is quickly converted into
nitrates.
3. Soil organic matter
This is the main sources of N in the soil and the N content of any soil will depend
upon the quality and quantity of organic matter of that soil.
4. N fixing organisms
The free living, Non-symbiotic E.g. Azatobactor and clostridium and symbiotic
E.g.: Rhizobium sp. Bacteria are found to fix considerable amounts of the elemental N in
a combined form. For example the non- symbiotic bacteria are found to fix 50 – 55 kg of
N per year per acre while the symbiotic organisms fix about 300-350 kg of N per year
per acre.

22 AgriMoon.Com
Manures Fertilizers & Agrochemicals

5. Industrial source
N is obtained from the industries in a combined form by the following processes.
a. Arc process
b. Cyanamid process and
c. Direct synthetic ammonia process.
Classification of Nitrogenous fertilizers and manners
Commercial N, both organic and inorganic is desired from a wide variety of
materials which are found to differ very widely in their sources, properties, method of
preparation and their reactions in the soil. Classification based on chemical form seems
to be more satisfactory as indicated below.

Industrial or synthetic fixation of nitrogen

For the commercial manufacture of the various nitrogenous 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 cyan amide process: Final product is CaCN2.
3. Synthetic ammonia or Haber –Bosch process: Final product is anhydrous or
aqueous NH3.

I. Direct oxidation 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. The basic reaction of this process involved 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 in the presence of electricity produced during thunderstorms
and lighting. In this commercial process, the reaction is secured by blowing air through a
flaming electric arc which has a temperature of about 3500°C. Only about 2 percent of
the air is heated and combined. The nitric oxide produced is converted to nitric acid
(HNO3) by the action of water and atmospheric oxygen.
N2 + O2 2 NO
2NO + O2 2 NO2
3NO2 + H2O 2HNO3 + NO.

23 AgriMoon.Com
Manures Fertilizers & Agrochemicals

But this process requires high amount of electric power and high capital cost. It
requires about five 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. Cyanamide process

This process was developed in Germany and is said to have been invented by
two Chemists Frank and Caro in 1898. At present, this process is probably the only
commercial method used for synthetic fixation of N other than the ammonia synthesis
process. Calcium cyanamide was first tried as a fertilizer in 1901. 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
The CaO obtained is reacted with coke in a continuous type electric furnace at 2200°C
to form fused calcium carbide (CaC2) which is withdrawn and solidified.
2200 ˚C
CaO +3C CaC2 +CO

In the third stage the air is liquefied by compressing and cooling from which the CO2 and
moisture are removed. The N is purified by fractional distillation. In the final stage, the
purified N is caused to permeate a mass of finely ground CaC2 in ovens under slight
pressure at 1100°C.

1100 ˚C
CaC2 +N2 CaCN2 +C

Ninety per cent of the CaC2 is found to be reacted completely. The crude
cyanamide is ground and treated with water to destroy residual CaC2 and is brought into
convenient physical condition. This method is not suitable where the coal supply is
limited.

III. Direct or synthetic ammonia process

This was developed between 1900 and 1910 by a team of German scientists,
Haber, Nernst, Bosch and others. The main principle of this method is when 3 moles of

24 AgriMoon.Com
Manures Fertilizers & Agrochemicals

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.
High temperature
High Temp &Pressure
3H2 + N2 2 NH3

This process consists of the following three main steps.

1. Preparation of H and N.
2. Purification and compression of three gases.
3. Catalytic conversion to ammonia.
To prepare H and N, the most famous water gas and producer gas procedures are
followed. The method consists of passing air and steam over red-hot coke to produce a
mixture of water gas (CO+H2) and producer gas (CO + N2). The coke is blasted with air
at 600°C and superheated steam is passed through the coke.
600 ˚C
Air + C (coke) +H2O (steam) CO +H2(water gas) CO+N2
(Producer gas)
After the formation of the CO2, pressure is raised to 50 atm for dissolving the
CO2 in water, which is removed and solidified for use in the later stages. The gas
mixture is now adjusted to one volume of N to three volumes of H and compressed to
250 atm and the last traces of CO and CO2 are removed by an ammoniacal solution of
cuprous formate.
In the final stage, the temperature is raised to 500°C and the gas mixture is
passed through special steel tower, capable of with standing high temperature and in the
presence of catalyst, either platinized asbestos or iron, the N and H will react to form
ammonia.
Catylyst
3H2 + N2 2 NH3
500 ˚C
The prepared ammonia can be used as anhydrous or aqueous or it can be
converted to HNO3 and used.

25 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Ammonia

Pure NH3 is made up of 82.25 % N and 17.75% H. It is the most concentrated

form and the lowest priced N fertilizer so far used either in the production of mixed
fertilizer or for dried application. As described earlier, NH3 can be obtained, either as a
by product during the destructive distillation of coal in coke oven, or from other coal
industries, or by synthetic process. For fertilizer are these are two forms available.

1. Anhydrous NH3 and 2. Aqua or aqueous NH3. Both the forms are extensively
used in ammoniation of superphosphate, in the preparation of mixed fertilizers and for
direct application.

Anhydrous ammonia is produced by compressing dry NH3 gas to form a liquid.

The fertilizer grade of anhydrous NH3 contains 99.5% NH3 equivalent to 82.0 per cent N.
It is an acid forming fertilizer and has a potential acidity equivalent to 148 lb of CaCO3
per 100 lb of ammonia. Aqueous ammonia is formed by dissolving NH3 gas in water.
Commercial grades are found to have 30% NH3 which is widely used for ammoniation of
superphosphate and mixed fertilizers and produce the same activity. Application of
liquid NH3 through irrigation water is called ‘Nitrogation’ and application of gaseous NH3
directly to the field by using special devices is called ‘Nitrojection’.

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 factories are
producing above 100 t p a.
Raw materials: NH3 and air are required for the manufacture of HNO3
Manufacture

Nitric acid is produced by NH3 oxidation process. The liquid NH3 is

evaporated,superheated and sent with compressed air to the converter, containing
platinum –rhodium catalyst. In the converter, NH3 is converted to nitric oxide, which is

26 AgriMoon.Com
Manures Fertilizers & Agrochemicals

then converted to nitrogen dioxide in oxidation vessel with the help of secondary air. In
the process, water absorbs nitrogen dioxide to from HNO3 while running in counter flow
to the raising nitrogen dioxide in absorption column.
The various processes used can be classified as medium pressure, high
pressure and combination of medium and high pressure, i.e, dual process. For fertilizer
industry HNO3 of concentration from 58 to 60% is used.
4NH3 + 7 O2 4 NO2 + 6 H2O - (1)
Nitrogen dioxide
4NO2 + 2H2O + O2 4 HNO3 - (2)
Concentrated nitric acid

Nitric acid / water form a constant boiling mixture at around 68% and cannot
therefore be separated by conventional distillation. The HNO3 can be further
concentrated by extractive distillation with concentrated H2SO4 or Mg(NO3)2. The
method involves high temperature reconcentration equipment operated under highly
corrosive conditions.

Handling, storage and packing

HNO3 is stored in stainless steel vessels. It is transported (large quantity) in stainless

steel tankers or (small quantity) in stoneware bottles and glass carboys. Bottles and
carboys shall be placed in an upright position on one layer of sand or ash free from
cinders and the empty surrounding space shall also be filled with the same material to
prevent movement.

27 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Flow chart for manufacture of HNO3

Water Ammonia AIR

aa

Vaporization

Catalytic
oxidation

Oxidation Oxides of N

Absorption Oxides of N

HNO3

28 AgriMoon.Com
Manures Fertilizers & Agrochemicals

SULPHURIC ACID

H2SO4 is one of the most important heavy chemicals produced in India. It has a
wider variety of industrial uses than any other chemical. Per capita consumption of
H2SO4 often has been used as an index of the industrial development of a country. The
fertilizer industries, by far, the greatest consumer of H2SO4 for acidulation of RP and for
the manufacture of (NH4)2 SO4. other important fields of its use are steel works, rayon
and staple fiber, alum and other inorganic chemicals and petroleum refining etc.
Raw materials/ sources
H2SO4 may be produced from elemental sulphur, pyrites (Sulphides of iron,
copper, zinc and lead), hydrogen sulphide as contained in sour gas and petroleum,
waste gases from the burning of fuel and smelting operations and sulphate salts such as
anhydrite, gypsum and iron sulphates. Elemental S, pyrites and sulphates are the true
basic raw materials. H2SO4 produced by burning of fuel and smelting operation is called
by products H2SO4. H2SO4 production from metallic sulphates is not economical. Thus
for H2SO4 production elemental S and pyrites are the only two important raw materials.
In India, all the factories are based an elemental S except for Hindustan copper Ltd.,
Khetri and Hindustan Zinc Ltd., Udaipur which are based on flue gases from copper and
Zinc smelters respectively. Also, one plant at Sindri is producing acid based on iron
pyrite and a similar plant of larger capacity is under construction by the Sindri unit of
FCI.
Methods of manufacture
S is burnt to sulphur dioxide and pyrites are roasted to oxidize the sulphide
content to SO2. SO2 after catalytic conversion to Sulphur trioxide is absorbed in water to
give H2SO4. the differences in H2SO4 processes are in the manner in which SO2 is
converted to SO3 and absorbed in H2O to produce H2SO4.

S + O2 SO2
2SO2 + O2 2SO3
SO3 + H 2O H2 SO4

(i) Chamber/tower process

The oldest process is the chamber process, so called because the reactions
which produce SO3 and H2SO4 take place within a lead chamber. The conversion to

29 AgriMoon.Com
Manures Fertilizers & Agrochemicals

SO3 and then to H2SO4 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, SO2 is converted to SO3 by the use of a metal or metal oxide
catalyst. The more common catalysts are platinum, iron oxide and vanadium pent oxide,
although never plants use the latter almost exclusively. SO3 is passed to a tower where
it is absorbed in recycling con.H2SO4.

Properties
i) Chemical formula - H2SO4
ii) Molecular weight - 98.08
iii) Appearance - Colorless, viscous liquid
iv) Specific gravity (18°C/4°C) - 1.834
v) Boiling point - Decomposes at 340°C
vi) Solubility in water - Miscible in all proportions.

30 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Flowchart for H2SO4 manufacture

Water Pyrites Sulphur AIR

ROASTING BURNING
CINDERS
-------------------------- SO2
OXIDATION

-------------------------- SO3

ABSORPTION

DILUTION

H2SO4

31 AgriMoon.Com
Manures Fertilizers & Agrochemicals

06. Manufacturing of ammonium sulphate, ammonium nitrate and ammonium

chloride
Ammoinum sulphate
(NH4)2 SO4 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. It is a white crystaline salt having good keeping quality in dry conditions.
Production capacity
The total installed capacity in the country is about one million tones of (NH4)2 SO4
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.
Method of manufacture
The following methods are used for producing (NH4)2 SO4.
(i) Recovery from coke-ovens
The coke-oven gas (obtained when coal is heated to make coke) contains about
1% NH3 by volume. The gas is cooled and passed into saturators containing weak
H2SO4 so as to form (NH4)2SO4 crystals which is then recovered, centrifuged, washed
and dried. This process is used in the steel plants where large coke- oven batteries are
in operation.
(ii) Direct neutralization
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.
Amorphous (NH4)2 SO4 is prepared by reacting gaseous NH3 and H2SO4 in spray
towers. The heat of reaction removes all the water present and the dry, fine product is
continuously removed from the base of the tower. This product is suitable for making
dry-mixed and granular fertilizers, FCI (Sindri), FACT (Alwaye) use the direct
neutralization process.
In the manufacture of some granular NPK fertilizers, (NH4)2SO4 is formed directly
with other ammonium salts. E.g. in the 16 – 20 – 0 grade product made by FACT, a

32 AgriMoon.Com
Manures Fertilizers & Agrochemicals

mixture of H3PO4 and H2SO4 is neutralized with NH3 to form a slurry of (NH4) PO4 and
(NH4)2 SO4, which is then granulated.
(iii) Gypsum process
NH3 gas is absorbed in water and then converted to (NH4)2CO3 by absorbing
CO2. The (NH4)2CO3 is reacted with gypsum (CaSO4. 6 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. Naturally occurring gypsum, or by product gypsum from
H3PO4 plants can be used for this process. CaCO3 produced can be used for cement
manufacture FCI (Sindri), FACT (Alwaye), EID-parry (Ennore), and GSFC (Baroda),
produce (NH4)2 SO4 from Ca SO4.
(iv) Byproduct
(NH4)2SO4 from caprolactum plants (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.
GSFC (Baroda) has commissioned a 20,000 t p a caprolactum plant which will produce
about 80,000 tonnes of (NH4)2 SO4 per year.
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

Handling storage and packing

Crystalline (NH4)2 SO4 is free flowing and 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.
Properties
• It is a white crystalline salt and to some extent hygroscopic
• It has good storage quality
• It is very soluble in water and so called as quick acting fertiliser
• It should not be used along with alkaline materials

33 AgriMoon.Com
Manures Fertilizers & Agrochemicals

• It is physiologically acidic in nature

Reactions in soil
(NH4)2 SO4 2 NH4 + + SO4 -

Soil colloid Soil colloid

Ca ++ + (NH4)2 SO4 NH4+ +CaSO4 (soluble)

Ammonia gas is evolved when ammonium sulphate reacts with alkaline materials
When lime and ammonium sulphate is used together in the soil, ammonia gas is
produced
Ammonium chloride (NH4 Cl) 26% N
This is sometimes called nitrate of ammonia. It is commercially prepared by
combining ammonia with HCl and the resultant product, NH4Cl is found to have very
good physical condition. 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. This fertilizer is also obtained as a by product of the Solvay process of
making (Na)2 CO3.
The commercial sample is a white, crystalline salt containing 26% N in the NH4 form.
The fertilizer is suitable for many crops except for those, which are sensitive to high
chlorine content. This is physiologically acidic fertilizer.
Manufacture
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

Ammonium chloride is also obtained as a byproduct of soda ash (Na2CO3) and

manufactured as Solvays process. It is prepared by reacting calcium chloride with
ammonium carbonate. Ammonium chloride is obtained by double decomposition
between ammonium sulphate and sodium chloride at 13000 C
Ammonium nitrate (NH4 NO3) – 33% N
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 is continuously produced with the aid of a neutralization tower. NH3 gas
is introduced near the bottom of the tower, while air is added at a higher point to cool the

34 AgriMoon.Com
Manures Fertilizers & Agrochemicals

solution and carry off the water vapor. The solution containing about 80% of NH4 NO3 is
with drawn and converted to crystals or pellets as the case may be.
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
completely utilized by crops and hence no residues are left in the soil. 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. It is an
excellent fertilizer both for direct application to the soil and for use in mixtures. It is an
economical source of fertilizer N, suited to a wide range of crops, soils and climatic
conditions. Its NO3 content contributes to rapid crop response while the NH4- N makes it
more resistant to leaching losses than other materials carrying their entire N in the NO3
form.

35 AgriMoon.Com
Manures Fertilizers & Agrochemicals

07.Manufacturing of urea

Urea: CO (NH2)2 (42 to 46% N)

The main principle involved in the process of manufacture is combining pure

ammonia with pure CO2 and removing one molecule of H2O from the resulting NH4 CO3
to form Urea. The CO2 and NH3 are allowed to react in the liquid phase under greatly
elevated pressure and temperature and this process requires highly specialized
equipment. The CO2 and NH3 are compressed and heated as they enter the converter
where urea is formed. A large excess of NH3 is used in order to increase the conversion
rate. The un reacted NH3 and CO2 are removed by means of an evaporator still and are
then recycled. The urea solution is pumped to the crystalizer where cooling and
crystallization take place. The urea crystals are centrifuged and dried.

FLOW CHART FOR UREA MANUFACTURE

Still CO2 + NH3 recycled

Compressor Crystallizer
Convertor
Conditioning
CO2 Centrifuge agent
High pressure
pump
Liquid Mixer Drier
NH3

36 AgriMoon.Com
Manures Fertilizers & Agrochemicals

08. Slow release N fertilizers – coated fertilizers – types of coating – lac coated-
neem cake blended and coal tar coated urea- chemically modified forms-urea
formaldehyde, IBDU, CDU

Slow-release fertilizers are excellent alternatives to soluble fertilizers. Because

nutrients are released at a slower rate throughout the season, plants are able to take up
most of the nutrients without waste by leaching. A slow-release fertilizer is more
convenient, since less frequent application is required. Fertilizer burn is not a problem
with slow-release fertilizers even at high rates of application; however, it is still important
to follow application recommendations. Slow-release fertilizers may be more expensive
than soluble types, but their benefits outweigh their disadvantages.

Slow-release fertilizers are generally categorized into one of several groups based on
the process by which the nutrients are released. Application rates vary with the different
types and brands, with recommendations listed on the fertilizer label.

Pelletized:
One type of slow-release fertilizer consists of relatively insoluble nutrients in
pelletized form. As the pellet size is increased, the time it takes for the fertilizer to
breakdown by microbial action is also increased. An example of this type is MagAmp,
a 7-40-0 fertilizer that is available in a coarse grade lasting two years and a medium
grade lasting one year. MagAmp is used commercially for container plants, but is
appropriate for use on turf, tree seedlings, ornamentals, vegetables, and flower
borders.
Chemically Altered:
A fertilizer may be chemically altered to render a portion of it water insoluble. For
instance, urea is chemically modified to make Ureaform (ureaformaldehyde) -- a fertilizer
that is 38 percent nitrogen, 70 percent of which is water-insoluble. This percentage is
often listed on fertilizer labels as the Percent W.I.N., or the percent of water-insoluble
nitrogen. This form of nitrogen is released gradually by microbial activity in the soil.
Because microbial activity is greatly affected by soil temperature, pH, aeration, and
texture, these variables can affect the release of nitrogen from Ureaform. For example,
there will be less fertilizer breakdown in acid soils with poor aeration -- an environment
unfavorable to soil microorganisms. Ureaform is used for turfgrass; landscaping;
ornamental, horticulture, and greenhouse crops.
37 AgriMoon.Com
Manures Fertilizers & Agrochemicals

IBDU (isobutylidene diurea) is similar to Ureaform, but contains 32 percent nitrogen, 90

percent of which is insoluble. However, IBDU is less dependent on microbial activity than
Ureaform. Nitrogen is released when soil moisture is adequate. Breakdown is increased
in acid soils. IBDU is used most widely as a lawn fertilizer.

Coated fertilisers
Controlled- or slow-release fertilizers are broadly divided into uncoated and
coated products. Uncoated products rely on inherent physical characteristics, such as
low solubility, for their slow release. Coated products mostly consist of quick-release N
sources surrounded by a barrier that prevents the N from releasing rapidly into the
environment. Different mechanisms, but similar (though not identical) end results.

The terms “controlled-release” and “slow-release” can mean different things to

different people, but for purposes of this discussion, the two terms are synonymous.
Except for a few slow-release K sources, almost all slow-release fertilizers are N
sources. They represent a relatively small segment of the total fertilizer industry (3 to 4
percent), but their use is growing faster than soluble (quick-release) materials. This is
primarily because they reduce the overall environmental impact of N fertilizers, as now
mandated in BMPs.

Coated:
Water-soluble fertilizers may be coated or encapsulated in membranes to slow the
release of nutrients. For example, Osmocote, a controlled-release fertilizer is composed
of a semipermeable membrane surrounding water-soluble nitrogen and other nutrients.
Water passes through the membrane, eventually causing enough internal pressure to
disrupt the membrane and release the enclosed nutrients. Because the thickness of the
coating varies from one pellet, or prill, to another, nutrients are released at different
times from separate prills. Release rate of these fertilizers is dependent on temperature,
moisture, and thickness of the coating. Osmocote is recommended for turf, floriculture,
nursery stock, and high-value row crops.

Another type of coated fertilizer is sulfur-coated urea (SCU), which is manufactured by

coating hot urea with molten sulfur and sealing with a polyethylene oil or a
microcrystalline wax. Nitrogen is released when the sealant is broken or by diffusion
through pores in the coating. Thus, the rate of release is dependent on the thickness of
the coating or the sealant weight. SCU is broken down by microorganisms, and chemical

38 AgriMoon.Com
Manures Fertilizers & Agrochemicals

and mechanical action. The nitrogen in SCU is released more readily in warm
temperatures and dry soils. SCU appears to be more effective when applied to the soil
surface, rather than mixed into the soil. Any method of application that crushes the
granules will increase the release rate to some extent.

SCU is best used where multiple fertilizer applications are normally necessary, such as
on sandy soils or in areas of high rainfall or irrigation. SCU is used on grass forages, turf,
ornamentals, and strawberries.

Nutricote is characterized by coating nitrate compound fertilizers with a special resin.

The duration of nutrient release is controlled by the porosity of the resin coating. A more
porous coating results in quicker release. This technology ensures consistency and
precision of nutrient release from Nutricote controlled release fertilizers.

When Nutricote is applied to the soil, the water in the soil enters the granule through
micropores which dissolves the nutrient elements. The nutrient elements will then be
released steadily through the same pores. Most Nutricote granules are 3 to 4 mm in
diameter and the nutrient content are NPK: 14-14-14 and NPK: 20-7-10.

Nutricote’s release rate is influenced by soil temperature, the higher the soil
temperature, the greater the release rate. Absorption of nutrients and water by plants is
generally increased with increasing temperature and plant growth will become more
vigorous as a result. Nutrient supply through Nutricote nicely matches the physiology of
plant response to temperature.

The release rate of Nutricote is not significantly influenced by soil moisture levels nor by
soil type or pH. Nutricote does not depend upon microbiological decomposition for its
action.

2.Polymer-coated fertilizers

Polymer-coated fertilizers (PCF) represent the most technically advanced state of

the art in terms of controlling product longevity and nutrient efficiency. Most PCFs
release nutrients by diffusion through a semipermeable polymer membrane, and the
release rate can be controlled by varying the composition and thickness of the coating.
The type of fertilizer substrate also may influence the rate of N release.

39 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Meister products : Meister products are produced by using thermoplastic resins as

coating materials. The coatings are applied to a variety of substrates including urea,
diammonium phosphate, potassium sulfate, potassium chloride and ammonium nitrate.
Release-controlling agents such as ethylene-vinyl acetate and surfactants are added to
the coating to obtain the desired diffusion characteristics, while coating thicknesses
remain similar for most products. Release rates can also be altered by blending talc
resin into the coating.

Reactive Layer Coating: A relatively new coating technology known as reactive layer
coating (RLC) combines two reactive monomers as they are simultaneously applied to
the fertilizer substrate. These reactions create an ultra-thin membrane coating, which
controls nutrient release by osmotic diffusion. RLC products include coated basic
fertilizer materials such as urea, potassium nitrate, potassium sulfate, potassium
chloride, ammonium sulfate, ammonium phosphate and iron sulfate, in various particle
sizes. Coating weights on urea vary from 1.5 to 15 percent, depending on the release
duration desired.

Multicote products: In the production of multicote products, fertilizer granules are

heated in a rotating pan and treated with materials that create multiple layers of a fatty
acid salt. This is followed by the application of a paraffin topcoat. Coating weights are
relatively large compared to other technologies, but this is offset by the comparatively
low cost of the coating materials. Substrates include potassium nitrate, urea and triple
superphosphate. The various coated components are blended together into different
grades.

Coated N Fertilizers;

1.Ureaformaldehyde reaction products

Ureaformaldehyde (UF) reaction products represent one of the oldest

controlled-release N technologies, having been first produced in 1936 and
commercialized in 1955. Urea and formaldehyde are reacted together to various extents
to produce polymer-chain molecules of varying lengths. The more these products are
reacted, the longer the chains tend to be. Chain length, in turn, affects release
characteristics.

40 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Ureaform is the oldest class of UF reaction products. It is sparingly soluble, and

contains at least 35 percent total N, with at least 60 percent of the total N as cold-water-
insoluble N (CWIN). Ureaform is composed largely of longer-chained molecules of UF
polymers. The unreacted (and, therefore, quick-release) urea N content in UF is usually
less than 15 percent of the total N.

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 to 40 percent, with between 25
and 60 percent of the N present as CWIN. The unreacted urea N content generally is in
the range of 15 to 30 percent of the total N.

UF solutions are clear water solutions. They contain only very-low-molecular-

weight, water-soluble UF reaction products, plus unreacted urea. Various combinations
of the UF solutions are produced. They contain a maximum of 55 percent unreacted
urea with the remainder as one or more of methylolureas, methylolurea ethers, MDU,
DMTU or triazone.

Isobutylidene diurea (IBDU) : Unlike the reaction of urea and formaldehyde,

which forms a distribution of different UF polymer chain lengths, the reaction of urea with
isobutyraldehyde forms a single type of molecule. Although similar in chemical structure
to methylene diurea (MDU), its physical properties are quite different. IBDU is a
white crystalline solid available in fine (0.5 to 1.0 mm), coarse (.7 to 2.5 mm) and chunk
(2.0 to 3.0 mm) particle sizes. The product contains a minimum of 30 percent N with 90
percent of the N in water-insoluble form. The typical commercialized product contains
about 31 percent N.

Crotonylidene Diurea (CDU) : This slow acting nitrogen compound is formed by

reaction with crotonaldehyde or acetaldehyde. Powdered CDU containing 30 percent N
has been directly used as a fertilizer. The microbial decomposition of the chemically
bound CDU is temperature dependant

Agronomic properties and nutrient release mechanisms of UF materials

The conversion of UF reaction products to plant-available N is a multi-step

process, involving dissolution first, and then microbial decomposition. Once in the soil
solution, UF reaction products are converted to plant-available N through either microbial
41 AgriMoon.Com
Manures Fertilizers & Agrochemicals

decomposition or hydrolysis. Microbial decomposition is the primary mechanism of N

release. Environmental factors such as soil temperature, moisture, pH and aeration
affect microbial activity and, therefore, the rate of N release.

The rate of N release from UF reaction products is directly affected by polymer chain
length. The longer the methylene urea polymer, the longer it takes for the N to become
available. For ureaform and methylene urea products, the rate of mineralization is
reflected by the CWIN content and its Activity Index. The higher the AI value, the more
rapidly the N will become available. It is questionable if the very long methylene urea
polymers (HWIN) are effectively used by the plant.

Agronomic properties and nutrient release mechanisms of IBDU: Nitrogen from

IBDU becomes available to plants through hydrolysis. In the presence of water, the
compound will hydrolyze (break down) to urea and isobutyraldehyde. The rate of
hydrolysis is accelerated by low pH and high temperature. Unlike UF polymers that rely
on soil microbial populations to make the N available, IBDU is primarily dependent on
water as the critical element in N availability. Its low water solubility controls the transport
of the product into the soil solution.

Agronomic properties and nutrient release mechanisms of SCU: The mechanism of

N release from SCU is by water penetration through micropores and imperfections (i.e.,
cracks) or incomplete sulfur coverage in the coating. This is followed by a rapid release
of the dissolved urea from the core of the particle. When wax sealants are used, a dual
release mechanism is created. Microbes in the soil environment must attack the sealant
to reveal the imperfections in the sulfur coating. Because microbial activity varies with
temperature, the release properties of the wax-sealed SCUs are also temperature
dependent.during the cool-season growth period.

42 AgriMoon.Com
Manures Fertilizers & Agrochemicals

09. Controlled release fertilizers and reaction in soil - nitrification inhibitors –

criteria and advantages

Controlled-Release Fertilizers Using Zeolites

The U.S. Geological Survey (USGS) has experimented with zeolites to help
control the release of fertilizer nutrients in soil. The use of soluble fertilizers can lead to
water pollution and to wasted nutrients. Nitrogen, for example, can leach into ground and
surface waters, especially in sandy soils, and phosphate may become fixed and
unavailable to plants, especially in tropical soils. Zeolites are porous minerals with high
cation-exchange capacity that can help control the release of plant nutrients in
agricultural systems. Zeolites can free soluble plant nutrients already in soil, and may
improve soil fertility and water retention. Because zeolites are common, these unique
minerals could be useful on a large-scale in agriculture.

Controlled-Release Nitrogen Fertilizer

Urea is one of the most common nitrogen fertilizers. It is very soluble in water, and can
be leached through the root zone. In addition, urea is converted into ammonium ions by
an enzyme found in most soils. Soil bacteria then convert these ammonium ions into
readily leachable nitrate ions. Using zeolitic rocks in fertilizer can help prevent these
nutrient losses.

Controlled-Release Phosphorous Fertilizers

Phosphate (H2PO4) can be released to plants from phosphate rock (P-rock) composed
largely of the calcium phosphate mineral apatite by mixing the rock with zeolite having
an exchange ion such as ammonium. The approximate reaction in soil solution is as
follows: (P-rock) + (NH4-zeolite) = (Ca-zeolite) + (NH4+) + (H2PO4-).

The zeolite takes up Ca2+ from the phosphate rock, thereby releasing both phosphate
and ammonium ions.

Growth responses to controlled-release fertilizers

Most controlled-release fertilizers are N-based, and most of the research involving
them has evaluated plant responses to N application. Additionally, because most

43 AgriMoon.Com
Manures Fertilizers & Agrochemicals

controlled-release N sources cost several times more per pound of N than the soluble
sources, most of the evaluation has been conducted on higher-cash-value crops such as
ornamentals, vegetables, citrus and turfgrasses. Little research has been conducted on
agronomic crops because their use in this sector is not considered economically
feasible. Technologies currently under development may reduce the cost of controlled-
release products to the point that they can be used on agronomic crops, but such is not
yet the case.
Nitrification inhibitors
It should be non-toxic plants, soil microorganisms,animals,fish and mammals
It should block the conversion of NH3 to NO3 by inhibiting Nitrosomonas activity
It should not interfere with the transformation of NO3 (nitrite) by Nitrobacter
It should be able to move with the fertilizer so that it will be distributed uniformly through
the soil zone contacted by nitrogen fertilizer
It should be stable for the inhibitory action to last for an adequate period of time
It should be relatively in expensive, so that it can be used on a commercial scale
There are various nitrification inhibitors, of which N-Serve or nitrapyrin and AM
are most important.
N-Serve- It is 2-choloro-6(trichloromethyl) pyridine and also referred to as nitrapyrin
AM- Chemically it is a substituted pyrimidine (2-amino-4-chloro-6- methyl pyrimidine)

44 AgriMoon.Com
Manures Fertilizers & Agrochemicals

10. P fertilizers – rock phosphate – bone meal – basic slag

The element was discovered in 1669 and was found to be widely distributed in
the lithosphere as phosphates. It is found to occur mostly as calcium phosphate
(Tricalcium phosphate). The Ca3(HPO4)2 is considered to be the basic material for the
manufacture of very many phosphatic fertilizers. More than 50 countries produce
phosphatic fertilizer. The top five fertilizer producing countries were United States,
China, Russia , India and Brazil. Phosphorus when heated in an abundant supply of O2,
it burns and forms P2O5 which, when dissolved in waters, forms metaphospheric acid.

4P + 5O2 2P2O5 - Phosphorus pent oxide

P 2O 5 + H 2O 2 HPO3 - Metaphospheric acid
When this meta phosphoric acid is heated with water, it forms orthophosphoric
acid which is commonly called as phosphoric acid.
HPO3 + H 2O H3 PO4 - orthophosphoric acid.
This orthophosphoric acid has three replaceable H+ atoms and hence it forms
three classes of salts replacing one or two, or all the three H+ atoms. The neutralization
is said to occur in stages as follows.
1. H3 PO4 + KOH KH2 PO4 + H 2O
Monopotassium phosphate
2. H3 PO4 + 2KOH K2 HPO4 + 2H2O
Dipotassium phosphate
3. H3 PO4 + 3KOH K3 PO4 + 3H2O
Tripotassium phosphate
The corresponding calcium salts are
1. Monocalcium phosphate - Ca (H2PO4)2 - Water soluble
2. Dicalcium phosphate - Ca2 (HPO4)2 - or Ca (HPO4) –
Soluble in citric acid
3. Tricalcium phosphate - Ca3 (PO4)2 - soluble in strong acids.
This monocalcium phosphate is an acid salt having a solubility of 100 g L-1 of
water. The di and tricalcium phosphates are almost neutral salts having the solubility of
0.25 g and 0.005g per liter of water respectively.
Sources of phosphorus
1. Mineral deposit
It occurs naturally, as mineral deposits consisting mainly of Ca3 (PO4)2 combined
with either CaF2, CaCO3, Ca (OH)2 or CaCl2. The naturally occurring mineral is called
“Apatite” or “Phosphorite” or “Phosphate rock” having the general formula (Ca3 (PO4)2)
45 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Ca X. These natural deposits serve as the basic material for the synthesis of all other
phosphoric fertilizers.
Classification of phosphatic fertilizers
1. Based on nature of source or manufacture Phosphatic materials

Natural Treated or Industrial Synthetic Phosphates

Phosphates Processed by product
phosphates
1. Bones 1. Super phosphate Basic stage Ammonium phosphates
2. RP 2. Bone ash
3. Bone super
2.Based on the solubility of the phosphate

Water soluble phosphates Citric soluble Insoluble or

(or) Phosphate or tricalcium
Monocalcium phosphate Dicalcium phosphate phosphate

1. Super phosphate 1. Basic – slag 1. Rock phosphate

16 % P2O5 14-18 % P2O5 30-40 % P2O5
2. 3Concentrated SP 2. Dicalcium phosphate 2. Raw bone meal
48 % P2O5 34 -38 % P2O5 20-25 % P2O5
3. Ammonium phosphate 3. Rhenania PO4
20 % P2O5 23-26 % P2O5
As in the case of N, the P is incapable of being utilized in the elemental form, but
only in the combined form as acid ions (anions). All plants absorbs P either in the
monovalent (H2PO4) or divalent (HPO4) ions.
1.Water soluble phosphate
These include either monocalcium phosphate Ca(H2PO4) or other water soluble
phosphates like ammonium phosphates. These fertilizers are readily soluble in water
which can be observed quickly, as plants absorb P as monovalent phosphate ion H2PO4.
But, when applied to the soil, the water – soluble form is converted to water insoluble

46 AgriMoon.Com
Manures Fertilizers & Agrochemicals

forms resulting in the reduced availability, though there may not be any total less to the
applied P. The fertilizers included in this group are found to be suitable for neutral and
alkaline soils but not for acid soils.
2.Citric –soluble phosphates
The materials, having water – insoluble phosphates, but soluble in one percent
citric acid, are included in this group. The availability of P is not as quick as in the case
of water – soluble P, but adequate quantities are found to be released in the available
form as divalent phosphates (HPO4) for plant utilization. This group is found to be useful
for acid soils, as under low pH of the soil the citrate soluble phosphates does not easily
get converted into monocalcium phosphates or water soluble phosphates, and there are
less chances of phosphate getting fixed up as iron and aluminum phosphates.
Moreover, due to their basic reaction and high Ca content, they act particularly well on
acidic soils and as such, this group is well suited for lateritic and acidic soils.
3.Insoluble phosphates
This group includes those materials having water and citric acid insoluble
phsophates. The phosphates are being present mainly as tricalcium phosphate. The
availability is very low and the phosphates will be converted to available form very slowly
through various chemical reactions. Though the solubility of phosphates is low, the
phosphates will be available for prolonged period of time.
These fertilizers are well suited for strongly acidic soils or organic soils which
require large quantities of phosphatic materials to raise the soil P status.
The following table illustrated the phosphate (P2O5) content and the form of
phosphate.
Sl. Fertilizers Total P2O5 Form of Avail.P2O5
No. (%) PO4
1. Ordinary super phosphate 16 Water 16.5 - 17.0
soluble
2. Concentrate super phosphate 46 – 48 -do-
3. Monoammonium phosphate 48 (11 N) -do-
4. Diammonium phosphate 53 (21 N) -do- 46 (18N)
5. Ammophos – A 48 (11 N) -do-
6. Ammophos – B 20 (20 N) -do-
7. Basic slag 14 – 18 Citric
soluble

47 AgriMoon.Com
Manures Fertilizers & Agrochemicals

8. Dicalcium phosphate 34 – 38 -do- 34.0

9. Fused tricalcium phosphate 28 -do-
10. Rhenania phosphate 23 – 26 -do-
11. Raw bone meal 20 – 25 Insoluble NA
12. Steamed bone meal 22 – 25 -do- NA
13. Rock phosphate 30 – 40 -do- NA

1.Rock phosphate
The phosphate mineral in soil is found to occur as tricalcium phosphate Ca3
(PO4)2 in combination with either CaCO3, Ca F2, Ca(OH)2 or CaCl2. The primary mineral
is called ‘apatite’ and its massive form is sometimes called as ‘Phosphorite’. The
apatite is of igneous origin found as a constituent of granites, gneisses and basalt. The
apatite is usually found as crystals having a clear and transparent colour. 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)5 x 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
All the above five apatite are primary minerals, of which the fluor apatite is the
most commonly occurring one. In some acid soils the phosphate may be founding
combination with titanium and iron in varying quantities and there when present in the
soil are classified as secondary mineral. The apatite as such is found to occur in the
amorphous form and it may be in the compact, concretionary or earthy form and these
forms are commonly referred as rock or boulder phosphate, pebble phosphate and soft
phosphate respectively. The apatite deposits are classified into residual deposit,
replacement deposit and sedimentary deposit.
Deposits of apatite of economic importance have been found in every continent
and in many island of the world. In India, the phosphoric deposits are found in Trichy
district of Tamil Nadu, Udaipur of Rajasthan and Singhbum of Bihar. The deposits in
Trichy are found in the form of nodules in a bed of clay and hence are called Trichy
phophatic nodules. The exact locality is Uttalur about 30km from Trichy and the deposit

48 AgriMoon.Com
Manures Fertilizers & Agrochemicals

is found to spread over an area of 11 to 12 square miles. The Trichy phosphatic nodule
analyses as follows
P 2O 5 - 24 – 27%
CaCO3 - 42 – 47 %
F - 2–3%
Fe2O3 & Al2O3- 4–9%

As compared to the phosphatic deposits found in other countries, this phosphate

deposit contains a high content of F (2-3%), high content of sesquioxides (4-9%) and low
content of phosphate. The high contents of F and R2O3 made the RP unsuitable for the
manufacture of other phosphatic fertilizers at a lower cost. Larger quantities of acids are
required to eliminate the F and R2O3 which will thus increase the cost of production.
Moreover, the Trichy deposit is not suitable for direct use as fertilizer because of high F
and R2O3 contents. The deposit is mainly in the form of carbonate apatite and fluor
apatite. The fertilizing value is nil unless the F and R2O3 are removed. The ground RP
is marketed, which passes through 200 mesh sieve.
Bone meal
Bone meal contains tri calcium carbonate or hydrated tri-calcium phosphate. This also
contain sodium, magnesium and carbonate. Bone meal is prepared by crushing bones
and availability of phosphorus in bone meal increases as material is crushed to a finer
size.
Raw bone meal
It is prepared by grinding the bones as such without any treatment. The bones are
collected, dried before grinding. The protein present in the form of remaining flesh
provides nitrogen ranging between 2 to 4%. This contains fat of glue which prevents the
decomposition of bone when applied in the soil.
Total P2 O5 on dry weight basis (Max.) : 20 %
Available P2 O5 soluble in 2% citric acid (Min.) : 8%
Total nitrogen, % by weight (Min.) : 3%

Steamed bone meal

Steamed bone meal is obtained by the boiling the bones under steam pressure. Under
this process the fat and some other materials are removed so that decomposition can
take place readily in the soil after it is applied. However this process reduces the
nitrogen content but phosphate content is increased. The bones are then ground and

49 AgriMoon.Com
Manures Fertilizers & Agrochemicals

sold as fertilizer material in the market. The steamed bone meal should have the
following standard according to fertilizer quality control order (1957) if Government of
India:
Free moisture percentage by weight (Max.) : 7.0
Total phosphates as P2 O5 percentage by weight (Min) : 22.0
Available phosphates as P2 O5 soluble in 2 %
Citric acid solution % by weight (Min.) : 16.0
Bone meal consists of P2 O5 in citric acid soluble form hence it should always be
applied as basal. The bone meal sources are limited and hardly 30,000 to 35,000
tonnes of bone meal is produced and consumed annually in the country. Now-a-days it
is also used as feed to the animals in the form of concentrate hence the materials, as
fertilizers, is further reduced.
Basic slag
It is a by-product from the steel industry. During the steel manufacture, the P in
the iron ore is removed to get a high quality steel as the steel containing more than 2%
of P is brittle. The basic slag is obtained by the various processes of steel manufacture.
1. Thomas and Gilchrist method
The method was introduced as a modification to the old Bessemer process in
1877. In this, molten pig iron containing the various impurities like Ca, SiO2S and P 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.

2. 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 pig iron is then added. This
carries not more than 15% P2O5 and not less than 8% P2O5.
Properties
The name ‘basic slag’ is derived from metallurgy. Any flux that is added to
remove the impurities is recovered mixed with the impurities as a slag. The flux that is
added to remove basic impurities produces acid slag and the one that is added to
remove acid impurities forms basic slag. The basic slag is a heavy dark powder send is
alkaline to litmus. The availability of P is found to increase with the fineness of the
product as well as with silica content and decrease as the F content increase. Basic

50 AgriMoon.Com
Manures Fertilizers & Agrochemicals

slag should not be used as an ingredient in manure mixtures. 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 (Ca4 P2O5) and still others consider it is a basic silicon oxy
apatite. It is only a slow acting fertilizer. This more useful for acid soils and in addition to
the phosphate it is valued for the magnesium and Mn content. Following is the average
composition of basic slag.
Phosphate (P2O5) - 12 - 20 %
Lime (CaO) - 40 - 50 %
Silica (SiO2) - 5 - 16 %
Sesquioxides (R2O3) - 12 - 16 %
Manganese oxide (MnO) - 5 – 10 %
Magnesium Oxide (MgO) - 2–3%
Artificial Basic slag
When PR is fused with Mg containing minerals like serpentine and olivine, the
resultant product is called as artificial basic slag. The fertilizing value of basic slag is
influenced by the fineness of the fertilizer and material passing through a 100 mesh
sieve is found to be better. It is more suitable for acid soils because of high lime content.
The presence of Mg and Mn corrects the deficiency of these elements in the soil.

51 AgriMoon.Com
Manures Fertilizers & Agrochemicals

11. Single and triple super phosphates – thermophosphates – method of

manufacturing Super phosphate
The term super phosphate is generally applied to phosphates which are present
in a readily available form to plants. After the resolution passed in the meeting of the
first world International congress on chemical fertilizers, 1938, the term super phosphate
is restricted to refer those phosphates having less than 25% of P2O5 and the term
concentrated SSP for all those phosphates containing more than 25% P2O5.
The super phosphates are generally manufactured from phosphate rock, but
bones and phosphatic guanoes are also extensively used for the manufacture. The
super phosphates prepared from organic sources (bones & guano) are said to be having
good physical condition, but with a lower P2O5 content. In recent times only the
phosphate rock is being utilized for the manufacture of various super phosphate.
Phosphate rock containing less than 50% of tricalcium phosphate are not
suitable for manufacture of phosphatic fertilizers and are not used in the industry.
Phosphate rocks containing > 4% total R2O3 are considered unsuitable and the
phosphate rock should not contain > 2% iron oxide.
The following method are commonly followed to convert the insoluble phosphate
found in RP into more soluble forms.
1. Acid treatment method.
2. Phosphorus volatilization method
3. Decomposition with an alkali or silicate, and
4. Method followed in steel industry.
a. Ordinary super phosphate
This is also called as Den super phosphate. Often the term ‘super’ is used to
refer only to this product. This is the most extensively used fertilizers among the
farmers.
Manufacture
The principle involved in the process is the treatment of RP with acids, mainly
H2SO4 to convert the insoluble and unavailable tricalcium phosphate to available
dicalcium and monocalcium phosphates. Concentrated HNO3, HCl, H3PO4 and H2SO4
can be used, but sulphuric acid is found to be more suitable because of the fact that
when it reacts with the RP, CaSO4 is formed, which is a dehydrating agent and improves
the physical condition of the final product to a better condition.
The method consisted of mixing equal quantities of RP with H2SO4 in open tanks
and then powdering the resultant product after the reactions are over. The calculated
52 AgriMoon.Com
Manures Fertilizers & Agrochemicals

quantity of H2SO4 and ground phosphate rock (material passing through a four-mesh
sieve only has to be used) are introduced and mixed very thoroughly and then dropped
in a pit or den. The process is also called Den method. Sufficient time of 24 to 36 hrs is
allowed for the completion of the reaction. Temperature rises to 100°C and there is a
loss of volume by 10% due to evaporation of water, CO2 and F. The CaSO4 act as a
dehydrating agent and artificial drying is also done wherever necessary. Then the
product is ground to a very fine powder and stored for sufficient time for the curing of the
material.

1. (Ca3(PO4)2)2 CaF2 + 7 H2 SO4 3 Ca (H3PO4)2 + 7 CaSO4 + 2HF

(mcp)
2. (Ca3(PO4)2)2 Ca X + 7 H2 SO4 3 Ca (H3PO4)2 + 7 CaSO4 + H2 X
Precautions
1. An excess quantity of H2SO4 should not be used.
2. The quality of the RP must be pre decided.
Properties
The commercial super phosphate is grey in colour and it is only partly soluble in
water. It has an acid odour and acid reactions due to the presence of some free acids
and the acid salt monocalcium phosphate. It addition to the presence of phosphate, it
contains gypsum, silica and aluminum sulphate, CaF etc. It contains about 20% Ca and
12% Sulphur which are the secondary nutrient elements required for the plants.
b. Concentrated super phosphate
The main principle involved in the preparation is to first manufacture, phosphoric
acid (H3 PO4) by treating the RP with excess quantity of HCl or HNO3 or H2SO4 and
secondly the H3PO4 so obtained is used for the treatment of another quantity of
phosphate rock to get this fertilizer. Hence, there are two acid treatments involved and
so the product in called double super phosphate (double insulation). Following are the
main steps in the manufacturer of concentrated super phosphate.
1. Preparation of H3PO4 using RP and one of the mineral acids.
2. Preparation of the concentrated super phosphate by treating fresh quantity of
RP with the prepared H3PO4.

1. (Ca3(PO4)2)3 Ca X + 10H2 SO 4 6 H3PO4 + 10 CaSO4 + H2 X

2. (Ca3(PO4)2)3 Ca X + 20 HNO3 4 H3PO4 + 10 Ca(NO3)2 + H2 X
3. (Ca3(PO4)2)3 Ca X + 20 HCl 6 H3PO4 + 10 CaCl2 + H2 X

53 AgriMoon.Com
Manures Fertilizers & Agrochemicals

2. (Ca3(PO4)2)3 Ca X + 14 H3 PO4 10 Ca (H3PO4)2 + H2 X

PR is ground and allowed to pass through a constant weight feeder to which a

measured flow of H3PO4 under pressure enters. All the mixing is done in the funnel like
mixer and the mixture is allowed to stand for sufficient time for the reaction to take place.
The slurry is conveyed to a troughed belt conveyor where the product sets in a few
seconds to plastic mass. To get a dried material, sufficient retention time is allowed and
at the end of the belt- conveyor, a rotary disintegrator reduces the lumps to less than 2”
size. The disintegrated super phosphate a stored for curing at least for a period of 15
weeks.
Properties
This fertilizer resembles in all respects the ordinary super phosphate. It is grey in
color, a major portion being soluble in water. It contains 45 to 48% water soluble P2O5.
It contains lesser quantity of other ingredients.

Thermophosphates

These are manufactured by heating phosphate rock in varying temperatures.

The main drawbacks in thermal phosphates are

They are generally more expensive than acid derived phosphates. It contains no water
soluble P. They do not have any value in the manufacture of NPK fertilizers

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
hydrolyze 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.

54 AgriMoon.Com
Manures Fertilizers & Agrochemicals

12. Potassic fertilizers – manufacturing of KCl, K2SO4 and Schoenite

Potassium found to occur very commonly in the combined form as naturally
occurring minerals. Common soil forming rocks like granite and gneiss are found to
have about 3% K. For many years, K has been considered as important plant nutrient
element. 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
until eighteenth century. The first product to be used as K manure was the wood ash
and the practice of using wood ash existed for centuries.
In olden days, the wood ash was primarily used to get the potassium salts. The
wood was burnt and the resultant ash was leached in mud pots to get the salt mixture
containing chlorides, SO4 and CO3 of K, Ca and Mg. (Pot + ash = Potash). It would be
advantageous and more correct to use P and K to refer to P and K, instead of P2O5 and
K2O in the fertilizer technology i.e.,
% K = % K 2O 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 potassic fertilizers
Potassic fertilizer are classified broadly into chlorides and non- chlorides. The
following are the most important K containing materials. Wood ash, tobacco stems, wool
waste, flue dust, by products from sugar and alcohol industry. Sea weed, sea water, K
minerals, processed fertilizer like muriate and SO4 of potash and synthetic fertilizers.
K Fertilizer and manure

Natural Processed Synthetic

1. Potassic minerals 1. Muriate of potash 1. KNO3
2. Wood ash 2. Sulphate of Potash 2. K HP O4
3. Sea weed

A. Organic K fertilizer Sources

1.Wood ash
Use of wood ash as K fertilizer has been there for centuries. Wood twigs and
branches are burnt to get the ash. Sawdust is also used. The burnt material will contain

55 AgriMoon.Com
Manures Fertilizers & Agrochemicals

varying amounts at K2O from 5 to 25%. Since wood ash is highly alkaline it should not
be applied to germinating crops.
2.Tobacco stem
In the manufacture of cigarette, cigar and chewing tobacco, there results
considerable wastes consisting of mainly the stems and midribs of the leaves. This
waste material is collected, ground and sold as manure. It Tobacco stem contains 4 to
10% K2O and 2 to 3% N. It is found to be a valuable conditioner and adds bulk to the
fertilizer mixtures.
3.Wool waste
Before the raw wool could be used for spinning, it must be treated for the
removal of ‘suint’ which is the dried sweat of sheep. This ‘suint’ consists largely of K
salts and contains 1.5 to 5.0 % K2O.
4.Flue dust
It is a by product from the steel and cement industry. For melting the iron a
mixture of iron are, coal, coke and limestone are introduced into a blast furnace. When
ignited, due to tremendous heat, the K contained in the iron ore volatilizes and when the
gases containing volatilized K are burnt, the K dust will settle in the flue through which
the gases pass and from time to time the dust accumulated will be collected and used.
This will have 3 to 18% K2O as Cl, SO4 and CO3 of K.
In the same way in cement manufacture also the raw materials used are found to
have appreciable amount of K and this volatilized during the cement manufacture. The
flue dust obtained from this is found to have 3 to 13% K2O. The dust can be used as a
straight fertilizer.

5.Sea weeds
This is referred to as the poor mans manure. It contains a high amount of K2O
varying with species of weeds. Out of many varieties ‘kelp’ is found to occur extensively
throughout the world. The Sea weeds ash is found to have more than 25% K2O.
6. Sea water
It contains can inexhaustible amount of K. It contains 0.04 % K, 0.14% Mg, 0.05
% Ca and 1.14 % Na.

B. Potassic minerals
There are as many as 50 minerals that are fond to contain K but all of them are
not economically important. The K containing minerals are roughly classified into

56 AgriMoon.Com
Manures Fertilizers & Agrochemicals

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. Mg SO4. 2 CaSO4 . 2 H2O
3. Minerals insoluble in water
Glauconite - KFeSi2O6. 2 H2O
Feldspars - orthoclase - KAlSi3O8
Micas - Muscovite and biotite.
The following are commercially used for the manufacture of potassic fertilizers.
1. Sylvinite - KCl - contains 63.1 % K2O
2. Carnallite _ KCl. MgCl2. 6 H2O - contains 17% K2O
3. Kainite - KCl. MgSO4. 3H2O - contains 18.9% K2O
4. Langbeinite - K2SO4. 2MgSO4 – contains 26.6% K2O
5. Polyhalite - K2SO4. MgSO4. 2CaSO4. 2H2O – contains 15% K2O

The deposits are found to occur at a depth of 650 to 2,500 feet below the earth’s
surface.
Processed K Fertilizers
1. Muriate of potash (KCl)
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.
Mining
The deposits are found to occur usually from 650 to 2,500 feet below the earth’s
surface. Many methods of mining are employed out of which the room and pillar method
of mining is found to be familiar. 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.

57 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Purification
This involves the following process: 1. Grinding 2. Lixiviation or converting
the ore into solution form 3.Crystallization 4. Separation, drying etc.
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.
Solutioning
The ore is dissolved in hot water and to that is added the NaCl solution (brine) for
obtaining a mixture of KCl + NaCl. 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.
This is continued till a saturated solution of KCl is obtained.

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.
Separation
Crystallized KCl can be separated out by mechanical means and it is dried,
powdered and used. The above process is called the crystallization method and the
principle involved 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.
Floatation method
Floatation is a metallurgical process in which small quantities of special reagents
are added to the pulp to coat or film some of the minerals selectively with respect to
other minerals present. 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, the
finely divided air bubbles attach themselves to the reagent filmed particles and float
them to the surface of the cell, where the froth rich with the selected mineral may be
skimmed off. Some are found to be very effective to NaCl that is present in sylvinite.
First, after grinding and passing through the screen, the desired sized sylvinite
mineral is dissolved in water to get a pulp and the reagent is added to the pulp. The
reagent will form a coating or film round the NaCl molecules and this reagent added pulp
is allowed to pass through a series of floatation cells in which air is introduced at the

58 AgriMoon.Com
Manures Fertilizers & Agrochemicals

bottom in such a manner as to form a small bubble froth that attaches to NaCl. The
commonly used 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 for NaCl.
It is found that at least 90% of the potassic fertilizers consumed is in the form of
muriate of potash. It contains 48 to 62% K2O and 35 to 47% Cl. The commercial
product is either granular or powdery having white or red colour.
2.Potassium sulphate – K2SO4
This is manufactured from kainite ( KCl. Mg SO4, 3H2O) or langbeinite (K2 SO4,
Mg SO4), the latter being commonly used. The raw materials required are the mineral
langbeinite and KCl
K2SO4. Mg SO4 + 2 KCl 2K2 SO4 + MgCl2.
The MgCl2 is rejected. The KCl is used in the form of a mother liquor obtained
from KCl manufacturing process.
The method is found to be efficient only in the presence of a proper ratio between
K2SO4 and MgSO4 of the raw material and to maintain a proper ratio, KCl or Kainite is
added. The reactions are found to take place in different ways
2(K2SO4. 2Mg SO4) + 2 KCl + 12 H2O 3(K2 SO4 Mg SO44H2O) + Mg Cl2
K2SO4. 2Mg SO4) + KCl + 2 H2O K2 SO4 Mg SO4 4 H2O + KCl Mg SO4
+ 3 H 2O
(K2SO4., Mg SO4 ) 4H2O + 2 KCl 2K2 SO4 + Mg Cl2 + 4 H2O
KCl. MgSO4 3 H2O + KCl K2 SO4 + Mg Cl2 + 3 H2O

Langbeinite, ground to pass through a 200 mesh sieve and the mother liquor
from the KCl process is mixed and then the salts are recycled with water and fresh
quantity of langbeinite. The reactions are allowed to take place in interconnected tanks
and the crystallized K2SO4 is separated out by means of centrifuge. The used K2SO4 is
separated out by means of centrifuge. The wet K2SO4 is dried and conveyed to storage
place. It contains 48% K2O. Only limited quantities of K2SO4 are manufactured, as the
cost of manufacture is more, but is preferred for those crops where quality is desired or
where chlorine toxicity will result when K Cl is used.
3.Potassium Magnesium sulphate
In U.S.A. it is manufactured by mere washing of langbeinite (K2SO4. Mg SO4) to
remove the impurities and is sold under the name sulphate of potassium and
magnesium. It contains 18.5% MgO and 22.6% K2O. Since, the langbeinite is soluble in

59 AgriMoon.Com
Manures Fertilizers & Agrochemicals

water; the washing is done very easily. In Germany, it is prepared by dissolving MgSO4
and adding KCl to it.
2 KCl + 2 MgSO4 + 7H2O K2 SO4.Mg SO4. 6 H2O + MgCl2 + H2O
Manure salts
The ground and partially processed potassium mineral is sold under the name
manure salt or mine run potassium salt. Various grades are available in different
counties; Carnalite of 9-12 % K2O and other salts of 12-15 % K2O, 18-22% K2O, 28-32 %
K2O, 38-42 % K2O are also marketed and used on a limited scale.
The muck, peat, sandy, lateritic and laterite soils are deficient in K and response
will be more in these soils for K fertilizers. Clayey soils are found to give poor response
for K fertilizers. Potassic fertilizers can be added to these soils in which heavy feeders
of K are grown such as tuber crops, coconut, arecanut, banana etc. The vegetables are
found to respond well to K application.
Reactions of potassic fertilizers in the soil
Application of any potassic fertilizer does not change the pH of the soil. When a
potassium salt is applied to a soil it is immediately dissolved and undergoes ionization. A
portion of K+ ions remains in the soil solution, another portion gets adsorbed to clay
complex by CEC reactions and a third portion is converted into unavailable form.
Ca K
Clay + 2KCl Clay K + CaCl2
Ca Ca
Hence, in the soil the K will be in the solution, exchangeable and fixed forms.
The solution form is readily available and the exchangeable form is slowly and steadily
available to plants. The fixed K is unavailable but always in any soil there is a constant
equilibrium among these three forms and hence mostly exists no deficiency of K. A small
quantity of K is fixed by clays like illite, and this fixation of K depends upon the type of
clay, temperature, wetting and drying and soil pH. In this case the fixation is beneficial
as it reduces leaching loss and the availability of K will be there for a long time.
Factor affecting K fixation in soils
1. Nature of Colloids
The ability of various soil colloids to fix K varies widely. Kaolinite fixes
little, while montmorillonite and illite fix more.
2. Wetting and Drying
When soils containing exchangeable K are alternatively wetted and dried,
a large portion of exchangeable K is converted to the less available form.

60 AgriMoon.Com
Manures Fertilizers & Agrochemicals

This has been explained by assuming an entrapment of K ions between

contracting structural units when the soil dries some release of the ions
thus held occurs upon rewetting but the liberation is slow.
3. Influence of lime
Soils with high degree of base saturation lose less of their exchangeable
K by leaching than the soils with a low degree of base saturation. Liming
is the common means by which the base saturation of soils is increased
and so liming decreased the loss of exchangeable K. The K ions are
more readily replaced by calcium.
Application
The K fertilizers are usually applied before the crop is planted or sown, that is the
basal dressing. Since the applied K is not lost from the soil either by leaching or by
fixation, K fertilizers can be applied well in advance but it is preferable to apply only just
before planting. Top dressing with K fertilizers can also be done for vegetables and
other crop.

61 AgriMoon.Com
Manures Fertilizers & Agrochemicals

13. SECONDARY AND MICRONUTRIENT FRTILIZERS-Manufacturing of Zinc

sulphate and Ferrous sulphate

Zinc
Zinc is the fourth most common metal in use, trailing only iron, aluminium, and copper
with an annual production of about 12 million tonnes.[14] The world's largest zinc
producer is Nyrstar, a merger of the Australian OZ Minerals and the Belgian
Umicore.[74] About 70% of the world's zinc originates from mining, while the remaining
30% comes from recycling secondary zinc.[] Commercially pure zinc is known as Special
High Grade, often abbreviated SHG, and is 99.995% pure.

Worldwide, 95% of the zinc is mined from sulfidic ore deposits, in which sphalerite ZnS is
nearly always mixed with the sulfides of copper, lead and iron.[77] There are zinc mines
throughout the world, with the main mining areas being China, Australia and Peru. China
produced 29% of the global zinc output in 2010.

Zinc metal is produced using extractive metallurgy.[78] After grinding the ore, froth
flotation, which selectively separates minerals from gangue by taking advantage of
differences in their hydrophobicity, is used to get an ore concentrate.[78] A final
concentration of zinc of about 50% is reached by this process with the remainder of the
concentrate being sulfur (32%), iron (13%), and SiO2 (5%).[78]

Roasting converts the zinc sulfide concentrate produced during processing to zinc
oxide:[77]

2 ZnS + 3 O2 → 2 ZnO + 2 SO2

The sulfur dioxide is used for the production of sulfuric acid, which is necessary for the
leaching process. If deposits of zinc carbonate, zinc silicate or zinc spinel, like the
Skorpion Deposit in Namibia are used for zinc production the roasting can be omitted.
For further processing two basic methods are used: pyrometallurgy or electrowinning.
Pyrometallurgy processing reduces zinc oxide with carbon or carbon monoxide at 950 °C
(1,740 °F) into the metal, which is distilled as zinc vapor.[80] The zinc vapor is collected
in a condenser.[77] The below set of equations demonstrate this process

2 ZnO + C → 2 Zn + CO2
ZnO + CO → Zn + CO2
Electrowinning processing leaches zinc from the ore concentrate by sulfuric acid
62 AgriMoon.Com
Manures Fertilizers & Agrochemicals

ZnO + H2SO4 → ZnSO4 + H2O

After this step electrolysis is used to produce zinc metal.[77]

2 ZnSO4 + 2 H2O → 2 Zn + 2 H2SO4 + O2

The sulfuric acid regenerated is recycled to the leaching step.

Ferrous Sulfate
In the finishing of steel prior to plating or coating, the steel sheet or rod is passed
through pickling baths of sulfuric acid. This treatment produces large quantities of iron(II)
sulfate as a by-product.[2]

Fe + H2SO4 → FeSO4 + H2
Another source of large amounts results from the production of titanium dioxide from
ilmenite via the sulfate process.

Ferrous sulfate is also prepared commercially by oxidation of pyrite:

2 FeS2 + 7 O2 + 2 H2O → 2 FeSO4 + 2 H2SO4

[edit]
Reactions

On heating, iron(II) sulfate first loses its water of crystallization and the original green
crystals are converted into a dirty-yellow anhydrous solid. When further heated, the
anhydrous material releases sulfur dioxide and white fumes of sulfur trioxide, leaving a
reddish-brown iron(III) oxide. Decomposition of iron(II) sulfate begins at about 480 °C.

2 FeSO4 → Fe2O3 + SO2 + SO3

Like all iron(II) salts, iron(II) sulfate is a reducing agent. For example, it reduces nitric
acid to nitrogen oxide and chlorine to chloride:

6 FeSO4 + 3 H2SO4 + 2 HNO3 → 3 Fe2(SO4)3 + 4 H2O + 2 NO

6 FeSO4 + 3 Cl2 → 2 Fe2(SO4)3 + 2 FeCl3
Ferrous sulfate outside titanium dioxide factory in Kaanaa, Pori.
Upon exposure to air, it oxidizes to form a corrosive brown-yellow coating of basic ferric
sulfate, which is an adduct of ferric oxide and ferric sulfate:

12 FeSO4 + 3 O2 → 4 Fe2(SO4)3 + 2 Fe2O3

63 AgriMoon.Com
Manures Fertilizers & Agrochemicals

14. Complex fertilizers – manufacturing ammonium phosphates – nitrophosphates

and NPK complexes

COMPLEX FERTILIZERS

Complex fertilizers is defined as a material containing all three prirnary, nutrients ( N,P
and K) and it is also designated as complete complex fertilizers while a fertilizer material
containing one or two of the primary nutrient elements (N and P or P and K etc ) are
known as incomplete complex fertilizers. They are produced by a process of chemical
reaction. Most important complex fertilizers are Nitro phosphates & polyphosphate
based fertilizers etc

Nitro phosphates

It is a granular fertilizer containing stabilizer which prevents reversion of citrate soluble

phosphates to insoluble phosphate. Being granulated it maintains excellent physical
condition during storage and handling.Nitrophosphate contains nitrogen and phosphorus
in different proportions depending upon the process of manufacture. It also contains
easily soluble and readily available N03 N as well as NH4-N. Phosphorus is also present
as water soluble as well as citrate soluble forms. All nitrophosphates have less acidic
effect on soil compared to other fertilizers.

Ammonium Phosphate

Ammonium phosphate is an incomplete complex fertilizer and both monoammonium and

diammonium phosphates are manufactured by the combination of ammonia with H3PO4
and also by treating with rock phosphate with H2 SO 4and (NH4 )2SO4 as follows:
NH3+ H3PO4 = NH4H2PO4
(Mono-ammonium phosphate)
2 NH3+ H3PO4 = (NH4 ) 2 H2PO4
(Diammonium phosphate)
Ca3PO4) 2 + (NH4 )2SO4 + 2H2 SO 4 = 3 CaSO4 + 2NH4H2PO4
(Rock phosphate)

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. Product
that is too small or too large is recycled to the granulator.

64 AgriMoon.Com
Manures Fertilizers & Agrochemicals

In India, different types of nitrophosphates are manufactured with different

chemical reactions and mixing process by different fertilizer company. They marketed
the complex fertilizers as their different grades and commercial names. Most important
grades of nitrophosphate is 20: 20 : 0 and it means that nitrophosphate contains 20
percent nitrogen. 20 per cent phosphorus and no potassium. Besides these there are
various other commercially produced complex fertilizers suphala of different grades e.g.
15: 15 : 15: 20: 20 : 20 etc.

Polyphosphate based fertilizers

Ammonium polyphosphate. potassium polyphosphate. zincated poly phosphates
etc. are the most popular complex fertilizers that have been recently developed.
Ammonium polyphosphate
It is a complex fertilizer.Although it contains Nand P but it contains chiefly
phosphorus because polyphosphate is a compound derived from the condensation of
two or more phosphoric acids.
Ammonium polyphosphates may be granular and liquid. Different grades of
polyphosphates are marketed like 15-62-0; 12-53-0, 15-60-0; etc. as solid or granular
and 10-54-0, 11-37-0 as liquid. In addition to these there are Sulphated and Zincated
ammonium polyphosphates which are also available in the market to supply secondary
and micronutrient to the plant along with nitrogen and phosphorus. So the
polyphosphate based different micronutrient fertilizers which acts as slow-release
micronutrient are going to be developed recently.

Zincated polyphosphates can also be manufactured with the rock-phosphate

containing Zn and polyphosphates and that is also soluble in water and available to
plants.

A potassium polyphosphate solution of grade 0-26-26 was produced and this

was made by reacting superphosphoric acid and potassium hydroxide and contained a
mixture of ortho- pyro-and higher polyphosphates. Solid potassium polyphosphates of
grades 0-42-42 to 0-47-47 are also available

When polyphosphatic fertilizers are applied to soils, these are hydrolysed step
by step either chemically or biologically to form orthosphosphate.

65 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Diammonium phosphate (DAP) (chemical formula (NH4)2HPO4 )

It is one of a series of water-soluble ammonium phosphate salts which can be

produced when ammonia reacts with phosphoric acid. DAP is used as a fertilizer and a
fire retardant. When applied as plant food, it temporarily increases the soil pH (more
basic), 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.

Product containing diammonium phosphate as essential ingredient with small

amount of mono ammonium phosphate

Total nitrogen: x (18-21)%

P2O5 soluble in neutral ammonium citrate and water: y (45-53)%

66 AgriMoon.Com
Manures Fertilizers & Agrochemicals

15. Mixed fertilizers – sources – preparations- their compatibility – advantages

Mixed fertilizers
For over hundred years the mixed fertilizers are in use besides straight fertilizers.
Many fertilizer mixtures are made available now and this account for a major portion of
the consumption of N, P and K. Present day statistics show that numerous grades of
fertilizers mixtures are manufactured and the fertilizer mixing industry is being
considered as one of the major agro- industry.
The following are some of the common term frequently used in the mixed
fertilizer industry.
Fertilizer : The substance which is used for the supply of plant nutrients

Mixed fertilizer : A mixture of more than one straight fertilizer which can supply more
than one plant nutrient element

Complete fertilizer : A single fertilizer material containing the entire three major plant
nutrients viz, N, P and K

Fertilizer grade : This refers to the minimum guarantee with regard to the nutrient
content of the fertilizer mixture in terms of N, P and K.

Fertilizer formula : This related to the quantitative expression of the analysis of the
different ingredients included in the mixed fertilizer in terms of N, P and K.

Fertilizer ratio : This indicates the relative percentage of N, P2O5 and K2O in the
manure mixture.

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

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.

67 AgriMoon.Com
Manures Fertilizers & Agrochemicals

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.
Improper mixing and storage of fertilizers can result in large nutrient losses. Some
important aspects to consider in fertilizer mixing and storage include the following:

• Urea should not be mixed with ammonium calcium nitrate (CAN), KCl, SSP or
TSP.
• Urea can be mixed with most other fertilizers but fertilizer mixtures containing
urea should be applied immediately after mixing. Do not store fertilizer mixtures
containing urea.
• Ammonium phosphates and super phosphates should not be mixed with lime,
slag, rock phosphate or CAN.
• Potassium chloride and sulfate of potash can be mixed with most fertilizers, but
mixtures of these fertilizers with urea and calcium ammonium nitrate should not
be stored.
• CAN should not be mixed with basic slag but can be mixed with urea, single
superphosphate, and ammonium phosphates immediately prior to application.

Do not store fertilizers in damp or dirty places. Make sure that bags of fertilizer in the
store do not absorb moisture from leaky roofs or water seepage through walls and floors.
Preparation of mixed fertilizers

68 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Many kinds of materials are used in the manufacture of fertilizer mixtures. The
materials are found to be highly varying in their properties. However, only a limited
number of materials are being used like (NH4)2SO4, CO(NH2)2, Super phosphate,
ammonium phosphate, muriate of potash, limestone, gypsum and some fillers.
The manufacture 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. All the above operations are done both
mechanically and by hand operation. Different kinds of machineries are being used.
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)

R x T
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).

10 x 1000
1. Ammonium sulphate = = 500 Kg.
20

5 x 1000

69 AgriMoon.Com
Manures Fertilizers & Agrochemicals

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.

Changes that occur while manufacturing mixed fertilizer

The ingredients used in fertilizer mixtures vary widely in their physical and
chemical characteristics. When such widely varying materials in physical and chemical
properties are mixed together, naturally many changes are expected to take place during
or after the mixing. Some changes will be of physical nature and some will be of
chemical nature. The following are the most important physical changes that will take
place during or after the mixing of fertilizers.
Hygroscopicity
It is a property of any substance which absorbs from air and gets converted to
semi- solid or liquid condition. Fertilizer like Ca(NO3)2, NH4NO3, NaNO3 and CO(NH2)2
are capable of absorbing moisture from air and become hygroscopic. In such cases
handling will be very difficult for such mixtures.
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 knit 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.
Another was of preventing the caking up is manufacture of granulated fertilizer mixture.

70 AgriMoon.Com
Manures Fertilizers & Agrochemicals

The granulation aims at preparation of uniform sized particles with reasonable stability,
which presents caking up.
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. To prevent this bad effect,
granulation is conveniently followed.
The following are some of the most important chemical changes that take place
either during or after the manufacture of fertilizers mixtures. These changes are found to
be influenced by temperature, moisture content and particle size of the in gradients.
(a) 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 NH4 H2 PO4

NH4 NO3 + KCl NH4 Cl + KNO3
(NH4)2 SO4 + 2 KCl 2 NH4 Cl + K2 SO4
(b) 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.
H2PO4 + NH3 NH4 H2 PO4
2H3 PO4 + CaCO3 Ca (H3 PO4)2 + H2CO3

(c) 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 + 2H2O CaSO4 .2 H2O
Ca HPO4 + 2H2 O CaHPO4. 2 H2O

(d) Decomposition
Under certain conditions of moisture and temperature, there will be break down
in the composition of molecules forming new compounds.
CO(NH2)2 + H2 O 2 NH3 + CO2
(NH4)2 HPO4 NH4H2 PO4 + NH3

71 AgriMoon.Com
Manures Fertilizers & Agrochemicals

However, the following important principles must be taken into consideration while
preparing mixed fertilizers.
1. All 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.
Manufacturing process
The principal steps in the manufacture of solid mixed fertilizers are calculating,
weighing, sieving, sizing, mixing the materials and packing the product.

Calculating and weighing

With a good weighing device the calculated quantities of the various
ingredients are weighed accurately for preparing mixtures.
(1) Seiving and sizing
If the raw materials have undergone too much of caking in the storage piles, it
may be necessary to subject them to preliminary grinding, sieving and sizing. The
raw materials must be converted into uniform sized particles to have effective making
and to avoid segregation during subsequent handling.
(2) Mixing
Many kinds of fertilizer mixing machines have been proposed and used at present.
Rotary drum type is found to be more common than the vertical cylinder type. Weighed
quantities of different materials are introduced into the mixer and mixed thoroughly.
(3) Packing
Equipments for packing fertilizer mixture range from the simplest types of hand operated
facilities to highly sophisticated automatic machines.
Granular mixtures
Compared to pulverized or powdered mixture, the advantages of granular
mixtures are reduced caking up tendency, less dusting loss and easy handling. Of late,
attention is found in the manufacture of only granular mixtures.

72 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Ingredients used in mixtures

Different types of materials are used for the manufacture and they can be roughly
classified according to the main functions they serve in the fertilizer mixture.
(i) Supplier of plant nutrients
Various sources supplying the plant nutrients used according to the requirement and
availability of the raw materials. The selection of the different materials will be based
mainly on the prices of the various fertilizers.

Initial ingredients

Mixing

Screening oversize grinding

Wetting and Agitation

Drying

Dust cooling

Fines sizing oversize crushing

Bagging

(ii) Conditioners
To avoid caking up and other bad physical changes during or after mixing,
some materials are added to have a better physical condition. Usually low – grade
organic materials are added to reduce the caking up property, tobacco stem,
groundnut hull; paddy husk and peat are commonly used as conditioners. A
maximum of 50kg/ tonne is used as conditioner.

(iii) Neutralizer

73 AgriMoon.Com
Manures Fertilizers & Agrochemicals

If acidic fertilizer likes (NH4)2SO4, NH4NO3 and urea are used, the mixture
may be acidic or the acidity may be formed due to the interaction between the
various fertilizers used. To neutralize this acidity a basic material like dolomitic
limestone is added. The material is designated as neutralizers of residual acidity
in the fertilizer mixture.

(iv) Filler
A filler is a ‘make –weight’ material added to a fertilizer mixture. It is added to
make up the difference between the weight of the added fertilizer required to
supply the plant nutrients and the desired quantity of fertilizer mixture usually, the
filler are inert materials like sand and sawdust which are commonly used. This
must be usually less than 50 kg per tonne of mixture.

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 in one tonne of the
material. The cost per unit is arrived at by dividing the cost per tonne by the percentage
of nutrient contained in it. For example, if the cost of a tonne 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.

74 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Mid
Semester
Examination

**Best of Luck**
75 AgriMoon.Com
Manures Fertilizers & Agrochemicals

BIOFERTILIZERS

Biofertilizers are defined as preparations containing living cells or latent cells of

efficient strains of microorganisms that help crop plants uptake of nutrients by their
interactions in the rhizosphere when applied through seed or soil. They accelerate certain
microbial processes in the soil which augment the extent of availability of nutrients in a
form easily assimilated by plants.
Use of biofertilizers is one of the important components of integrated nutrient
management, as they are cost effective and renewable source of plant nutrients to
supplement the chemical fertilizers for sustainable agriculture. Several microorganisms and
their association with crop plants are being exploited in the production of biofertilizers. They
can be grouped in different ways based on their nature and function.
I. N2 fixers

a. Free living : Aerobic – Azotobacter, Beijerinckia, Anabaena

Anaerobic – Clostridium
Faultative anaerobic – Klebsiella

b. Symbiotic : Rhizobium, Frankia, Anabaena azollae

c. Associative symbiotic : Azospirillum

d. Endophytic : Gluconacetobacter
Burkholdria
II. Phosphorus solubilizers

Bacteria : Bacillus megaterium var. phosphaticum

B. subtilis, B. circulans
Pseudomonas striata

Fungi : Penicillium sp.

Aspergillus awamori

III. P mobilizers
a) AM fungi
b) Ectomycorrhizal fungi
c) Ericoid Mycorrhiza
d) Orchid mycorrhiza
IV. Silicate and Zinc solubilizers: Bacillus sp,
V. Plant growth promoting Rhizobacteria: Pseudomans spp.,and many more

76 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Importance of Biofertilizers
Biofertilizers are known to make a number of positive contributions in agriculture.
• Supplement fertilizer supplies for meeting the nutrient needs of crops.
• Add 20 – 200 kg N/ha (by fixation) under optimum conditions and solubilise/mobilise
30-50 kg P2O5/ha.
• They liberate growth promoting substances and vitamins and help to maintain soil
fertility.
• They suppress the incidence of pathogens and control diseases.
• Increase the crop yield by 10-50%. N2 fixers reduce depletion of soil nutrients and
provide sustainability to the farming system.
• Cheaper, pollution free and based on renewable energy sources.
• They improve soil physical properties, tilth and soil health.
1. Rhizobium
Rhizobia are soil bacteria, live freely in soil and in the root region of both leguminous
and non-leguminous plants. However they enter into symbiosis only with leguminous plants,
by infesting their roots and forming nodules on them. Non legume nodulated by Rhizobia is
Trema or Parasponia sp.
The nodulated legumes contribute a good deal to the amount of N2 fixed in
the biosphere, (50-200 kg N/ha) varied with crops.

Clover - 130 kg N/ha

Cowpea - 62 – 128 kg N/ha

Beijerinck first isolated and cultivate a microorganism from the roots of legumes in
1888 and he named this as Bacillus radicola and latter modified as Rhizobium.
Legume plants fix and utilise this N by working symbiotically with Rhizobium in
nodules on their roots. The host plants provide a home for bacteria and energy to fix
atmospheric N2 and in turn the plant receives fixed N2 (as protein).
Cross inoculation group (CGI)
It refers the group of leguminous plant that will develop nodules when inoculated
with the rhizobia obtained from the nodules from any member of that legume group.

Genera/species Principal and other reported hosts

Rhizobium
R.etli Phaseolus vulgaris, Mimosa affinis

77 AgriMoon.Com
Manures Fertilizers & Agrochemicals

R.galegae Galega orientalis, G.officinalis

R.gallicum Phaseolus vulgaris, Leucaena, Macroptilium, Onobrychis
R.giardini Phaseolus vulgaris, Leucaena, Macroptilium
R.hainanense Desmodium sinuatum, Stylosanthes, Vigna, Arachis,
Centrosema
R.huautlense Sesbania herbacea
R.indigoferae Indigofera
R.leguminosarum
bv trifolii Trifolium
bv viciae Lathyrus, Lens, Pisum, and Vicia,
bv.phaseoli Phaseolus vulgaris
R.mongolense Medicago ruthenica, Phaseolus vulgaris
R.sullae Hedysarum coronarium
R.tropici Phaseolus vulgaris, Dalea, Leucaena, Macroptilium,
Onobrychis
Mesorhizobium
M.amorphae Amorpha fruticosa
M.chacoense Prosopis alba
M.ciceri Cicer arietinum
M.huakuii Astragalus sinicus, Acacia
M.loti Lotus corniculatus
M. mediterraneum Cicer arietinum
M.plurifarium Acacia senegal, Prosopis juriflora, Leucaena
M.tianshanense Glycyrrhiza pallidflora, Swansonia, Glycine, Caragana,
Sophora
Sinorhizobium
S.abri Abrus precatorius
S.americanus Acacia spp.
S.arboris Acacia senegal, Prosopis chilensis
S.fredi Glycine max
S.indiaense Sesbania rostrata
S.kostiense Acacia senegal, Prosopis chilensis
S.kummerowiae Kummerowia stipulacea
S.meliloti Medicago, Melilotus, Trigonella

78 AgriMoon.Com
Manures Fertilizers & Agrochemicals

S.medicae Medicago truncatula, M. polymorpha, M.orbicularis

S.morelense Leucaena leucocephala
S.sahelense Acacia, Sesbania
S.terangae Acacia, Sesbania
Azorhizobium
A.caulinodans Sesbania rostrata
Allorhizobium
A.undicola Neptunia natans, Acacia, Faidherbia, Lotus
Bradyrhizobium
B.elkanii Glycine max
B.japonicum Glycine max
B.liaoningense Glycine max
B.yuanmingense Lespedeza, Medicago, Melilotus

Description and characteristics

Classification

1. Family : Rhizobiaceae

2. Genus : Azorhizobium-for stem nodulation

Bradyrhizobium
Rhizobium
Sinorhizobium

Morphology
1. Unicellular, cell size less than 2µ wide, short to medium rod, pleomorphic.
2. Motile with Peritrichous flagella
3. Gram negative
4. Accumulate PHB granules.
Physiology

1. Nature : Chemoheterotrophic, symbiotic with legume

2. C source : Supplied by legume through photosynthates,

monosaccharides, disaccharide

3. N source : Fixed atmospheric N2

79 AgriMoon.Com
Manures Fertilizers & Agrochemicals

4. Respiration : Aerobic

5. Growth : Fast (Rhizobium), slow (Bradyrhizobium)

6. Doubling time : Fast growers – 2-4 hrs

Slow growers – 6-12 hrs

7. Growth media : YEMA

Contribution
1. Direct contribution of N symbiotically with legumes.
2. Residual nitrogen benefit for the succeeding crop.
3. Yield increase is by 10-35%.
4. Improve soil structure.
5. Produces exopolysaccharides.
6. Produces plant growth hormone.
Recommended for legumes (Pulses, oilseeds, fodders)
Promising strains: NGR 6, NC 92, CC 1, CRR 6, CRU 14, COBE 13.
2. Azotobacter
It is a free living N2 fixer, the cells are not prevent on the rhizoplane, but are
abundant in the rhizosphere region. It is classified under the family Azotobacteriaceae. It
requires more of organic matter and depend on the energy derived from the degradation of
plant residues. Beijerinck was the first to isolate and describe Azotobacter.
Species
Cell size, flagellation, pigmentation and production of extracellular slime are
considered as diagnostic features of these bacteria in distinguishing species.

A. chroococcum : Black to brown insoluble pigment.

A. vinelandii, A. paspali, : Green fluorescent and soluble pigments

A. agilis

A. beijerinckii : Yellow to light brown insoluble pigments

A. macrocytogenes : Pink soluble pigments

A. insignis : Yellow brown pigments

80 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Azotobacter cells are polymorphic, gram negative, form cyst and accumulate Poly
Beta hydroxy butyric acid and produces abundant gum.
Morphology

Cell size : Large ovoid cells, size 2.0 – 7.0 x 1.0 – 2.5 µ

Cell character : Polymorphic

Gram character : Negative

Physiology

1. Nature : Chemoheterotrophic, free living

2. C source : Mono, di saccharides, organic acids

3. N source : N2 through fixation, amino acids, NH4+, NO3-

4. Respiration : Aerobic

5. Growth : Ashby / Jensen's medium

6. Doubling time : 3 hours

Benefits
• Ability to fix atmospheric N2 – 20-40 mg BNF/g of C source in laboratory equivalent to
20-40 kg N/ha.
• Production of growth promoting substances like vitamin B, Indole acetic acid, GA.
• Ability to produce thiamine, riboflavin, pyridoxin, cyanogobalanine, nicotinic acid,
pantothenic acid, etc.
• Biological control of plant diseases by suppressing Aspergillus, Fusarium.
- Recommended for Rice, wheat, millets, cereals, cotton, vegetables, sunflower, mustard
and flowers.
3. Azospirillum
Azospirillum was I isolated by Beijerinck (1922) in Brazil from the roots of Paspalum
and named it as Azotobacter paspali and later named as Spirillum lipoferum. Dobereiner and
Day (1976) reported the nitrogen fixing potential of some forage grasses due to the activity
of S. lipoferum in their roots. Dobereiner coined the term "Associative symbiosis" to
denote the occurrence of N2 fixing spirillum in plants. Taxonomy was re-examined and
Tarrand et al. (1978) designated this organism as Azospirillum.

81 AgriMoon.Com
Manures Fertilizers & Agrochemicals

It is an aerobic or micro aerophilic, motile, gram negative bacterium. Non spore

former and spiral shaped bacterium, inhabiting the plant roots both externally and
internally. Being a micro aerophilic organism, it can be isolated on a semi solid malate
medium by enrichment procedures.
Classification
Species: (7) Family – Spirillaceae
1. A. brasilense
2. A. lipoferum
3. A. amazonense
4. A. halopraeferens
5. A. irkense
6. A. dobereinerae
7. A. largimobilis
Morphology

1. Cell size : Curved rods, 1 mm dia, size and shape

vary

2. Accumulate : PHB

3. Gram reaction : Negative

4. Development of white pellicles : 2-4 mm below the surface of NFB medium

Physiology

1. Nature : Chemoheterotrophic, associative

2. Sole carbon source : Organic acids, L-arabinose, D-gluconate,

D-fructose, D-glucose, sucrose, Pectin

3. N source : N2 through fixation, amino acids, N2, NH4+, NO3-

4. Respiration : Aerobic, Microaerophilic

5. Growth media : NFBTB (NFB) medium

6. Doubling time : 1 hr in ammonia containing medium

5.5 – 7.0 hrs in malate containing semisolid
medium
Mechanism of Action
1. Contribution by BNF
2. Production of PGP substances by bacteria
– Increases root hair development, biomass.

82 AgriMoon.Com
Manures Fertilizers & Agrochemicals

3. Production of PGP substances by plant

– Morphological changes in root cells.
– Increased activity of IAA oxidase
– Increase in endogenous IAA
– Increased mineral and water uptake, root development, vegetative growth and crop
yield.
4. Competition in the rhizosphere with other harmful microorganism.
5. Polyamines and amino acids production.
6. Increased extrusion of protons and organic acids in plants.
Benefits
1. Promotes plant growth.
2. Increased mineral and water uptake, root development, vegetative growth and crop
yield.
3. Inoculation reduced the use of chemical fertilizers (20-50%, 20-40 kg N/ha)
4. Increases cost benefit ratio.
5. Reduces pathogen damage.
6. Inhibit germination of parasitic weeds.
7. Restoration of arid zone, margine mangrove ecosystem.
8. Reduces humic acid toxicity in compost.
- Recommended for rice, millets, maize, wheat, sorghum, sugarcane and co-inoculant
for legumes.
4. Gluconacetobacter diazotrophicus
It is an endophytic N2 fixer and form to occur on large numbers in roots, stem and
leaf of sugarcane and other sugar rich crops. It was first isolated from sugarcane. Cavalcanti
and Dobereiner (1988) reported this new endophytic N2 fixer and recently called as from G.
diazotrophicus. It can tolerate upto 30% sucrose concentration and pH upto 3.0. Optimum
sucrose concentration is 10-15%.
Produce surface yellow pellicle on semisolid medium. Does not grow at pH 7.0.
Optimum is 5.5.
Benefits
- Fixes atmospheric N2
- Production of PG hormones (GA, DAA is double than Azospirillum).
- Suitable for sugar rich crops with acidic pH.

83 AgriMoon.Com
Manures Fertilizers & Agrochemicals

5. Azorhizobium
These genera can produce stem nodules. Stem nodulation has been reported in 3
genera of legumes: Aeschynomene, Neptunia and Sesbania.
Stem nodulating Rhizobium comprises both fast and slow growing types having the
generation time of 3-4 hr and 10 hrs respectively. Those nodulate Aeschynone can cross
inoculate with S. rostrata strains Azorhizobium caulinodans.
- fix N2 in free living conditions without differentiating into bacteroids.
- have O2 protection mechanisms, to fix N2 under free living conditions.
- Mode of entry is through lateral root cracks. No infection thread is formed during
colonization.
- Form both stem and root nodules in S. rostrata.
- Gram negative, motile rods.
- Produces root nodules in rice, wheat.
6. Algal Biofertilizers
The agronomic potential of cyanobacterial N2 fixation in rice fields was recognised in
India during 1939 by De who attributed the natural fertility of tropical rice fields to N2 fixing
blue green algae. The rice field ecosystem provides an environment favourable for the
growth of blue green algae with respect to their requirements for light, water, high
temperature and nutrient availability.
Algal biofertilizers constitutes a perpetual source of nutrients and they do not
contaminate ground water and deplete the resources. In addition to contributing 25-30 kg N
ha-1 of biologically fixed N2, they can also add organic matter to the soil, excrete growth
promoting substances, solubilises insoluble phosphates and amend the physical and
chemical properties of the soil.
Blue green algae are a group of prokaryotic, photo synthetic microscopic plants,
vigorously named as Myxophyceae, Cyanophyceae and Cyanobacteria. They show striking
morphological and physiological similarities like bacteria and hence called as cyanobacteria.
Cyanobacteria
They are the photosynthetic bacteria and some of them are able to fix N2. They can
be divided into two major groups based on growth habit.

a) Unicellular forms and

b) Filamentous forms.

N2 fixing species are from both groups, found in paddy fields, but the predominant
ones are the heterocystous filamentous forms.

84 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Cyanobacteria are not restricted to permanently wet habitats, as they are resistant
to desiccation and hot temperatures, and can be abundant in upland soils. However wet
paddy soils and overlying flood waters provide an ideal environment for them to grow and
fix N2.
Natural distribution
BGA are cosmopolitan in distribution and more widely distributed in tropical zone.
Free living cyanobacteria can grow epiphytically on aquatic and emergent plant as well as in
flood water or on the soil surface. Heterocystous cyanobacteria formed less than 10% of the
population of eukaryotic green algae and the abundance increased with the amount of
available phosphorus and with the pH value over the range 4 – 6.5. In rice soil, population
ranges from 10 – 107 cfu g-1 soil.

The main taxa of N2 fixing cyanobacteria

Group Genera DNA
(mol % GC)
Group-I. Unicelluar: single Gloeothece, 35-71
cells or cell aggregates Gloeobacter,Synechococcus,
Cyanothece, Gloeocapsa,
Synechocystis, Chamaesiphon,
Merismopedia
Group-II. Pleurocapsalean: Dermocarpa, Xenococcus, 40-46
reproduce by formation of small Dermocarpella, Pleurocapsa,
spherical cells called baeocytes Myxosarcina, Chroococcidiopsis
produced through multiple
fission.
Group-III. Oscillatorian: Oscillatoria, Spirulina, Arthrospira, 40-67
filamentous cells that divide by Lyngbya, Microcoleus,
binary fission in a single plane. Pseudanabaena.
Group-IV. Nostocalean: Anabaena, Nostoc, Calothrix, 38-46
filamentous cells that produce Nodularia, Cylinodrosperum,
heterocysts Scytonema
Group-V.Branching: cells Fischerella, Stigonema, 42-46
divide to form branches Chlorogloeopsis, Hapalosiphon

The N2 fixing forms generally have a specialized structure known as heterocyst. The
BGA have minimum growth requirement needing only diffused light, simple inorganic

85 AgriMoon.Com
Manures Fertilizers & Agrochemicals

nutrients and moisture. The heterocysts which are modified vegetative cells, because of
their thick walls and absence of photonactin II in photosynthesis, act as ideal sites for N2
fixation under aerobic conditions. Although the nitrogenase is present in vegetative cells, it
remains inactive because of the presence of oxygenic photosynthesis. They built up natural
fertility (C, N) in soil.
N2 fixing BGA: Anabaena, Nostoc, Cylindrospermum, Tolypothrix, Calothrix, Scytonema,
Westiellopsis belonging to orders Nostocales and Stignematales. Many non-heterocystous
forms are also fix N2. eg: But need microaerobic or anaerobic conditions. Gleocapsa fix in
aerobic condition.

The species of BGA, known to fix atmospheric N2 are grouped as 3 groups.

(i) Heterocystous – aerobic forms

(ii) Aerobic unicellular forms

(iii) Non-heterocystous, filamentous, micro aerophilic forms.

The blue green algal culture's composite inoculum consists of Nostoc, Anabaena,
Calothrix, Tolypothrix, Plectonema, Aphanotleca, Gleocapsa, Oscillatoria, Cylindrospermum,
Aulosira and Scytonema.
Contributions of algal biofertilizer
- Important component organic farming.
- Contribute 20 – 25 kg N ha-1.
- Add organic matter to the soil.
- Excrete growth promoting substances.
- Solubilize insoluble phosphates.
- Improve fertilizer use efficiency of crop plants.
- Improve physical and chemical properties of soil.
- Reduce C:N ratio.
- Increase the rice yield by 25-30%.
- Cyanobacteria are more compatible with nitrate N than ammonium N.
It increases FUE of the crop plants through exudation of growth promoting
substances and preventing a part of applied fertilizer N from being lost.

86 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Phosphobacteria and Mycorrhizae

I. Phosphate solubilising Microorganisms
Introduction
Though most soils contain appreciable amounts of inorganic P, most of it being
insoluble forms, cannot be utilized by crops unless they are solubilzied. Soils also contain
organic P that could not be utilized by plants only when it is mineralized. Phosphate
solubilizing microorganisms not only able to solubilize insoluble forms of inorganic P but are
also capable to mineralize organic forms of P, thus improving the availability of native soil P
making their P available to plants. PSM can also solubilize P from rock phosphate (RP), slag
or bone meal making their P available to plants.
Thus PSM biofertilizer being economical and environmentally safe offers a viable
alternative to chemical fertilizers.
Microorganisms involved
Many microorganisms can solubilize inorganic phosphates, which are largely
unavailable to plants. Microbial involvement in solubilization of inorganic phosphate was first
shown by Stalstron (1903) and Sacket et al. (1908) gave conclusive evidence for bacterial
solubilization of RP, bonemeal and TCP.
Various bacteria and fungi reported to solubilize different types of insoluble
phosphates. Not only solubilizes but also mineralize organic P compounds and release
orthophosphates.
In general PSM constitute 0.5 – 1.0% of soil microbial population with bacteria and
out numbers the fungi by 2 – 150 folds. But bacteria may loose the P solubilizing ability
while sub culturing and fungi do not lose. Among bacteria, aerobic spore forming bacteria
are more effective P solubilizers.
Mechanism of PO4 solubilization
Different mechanisms were suggested for the solubilization of inorganic phosphates.
Ø Production of organic acids

Ø Chelating effect

Ø Production of inorganic acids

Ø Hydrogen sulphide production (H2S)

Ø Effect of carbon dioxide

Ø Proton extrution
Ø Siderophore production

87 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Siderophores, bind iron tightly to prohibit its reaction with soluble phosphate and
rather help release PO4 fixed as ferric phosphate. It is important in acid soils, where ferric
PO4 is one of the major forms.
The extent of PO4 solubilization depends on the type of organisms involved. The
genus Bacillus showed maximum activity followed by Penicillium and Aspergillus.
Streptomyces was least effective.
A. awamori & A. niger, Bacillus polymixa & Penicillium striata are effective in
solubilization of phosphate solubilizarion
II. Mycorrhizae
Mycorrhiza (fungus root) is the mutualistic association between plant roots and
fungal mycelia. Frank (1885) gave the name "mycorrhiza" to the peculiar association
between tree roots and ectomycorrhizal fungi. 95% of the plant species form mycorrhizae.
It can act as a critical linkage between plant roots and soil. This association is characterized
by the movement of plant produced carbon to fungus and fungal acquired nutrients to
plants. Mycorrhizal fungi are the key components of the rhizosphere are considered to have
important roles in natural and managed ecosystems.
Types of mycorrhiza
Mycorrhizal associations vary widely in structure and function. Two main groups of
mycorrhizae are recognized; the ectomycorrhizae and endomycorrhizae, although the rare
group with intermediate properties, the ectendotrophic mycorrhizae.
1. Ectomycorrhiza
The fungal hyphae form a mantle both outside the root and within the root in the
intercellular spaces of the epidermis and cortex. No intracellular penetration into epidermal
or cortical cells occurs, but an extensive network called the Hartignet is formed between
these cells. Sheath or Mantle increases the surface area of absorbing roots and offers
protection to the roots. Hartignet can act as storage and transport organ for P.
Ectomycorrhizae are common on trees, including members of the families pinaceae
(Pin, Fir, Spruce, Larch, Semlock), Fagaceae (Willow, Poplar, Chesnut), Betulaceae (Birch,
Alder), Salicaceae (Willow, Poplar) and Myrtaceae.
The fungi forming Ectomycorrhizal association are coming under Basidiomycotina and
Ascomycotina. eg: Laccaria laccata, Suillus, Rhizopogan, Amanita
2. Endomycorrhizae
Endomycorrhizae consist of three sub groups, but by far the most common are the
Arbuscular Mycorrhizal fungi. Fungi under AM are the members of Endogonaceae and they
produce an internal network of hyphae between cortical cells that extends out into the soil,

88 AgriMoon.Com
Manures Fertilizers & Agrochemicals

where the hyphae absorb mineral salts and water. This fungus do not form an external
mantle but lives within the root. In all forms, hyphae runs between and inside the root cells
which includes,

Ericoid mycorrhiza - Associated with some species of Ericaceous plants

Orchid mycorrhiza - associated with orchid plants

Arbuscular mycorrhiza - associated with most of the plant families

Arbuscular Mycorrhizal fungi

The most important one is AM
AM, an endomorphic mycorrhizae formed by the aseptate phycomycetous fungi are
associated with majority of agricultural crops, growing under broad ecological range.

Class : Zygomycotina

Order : Endogonales

Family : Endogonaceae

150 species of AMF are known.

Colonization Process
Roots do not show visual morphological changes due to AM colonization. AM fungal
infection into a host occurs by germination of spore, hyphal growth through soil to host
roots, penetration of host roots and spread of infection inter and intracellularly in the root
cortex. Colonization occurs under two phases: (1) Extra matrical phase and (2) Intra radical
phase.
Extra matrical phase: Events occurring outside the root after the germination of
chlamydospores. Mycelium explores larger soil volume. Fungal growth can be 80-130 times
the length of root. Extra matrical hyphae (EMH) are larger in diameter than inner hyphae.
Once the fungus recognises the plant, appresorium is formed in the host roots and
penetration occurs via the appresorium. EMH ends with resting spores in soil.
Intra radical phase: Events occurring inside the root cortex. After penetrating the cortex,
the fungus may produce intercellular as well as intracellular hyphae in the cortical cells.
Forms two morphological structures namely arbuscules and vesicles inside the cortical cells.
Arbuscules: are the first formed structures after the hyphal entry into the cortical cells.
Arbuscules are the fine dichotomously branched hyphal filaments look like little trees.
Arbuscules start to form approximately 2 days after penetration. They are considered as the

89 AgriMoon.Com
Manures Fertilizers & Agrochemicals

major site of exchange between the fungus and host root. They are short lived (4-13 days)
and degenerate.
Vesicles: Following the formation of arbuscules, some species of fungi also form vesicles in
the roots. Terminal or intercallery hyphal swellings of the hyphae called vesicles. Vesicles
contain lipids and cytoplasm. They act as P storage organ and they ever be present in the
root. Size of the vesicles is about 30-100 µm. In vesicles P can be accumulated as
polyphosphates.
EMH, vesicles and Arbuscules play a key role in nutrient transfer particularly in mobilisation
of phosphorus.
Mechanism of action
The beneficial effect on plant growth and yields following inoculation with VAM is
attributed to
(i) improved mineral nutrition, especially P (P, Zn, Cu, K, S, NH4)
(ii) Mobilization of nutrients through greater soil exploration.
(iii) Protection of host roots against pathogen infection.
(iv) Improved water relation
(v) Better tolerance to stress like salinity, heavy metal pollution
(vi) Protection against transplantation shock.

Continued…..

Arbuscules vesicles.

90 AgriMoon.Com
Manures Fertilizers & Agrochemicals

stained masses of fungal hyphae cells of the orchid are filled with coils
(arrowheads). of fungal hyphae

91 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Reasons for Enhanced P uptake by AM Fungi

- Physical exploration of soil.
- Higher affinity towards P
- Lower threshold concentration
- Rhizosphere modification
- Differences in anion and cation absorption due to exudation pattern.
- Siderophore production.
- Selective stimulation of microorganisms in the rhizosphere.
- Increased hyphal area for absorption (EMH).
- Absorb and transport P beyond the depletion zone around the root.
- P absorption by EMH is 1000 times faster than normal hyphae and 3-4 times greater.
Disease resistance
- Resist the parasitic invasion and minimises the loss.
- Mycorrhizal roots harbour more actinomycetes.
- Mycorrhizal roots have elevated levels of phenols, while offers resistance to fungal
hydrolytic enzymes.
- Mycorrhizal infection stimulates biosynthesis of phytoalexins.

92 AgriMoon.Com
Manures Fertilizers & Agrochemicals

18. IMPACT OF FERTILIZERS ON THE ENVIRONMENT

Fertilizer is one of the major contributors to increased crop production. Recently,

concern has been expressed that over-reliance on mineral fertilizers may cause
unsustainable environmental penalties like eutrophication of surface water, nitrate (NO3')
pollution of groundwater, heavy metal pollution of soil, atmospheric pollution due to
emission of nitrous oxide and ammonia, acid rain, etc. Though there are incidences of
these problems in several parts of the world, very few of such problems in India can be
linked to fertilizer use.
India has to produce 380 million tonnes against the present production of 206 million
tonnes of food grain per annum in order to feed a population of 4 billion by 2025..
As there is no scope for horizontal expansion of our agricultural land additional amount
of food grain has to be harnessed vertically in which fertilizer takes the lead role. Where
there is no doubt on the yield propelling effect concerns have been expressed about the
environmental impact of fertilizer use. There are some claims of dire consequences with
fertilizer use and more particularly against N fertilizers. This makes some sense as
fertilizer recovery efficiency of N " seldom exceeds 50 per cent. A major portion of the
applied fertilizer is lost from soil-plant system by leaching, runoff, denitrification and
volatilization and pollutes the soil, water and air; the vital resources of nature..

At present the country consumes about 17.8 million tones of fertilizer per annum and
more than 65 per cent of it is nitrogenous fertilizer. The consumption of fertilizer has
registered a spectacular growth during the last 3 decades and a very good correlation
has been seen between food grain production and fertilizer consumption. Average
consumption of fertilizer (N+P+K) in the country in 1999-2000 is about 106 kg ha" yr-1.
Though, this is much less in comparison to many other countries like China, Japan.
United Kingdom, Korea, and Netherlands, where the consumption of N+P+K are 271,
295, 343, 459, and 50 kg ha-' yr-1. respectively. Fertilizer consumption even in the
neighbouring countries like Bangladesh and Pakistan are higher i.e., 154 and 129 kg ha-I
yr·l, respectively, than that of India. Moreover there is regional disparity in terms of
fertilizer consumption. Farmers of Punjab use nearly 250 kg fertilizer ha" yr 1 , whereas in
North East Regions it is only 5-10 kg ha-I yr'.

Environmental Consequences of NPK Fertilizer Use

Fertilizer N. P and K. after their application in soil undergo various transformation

93 AgriMoon.Com
Manures Fertilizers & Agrochemicals

processes. A host of physical, chemical and biological processes are involved in such
turn over. For example, dynamics of N in the soil-plant-atmosphere system includes the
various soil processes like mineralization, immobilization, urea hydrolysis. nitrification,
volatilization and, denitrification. Phosphorus after its application in soil is either removed
by crop or gets converted into various insoluble forms (Fe and Al phosphate in acid soil
and Ca-phosphate in alkaline soils) arid gets fixed in soil -clays or organic matter. The
use efficiency of P does not exceed 20%. Significant amount of P is lost from the soil
through surface runoff and erosion resulting in eutrophication of water bodies. Potassium
is the most abundant plant nutrient in soil. It is more mobile than phosphate and is
susceptible to loss by leaching, runoff and erosion. The use efficiency of fertilizer K is
about 70%. Loss of K is a waste but carries no environmental concern.
Major environmental' consequences related to fertilizer use
Nitrate Pollution of Groundwater
Pollution of groundwater from fertilizer N is caused by leaching. The magnitude
of loss depends upon soil conditions, agricultural practices, agro-climatic. conditions,
and type of fertilizers and methods of application. The time taken by nitrate "to move
from the root zone to the water table, therefore, varies considerably. In sandy soils with
high water table and high rate of fertilizer application, it may reach the water table in
matter of days whereas in heavy soils, low rainfall and low rate of application' with deep
water table, it may take years.
Two main alleged health hazards are blue baby disease of young babies and cancer
due to nitrate ingestion in food and water. World Health Organization (WHO)
recommends that drinking water should not more than 10mg NO3-N L"I (50mg ,NO3]'
Lot). However. nitrate is non-toxic, the concern is with its microbial reduction to nitrite.
The nitrate is converted into nitrite in the intestine and then absorbed in the blood
stream. Young babies cannot detoxify this nitrite, which combine with hemoglobin to
form inactive form methaemoglobin thus reducing the capacity of blood to carry oxygen.
When the conversion of nitrate to nitrite exceeds 10% blood is incapable of carrying
oxygen and clinical symptoms such as gray or blue skin develop known as
"methaemoglobinaemia" or "blue baby syndrome".
Tamil Nadu in the south, Orissa (Ganjam district) and Bihar in the cast and
Gujarat on the west high average nitrate and high N fertilizer consumption. But there
were several exceptions. For example, in West Bengal, where the average nitrate level
was low inspite of high dosage of N fertilizers. There are very few cases of high nitrate
content in groundwater in India that can be related to fertilizer use. We argue that the

94 AgriMoon.Com
Manures Fertilizers & Agrochemicals

stray incidence of high nitrate levels in groundwater in certain pockets cannot be

attributed to mineral fertilizer consumption but to dumping of animal wastes and
extensive use of farmyard manure
.
Eutrophication
Another major problem associated with excess fertilizer use is the eutrophication
of surface water causing several diseases. Arable soils leak considerable amounts of
nitrate, phosphate, potassium and other nutrients mainly through run-off and erosion,
which enrich the water body in terms of nutrients leading to luxurious growth of algae
and other organisms and resultant eutrophication problems in ponds

Ammonia Volatilization

Volatilization of NH3 is not only a major loss of N but also a cause of

environmental pollution. From the atmosphere NH3, is washed out by clouds and
redeposit' on the terrestrial ecosystem In the atmosphere it is oxidized to N2O, which
acts as a greenhouse gas and is responsible for the destruction of ozone layer. It also
forms salts with acidic gases and these salt particles can be transported long distances
especially in the absence of clouds. The deposition close to the source is substantial,
but hard to estimate due to interaction with other pollutants. In northern Europe, it has
been estimated that 94% of the NH3, released from agricultural sources is redeposited
into surrounding ecosystems

Acid Rain

The effect of acid rain on ecosystems is gradually being documented, particularly

in temperate region Nitrogenous fertilizers contribute substantially towards emissions
of ammonia, one of the agents causing acid rain. A high atmospheric concentration of
ammonia can result in acidification of land and water surfaces, cause plant damage and
reduce plant bio-diversity in natural systems. Excess of ammonia deposited causes
eutrophication effect of N. Deposition of NH3 contributes to acidification of soils if
nitrified.
Greenhouse Gases

Greenhouse gases (GHGs) are atmospheric compounds that store energy, thus
influencing the climate. Each of the GHGs has a different global warming potential that
takes into account the effectiveness of each gas in trapping heat radiation and its
95 AgriMoon.Com
Manures Fertilizers & Agrochemicals

longevity in the atmosphere. For instance, one kilogram of methane (CH4) is estimated
to have the same warming potential as 21 kilograms of carbon dioxide (CO2), and one
kilogram of nitrous oxide (N2O) has an equivalent impact to approximately 310 kilograms
of CO2.

According to the Organization for Economic Cooperation and Development

(OECD), CO2, CH4 and N2O emissions in agriculture at global level are estimated to
account for 14 per cent of the total emission of GHGs. However, estimates of both
absorption and emission of these three gases are subject to significant uncertainties.

Nitrogen Gas (N2)

Large amounts of nitrogen gas are emitted to the atmosphere via denitrification,
including that of nitrogen fertilizers. Nitrogen gas constitutes 78 per cent of the
atmosphere and it has no direct greenhouse effect. Release of N2 reduces nitrogen (N)
available to crops, but is not otherwise detrimental to the environment.

Nitrogen Oxides (NO and NO2)

Nitrogen oxides are not GHGs. Nitrogen fertilizer input accounts for only 0.5 per
cent of NO emissions. Both nitric oxide (NO) and nitrogen dioxide (NO2) react in sunlight
with volatile organic compounds to form tropospheric ozone (O3). Ozone is toxic to
crops, even at low concentrations, and detrimental to the health of sensitive individuals.

Nitrous Oxide (N2O)

Nitrous oxide has a greenhouse effect and is considered to be detrimental to the
ozone layer. According to experts of the Intergovernmental Panel on Climate Change
(IPCC), N2O is responsible for 7.5 per cent of the calculated greenhouse effect caused
by human activity. The concentration in the atmosphere is increasing at a rate of about
0.2 per cent per year. Although nitrogen fertilizers can be a direct or indirect source, they
account for only 0.8 per cent of the N2O emissions. Moreover, new, more efficient
nitrogen fertilizers coupled with site-specific fertilization practices reduce N2O emissions.
Methane (CH4)
Methane is a GHG. Within agriculture, CH4 is emitted mostly by ruminant digestive
process and from livestock wastes. Rice paddy fields are also a major source of CH4 that
is formed by the anaerobic decomposition of organic matter. The addition of readily

96 AgriMoon.Com
Manures Fertilizers & Agrochemicals

decomposable organic matter significantly increases CH4 emissions. The impact of

mineral fertilizers on CH4 emissions is not clear, but seems minor.

Fertilizers and Gas Emissions

The use of phosphate and potash fertilizers does not contribute directly to GHG
emissions, but all forms of nitrogen fertilizers may lead to N2O emissions. Since there is
no significant uptake mechanism for N2O in agricultural systems, mitigation focuses on
emission reduction. In general, agricultural practices that increase nutrient use efficiency
and diminish nitrogen leaching are also appropriate for minimizing N2O emissions. Best
management practices, which match the nitrogen supply to crop requirements and
integrate animal manure and crop residue management into crop production, result in a
net reduction in N2O emissions. The proper balance of nutrients optimizes the efficiency
of applied and residual soil nitrogen. Other agricultural practices that minimize nitrogen
losses include the adoption of reduced tillage practices, the prevention of water-logging
through improved drainage and the treatment of sodic soils.

Replacing plant nutrients removed during harvests, and minimizing nutrient

losses to the environment are the goals of effective fertilization. This involves both
efficient and balanced fertilization to ensure adequate plant nutrition while maintaining
optimum soil fertility levels.

Trace Element and Heavy Metals Contamination

There is an increasing concern about the occurrence 'of trace elements in the
environment in concentrations which can be harmful for animal health. Many fertilizers.
phosphatic fertilizers in particular, contain varying amounts of trace elements such as F,
As, Cd, Co, Cr, Hg. Mo, Ni and Pb (Table). The main issues concerning these potentially
harmful elements are i)'soil accumulation and possibility of the long-term effects on crop
yields and quality, ii) plant uptake and the content of the element in animal feed and
human diet. iii) potentially damage to the soil micro flora. and iv) direct exposure to
humans through contact and ingestion. The famous incidences of "itai-itai" and
"minamata" diseases due to Cd and Hg toxicity. respectively are the examples of
potential threat of heavy metal pollution. In Japan excessive use of sulphate containing
fertilizers in paddy soils resulted in As toxicity, which was attributed to the displacement
of arsenate ions from soil particles by sulphate ions. Such situations may be observed in

97 AgriMoon.Com
Manures Fertilizers & Agrochemicals

the Deccan plateau of India, which are of volcanic origin.

Heavy metal contents (average) in fertilizers
Fertilizer Heavy metal (mg kg" fertilizer)
Cu Zn Mn Mo
Single super phosphate 26 115 150 3.3
Diammonium phosphate 109

Muriate of potash 3 3 8 0.2

Ca-ammonium nitrate 0.2 6 11

Urea 0.4 0.5 0.5 0.2

Ammonium sulpha.te 0.5 0.5 70 0.1

Triple super phosphate 7 75 200 0.1

Ammonium 'phosphate 3 80 160 2

.Complex fertilizer 22 276

Rock phosphate 100 200 0.5 --

Quality of Environment due to Fertilizer Use

While explaining the negative impacts of fertilizer application one should look into
the benefits the world is harvesting from fertilizer use. Fertilizer is an indispensable input
of intensive agriculture. The success of green revolution also goes to fertilizer use as Dr.
N.E. Borlaugh said, "If the high yielding varieties were the catalysts that ignited
the green revolution, the chemical fertilizers were the fuel that powered its
forward thrust". It improves soil-health and the deteriorating health of soil due to
excess mining of nutrients. Availability of organic manures would not be sufficient to
replenish the whole of harvested nutrients. Even it were possible to supply the entire
amount of N needed by organic sources, the" pollution problem would be greater. It is
reported that
losses of N from organic sources were more than that of inorganic sources. Fertilizer
also improves farming efficiency. The extensive-intensive type of farming would be
impossible without fertilizers. Moreover, the mineral, protein and vitamin content of crops
may be improved as judicious fertilization corrects the inadequate level of nutrient

98 AgriMoon.Com
Manures Fertilizers & Agrochemicals

availability.

Fertilizer application also retards erosion as the better developed canopy and
extensive root system of fertilized crop protects the soil against wind and water erosion,
The residual effects of the greater organic production are significant in the improved soil
aggregation imparted by the larger quantity of fresh organic return. It also conserves
water because only well nourished crops use water efficiently thereby producing more
yields per unit amount of water. Use of fertilizer promotes air purification by stimulating
vegetative production absorbing more CO2 from atmosphere and purifies the air.
Fertilizer, by increasing productivity reduces the encroachment of farming onto marginal,
erodible and forest land.

99 AgriMoon.Com
Manures Fertilizers & Agrochemicals

19.FERTILIZERS CONTROL ORDER (FCO) 1985

ORDER

Under the Essential Commodities Act, 1955 (10 of 1955), the Central Government
makes the Fertilizers (Control) Order, 1985. It shall come into force on the date of its
publication in the Official Gazette. In this Order,some of the definitions are used

Act means the Essential Commodities Act, 1955 (10 of 1955).

"certificate of source" means a certificate given by a State Government, Commodity

Board, manufacturer, + importer, pool handling agency

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)

compound or complex fertilizers means a fertilizers containing two or more nutrients

during the production of which chemical reaction takes place

controller means the person appointed as Controller of Fertilizers by the Central

Government and includes any other person empowered by the Central Government to
exercise or perform all or any of the powers, of the Controller under this Order.
"dealer" means a person carrying on the business of selling fertilizers 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.
fertilizer means any substance used or intended to be used as a fertilizer of the soil
and/or crop and specified in Part A of Schedule I and includes a mixture of fertilizers and
special mixture of fertilizers.

"grade" means the nutrient element contents in the fertilizer expressed in percentage
"granulated mixture" means a mixture of fertilizers made by intimately mixing two or more
fertilizers with or without inert material, and granulating them together, without involving any
chemical reaction.

100 AgriMoon.Com
Manures Fertilizers & Agrochemicals

“importer" means a person who imports fertilizers in accordance with the Export and
Import Policy of the Central Government, as amended from time to time.
inspector" means an Inspector of Fertilizers appointed under clause 27.
"manufacturer" means a person who produces fertilizers or mixtures of fertilizers and the
expression "manufacture" with its grammatical variations shall be construed accordingly.
"mixture of fertilizers" ***means a mixture of fertilizers made by physical mixing two or
more fertilizers with or without inert material in physical or granular form and includes a
mixture of NPK fertilizers, a mixture of micronutrient fertilizers and a mixture of NPK with
micronutrient fertilizers.
"physical mixture" means a mixture of fertilizers made by physically mixing two or more
fertilizers with or without inert material necessary to make a required grade, without
involving any chemical reaction.
"prescribed standard" means-in relation to a fertilizers 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

PRICE CONTROL-Fixation of prices of fertilizers

The Central Government may, with a view to regulate equitable distribution of

fertilizers and making fertilizers available at fair prices, by notification in the Official Gazette,
fix the maximum prices or rates at which any fertilizers may be sold by a dealer,
manufacturer, +importer or a pool handling agency. The Central Government may consider
the local conditions of any area, the period of storage of fertilizers and other relevant
circumstances, fix different prices or rates for fertilizers having different periods of storage or
for different areas or for different classes of consumers. No dealer, manufacturer +importer
or pool handling agency shall sell or offer for sale any fertilizers at a price exceeding the
maximum price or rate fixed under this clause.

Display of stock position and price list of fertilizers

Every dealer, who makes or offers to make a retail sale of any fertilizers, shall prominently
display in his place of business:-the quantities of opening stock of different fertilizers
held by him on each day & a list of prices or rates of such fertilizers fixed under clause 3
and for the time being in force.

Issue of cash/credit memorandum

101 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Every dealer shall issue a cash or credit memorandum to a purchaser of a fertilizers in FormM*
CONTROL ON DISTRIBUTION OF FERTILIZERS BY MANUFACTURER/ IMPORTER

Allocation of fertilizers to various States

The Central Government may, with a view to secure equitable distribution and availability
of fertilizers to the farmers in time, by notification in the Official Gazette, direct any
manufacturer/importer to sell the fertilizers produced by him in such quantities and in such
State or States and within such period as may be specified in the said notification.

AUTHORISATION OR REGISTRATION OF DEALERS”

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 clause 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 While, a manufacturer,
an importer, a pool handling agency, wholesaler and a retail dealer intending to sell or
offer for sale shall make a Memorandum of Intimation to the Notified Authority, in Form A1
duly filled in, in duplicate, together with the fee prescribed under clause 36 and certificate
of source in Form O.
On receipt of a Memorandum of Intimation, complete in all respects, the Notified Authority
shall issue an acknowledgement of receipt in Form A2 and it shall be deemed to be an
authorization letter granted and the concerned person as authorised dealer for the
purposes of this Order.

A certificate of registration granted before the commencement of the Fertilizers

(Control) Amendment Order, 2003, shall be deemed to be an authorization letter granted
under the provisions of this Order: when the applicant is a State Government, a
manufacturer or an importer or a pool-handling agency, it shall not be necessary for it or
him to submit Form O.

102 AgriMoon.Com
Manures Fertilizers & Agrochemicals

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; no certificate of
registration shall be granted to a person: -if his previous certificate of registration is under
suspension; or
it has been cancelled within a period of one year immediately preceding the date of
application;or if he has been convicted of an offence under the Act, or if he fails to enclose
with the application a certificate of source ; or
if the application is incomplete in any respect;

Period of validity of certificate of registration and letter of authorization

Every certificate of registration granted, be valid for a period of three years from the
date of its issue.

Renewal of certificates of registration and authorization letters

Every holder of a certificate of registration granted make an application for renewal to the
Controller, in Form C, or to the Notified Authority in Form A1, respectively, in duplicate,
together with the fee prescribed under clause 36 for such renewal and a certificate of source
as required under clause 8.
Manufacture of Mixtures of Fertilizers - Restriction on preparation of mixtures of
fertilizer

No person shall carry on the business of preparing any mixture of fertilizers. or special
mixture of fertilizers except under and in accordance with the terms and conditions of a
certificate of manufacture granted to him under clauses 15 or 16.

Standards of mixtures of Fertilizers

Subject to the other provisions of the order, no person shall manufacture any *mixture of
fertilizers whether of solid or liquid fertilizers unless such mixture conforms to the standards
set out in the notification to be issued by the Central Government in the Official Gazette;
Application for certificate of manufacture of mixtures of fertilizers

103 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Every person desiring to obtain a certificate of manufacture for preparation of any mixture of
fertilizers or special mixture of fertilizers shall possess such mixture, *and possess the
minimum laboratory facility as specified in clause 21A of this Order.
An applicant shall make an application to the registering authority if he is an applicant for a
certificate of manufacture for any mixture of fertilizers in Form D, in duplicate, together with
the fee prescribed there for under clause 36; or,
if he is an applicant for a certificate of manufacture for any special mixture, in Form E, in
duplicate, together with the fee prescribed there for under the said clause 36 and an attested
copy of the requisition of the purchaser.

Grant or refusal of certificate of manufacture for preparation of mixtures of fertilizers

On receipt of an application under clause 14, the registering authority shall, by order in writing,
grant or refuse within forty-five days from the date of receipt of the application, furnish
to the applicant a copy of the order so passed;
to the applicant in Form G

Period of validity of a certificate of manufacture for preparation of mixtures of fertilizers

Every certificate of manufacture granted under clause 15 for preparation of a mixture of

fertilizers shall, unless suspended or cancelled, be valid for a period of three years from the
date of issue.

Renewal of certificate of manufacture for preparation of mixtures of fertilizers

Every holder of a certificate of manufacture for preparation of a mixture of fertilizers desiring to

renew the certificate, shall, before the date of expiry of the said certificate of manufacture
make an application to the registering authority in Form D in duplicate, together with the fee
prescribed for this purpose under clause 36.
Manufacturers/Importers pool handling agencies to comply with certain requirements
in regard to packing and marking, etc.2

Every manufacturer/importer and pool handling agency shall, in regard to packing and
marking of containers of fertilizers, comply with the following requirements, namely:-Every
container in which any fertilizers is packed shall conspicuously be Superscribed with the word
“FERTILIZERS” and shall bear only such particulars in case of containers the gross weight of
which is 5 kg or less, no such printing of superscription and other particular shall be necessary

104 AgriMoon.Com
Manures Fertilizers & Agrochemicals

if such super superscription and other particulars are printed on a separate label which is
securely affixed to such container. in case fertilizer bags are in cut, torn or damaged condition
during transportation or is handling during loading or unloading operation, the manufacturer of
such fertilizer may, under intimation to the State Government and the Central Government,
repack the fertilizer in new bags or restandardise the quantity in terms of declared weight.
Every fertilizers bag in which any fertilizers is packed for sale shall be of such weight and size
as may be specified by the Central Government from time to time in this behalf

Manufacturers to comply with certain requirements for laboratory facilities:-

Every manufacturer shall, in order to ensure quality of their product, possess minimum
laboratory facility, as may be specified from time to time by the Controller.

Disposal of non-standard fertilizers

Notwithstanding anything contained In this Order, a person may sell, offer for sale, stock or
exhibit for sale or distribute, [any fertillser except any fertillser imported by the Central
Government] which, not being an adulterated fertilizers, does not conform to the prescribed
standard (hereinafter in this Order referred to as non-standard fertilizers) subject to the
conditions that:- the container of such non-standard fertilizers is conspicuously super scribed
in red colour with the words "non-standard" and also with the sign "X"; and an application for
the disposal of non-standard fertilizers in Form H is submitted to the [Notified authority] to
grant a certificate of authorization for sale of such fertilizers and a certificate of authorization
with regard to their disposal and price is obtained in Form such non-standard fertilizers shall
be sold only to the manufacturers of mixtures of fertilizers or special mixtures of fertilizers or
research farms of Government or Universities or such bodies. The price per unit of the non-
standard fertilizers shall be fixed by the notified authority If a manufacture or importer detects
or as reasonable doubt about the standard of the fertilizer manufactured or imported by him,
and dispatched for sale as deteriorated in quality during transit due to natural calamity and is
not of the prescribed standards, he may, within fifteen days from the date of dispatch from
factory or port, apply with detailed justifications to the Central Government for obtaining
permission for reprocessing the same in a factory to meet the prescribed standards and the
Central Government may, after considering the facts, permit the re-processing of such
fertilizer on the terms and conditions as may be notified by the Central Government in this
behalf.

105 AgriMoon.Com
Manures Fertilizers & Agrochemicals

ENFORCEMENT AUTHORITIES

Appointment of registering authority The State Government may, appoint such number of
persons, as it thinks necessary, to be registering authorities for the purpose of this Order for
industrial dealers, and may, define the limits of local area within which each such registering
authority shall exercise his jurisdiction.
Notified Authority- The State Government may, appoint such number of persons, 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.

Appointment of inspectors-The State Government, or the Central Government may, by

notification in the Official Gazette appoint such number of persons, to be inspectors of
fertilizers 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.

Qualifications for appointment of fertilizers Inspectors

No person shall be eligible for appointment as Fertilizers 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 recognized university; and
Training or experience in the quality control of fertilizers and working in the State or Central
Government Department of Agriculture.

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 fertilizers 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;
enter upon and search any premises where any fertilizers is manufactured/ Imported or
stored or exhibited for sale,;
seize any books of accounts or documents relating to manufacture, storage or sale of
fertilizers, etc. in respect of which he has reason to believe that any contravention of this
106 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Order has been or is being or is about to be committed; Where any fertilizers is seized by an
inspector under this clause, he shall forthwith report the fact of such seizure to the collector
whereupon the provisions of sections 6A, 6B, 6C, 6D and 6E of the Act, shall apply to the
custody, disposal and confiscation of such fertilizers. Every person, if so required by an
inspector, shall be bound to afford all necessary facilities to him for the purpose of enabling
him to exercise his powers under sub-clause (1).

ANALYSIS OF SAMPLES

Laboratory for analysis

A fertilizer sample, drawn by an inspector, shall be analyzed in accordance with the

instructions contained in Schedule II in the -Central Fertilizers Quality Control and
Training Institute, **Faridabad or Regional Fertilizers 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. Every laboratory in
order to ensure accurate analysis, of fertilizers samples, possess minimum equipment and
other laboratory facilities, as may be specified from time to time by the Controller in this
behalf

Qualifications for appointment of fertilizers analyst in the fertilizer control

laboratories

No person shall be eligible for appointment as fertilizers analyst for analysis of fertilizers
samples in the laboratories notified under clause 29 of the Order, unless he possesses the
following qualifications, namely:-graduate in Agriculture or Science with chemistry as one of
the subjects from a recognized university; and
training In fertilizers quality control and analysis at Central Fertlllzer Quality Control and
Training Institute, Faridabad.
Provided that the fertilizers analysts appointed before the commencement of this Order, who
do not possess the requisite training, shall undergo prescribed training, within a period of
three years, in the Central Fertilizers Quality Control " and Training Institute, Faridabad from
the date of commencement of this Order.

Laboratories for refree analysis

107 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Every laboratory referred to in sub-clause (1) of clause 29 shall be designated as referee

laboratory for the purpose of analysis of any sample of fertilizers :
Provided that no such laboratory which carried out the first analysis of the fertilizers sample
shall be so designated in respect of that sample:
Further in respect of any sample the analysis of which has been challenged, may be sent for
referee analysis to any one of the other laboratories except those which are located in the
State or where the first analysis has been done.
Central Fertilizers Quality Control and Training Institute and Regional laboratories shall be
considered as one group of laboratories and a sample first analysed by any one of them, shall
not be sent for referee analysis to any other in that group, but only to any other laboratory
notified by a State Government.
Time limit for analysis, and communication of result

Where sample of a fertilizer has been drawn, the same shall be dispatched along with a
memorandum in Form K to the laboratory for analysis within a period of seven days from the
date of Its drawl. The laboratory shall analyze the sample and forward the analysis report in
Form L within [30 days] from the date of receipt of the sample in the laboratory to the authority
specified in the said memorandum.
The authority to whom the analysis report is sent under sub-clause (2) shall communicate the
result of the analysis to the dealer/manufacturer/Importer/pool handling agency from whom
the sample was drawn within [15 days] from the date of receipt of the analysis report of the
laboratory.

Maintenance of records and submission of returns, etc.

The controller may by an order made in writing direct the dealers. manufacturers/ importers,
and pool handling agencies:- to maintain such books of accounts, records, etc. relating to
their business in Form 'N'. and to submit to such authority, returns and statements in such
form and containing such information relating to their business and within such time as may
be specified in that order. Where a person holds certificates of registration for retail sale and
wholesale sale of fertilizers, he shall maintain separate books of accounts for these two types
of sales made by him.
Fees

The fees payable for grant, amendment or renewal of an authorization letter or certificate of
registration or certificate of manufacture a duplicate of such certificates or, renewal thereof

108 AgriMoon.Com
Manures Fertilizers & Agrochemicals

under this Order shall be such as the State Government may, from time to time fix, subject to
the maximum fees fixed for different purposes by the Central Government and different fees
may be fixed for different purposes or for different classes of dealers or for different types of
mixtures of fertilizers or special mixture. Any fee paid under sub-clause (1) shall not be
refundable unless the grant or renewal of any certificate of registration or certificate of
manufacture or duplicate copy of such certificate or renewal under this Order has been
refused.
The fees payable for grant, amendment, renewal or duplicate copy of certificate of registration
for industrial dealer and the authority to whom and the manner in which such fee shall be paid,
shall be such as may be specified by the Controller from time to time by notification in the
Official Gazette*

109 AgriMoon.Com
Manures Fertilizers & Agrochemicals

20.ORGANIC CHEMISTRY AS PRELUDE TO AGROCHEMICALS - DIVERSE TYPE OF

AGROCHEMICALS

“Agrochemicals” - include chemicals, which enhance growth and yield of

crops apart from chemicals that destroys pests and diseases. Pesticides
are chemicals designed to combat attacks of various pests on agricultural
& horticultural crops.
Classification of pesticides:
Insecticides (for the control of insects)
Fungicides (for the control of fungal pathogens)
Herbicides ( for the control of weeds)
Rodenticides (for the control of vertebrate pests)
Nematicides (to kill microscopic worms),
Molluscides (to kill slugs and snails)
Acaricides (to kill mites).
Antifeedant,- inhibit feeding
Repellent - to prevent the pest species from attacking its hosts.
Chemosterilant- induces sterility.
Algicides (for the control of algae)
Aphicides (for the control of aphids)

Besides there are other classes viz., Antibiotics, Carcinogen,

Dessicants, Defoliants, Ovicide, Pheromone and Plant growth
regulators
Predominant classes of pesticides used in India are insecticides,
which accounted for about 57 per cent of total pesticide consumption
followed by fungicides (29%) and herbicides, which constituted about
14 per cent.

110 AgriMoon.Com
Manures Fertilizers & Agrochemicals

21.PESTICIDE FORMULATIONS
Pesticides are formulated to make their application easier and to improve their
effectiveness under field conditions. Formulation also improve the properties, storage,
handling and safety.
Formulation is the process by which the active ingredients are made ready to be
used by mixing with liquid or dry diluents by grinding or by addition of emulsifiers,
stabilizers and other formulation adjuvant to form a commercial product.
Classification of Formulations
a) Dry formulations
Dusts
Wetable Powders
Crannels
Seed disinfections
Others
b) Liquid Formulations
1. Emulsion concentrates
2. Oil concertrates
3. Others
c) Others
A) DUSTS
Dusts consist of a mechanical mixture of the active ingredients with or without an
inert diluent pulverized to a particle size of 3 to 30 µ. Dusts can be classified as follows:
1. Undiluted toxic agent (sodium fluoride)
2. Toxic agent with an active diluent (rotenone with sulphur)
3. Toxic agent with an inert diluent (DDT with pyrophyllite)
4. Inert dusts (silica)
Insecticides like calcium arsenate, sodium fluoride ground pyrethrum flowers may
be applied as dusts with diluent.
Others like rotenone can be mixed with insectides like sulphur and applied.
Others may be diluted with inert materials like talc in order to cover more area and also
to reduce the phytotoxicity of the chemical or to improve the chemical or physical
properties.

111 AgriMoon.Com
Manures Fertilizers & Agrochemicals

When inert materials like silica, saw dust, ash are used they may cause
abrasions on the pest surface or absorb moisture and desiccate them.
Method of Manufacture
Two methods are employed
1. Ball Mill Method
2. Solvent Mix Method / Toxicity Spray Method
1. Ball Mix Method
In this method the ingredients viz., the active ingredients and fillers like soap
stones, talc or pyrophyllite are intimately ground in a Ball Mill and mixed together by the
blending operations of a mechanical mixture. In the grinding process, heat develops and
increase the temperature, which melts the pesticide and thus gives a fine coating on the
inert material. Also in the grinding process the pesticide particles get distributed among
the diluents. Consequently grinding of the active ingredient together with the diluent
gives a more efficient formulation than separate grinding of the ingredients with
subsequent mixing. The finer the grinding more effective is the dust. However lumps
may be formed in this process and these lumps are broken into fine particles by means
of a powerful jet of air introduced from the sides. Particles of certain size alone are
taken upstream by the jet of air and those heavier than the limit prescribed fall back in
the ball mill to be ground again.
2. Solvent Mix Method/Toxicant Spray method
The toxicant in the form of a liquid is sprayed into the dust mixture during the
blending the blending process. The solvent may be allowed to evaporate or it may be a
higher boiling solvent of a petroleum fraction.
3. Bulk Density
It depends upon particle size, shape and actual density. It is an indication of
fluffiness. A good diluent is one which weights 300-450 kg/m3 (0.3 g/cc). Lighter
materials have low carrying power and remain in the air for a longer time. Heavier
materials fall rapidly.
4. Particle Density
Particle density is the actual density of the solid materials, only as if there were
no air spaces between them. It affects the feeding in the duster. Carrying power
segregation and settling of dust depend upon particle density.
5. Electrostatic Charge
It is produced due to the friction between particles and the dusting equipment.
Materials with high silica give type charge to the blower and recharge to the dust steam.

112 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Electrostatic charges on particles affect the attraction of dusts to the plant surfaces and
dust distribution.
6. Flowability
It indicates the feed rate of dusting equipment. The angle of slope which is a
measure of flowability is measured by allowing the dust to fall through a funnel upon
disc. Greater the angle poorer is the flowability. Dust with fibrous or needle shaped
particles have a slower feed rate than dusts with spherical particles.

7. Other Properties
a) Hardnes -causes abrasikon of the equipment
b) Absorption -affects caking
c) Asorption -tendency to form lumps
Though dusting is less effective compared to spraying it is suitable in areas of
water scarcity. Usually 10-50 kg is applied.

113 AgriMoon.Com
Manures Fertilizers & Agrochemicals

22.PESTICIDES FORMULATION
A) GRANULES
Granulated formulations are widely used for the control soil inhabiting pests and
also for making plants poisonous to the sucking pests. They are more convenient to
handle and leave a smaller residue on the plants.
Granules can be prepared by several methods
1. By impregnation of prepared granules or minerals like perlite or vermiculite with
liquid pesticides or their solutions.
2. By granulating the powder formulation on a suitable diluent with subsequent
screening.
The most widely used granular formulations are of 0.2 to 1 mm size. For the
treatment of plants, granules of low strength are used. While for the control of weeds
in water reservoirs, granules of high strength are used. Granulated formulations of
pesticides with fertilizers are also being prepared on a limited scale since many of
the pesticides degrade when mixed with fertilizers.

B) FUMIGANTS
Fumigants are substances sufficiently volatile to produce toxic concentration of
vapour in closed space. Diffusion is faster with gases of lower molecular weights.
Fumigant concentration is expressed in weight volume, eg. mg/l or 1bs/1000 c. ft. of
fumigated space. Adsorption and leakage as well as setting and actual layering of the
initially heavy vapour of most fumigants interfere with diffusion to such an extent that
artificial means of stirring the gas mixture are usually employed.
Insect control of fumigation is practised in a number of fields like building
fumigation, product fumigation crop fumigation and soil fumigation.

INSECTICIDE CLASSIFICATION – ORGANOCHLORINES – MODE OF ACTION –

LINDANE, ENDOSULFAN – CHARACTERISTICS AND USE

LINDANE

Lindane is a contact, stomach and respiratory poison is lethal to chewing and

sucking insects but not to spider mites. The vapour pressure and good water solubility
(~10 ppm) make lindane an excellent soil insecticide.
The method of use permits effective control of economically important soil pests
(eg. Beetle larvae, wireworms, white grubs, flea beetles, cutworms, fruit fly). The tainting
property even of highly pure lindane prevents use on fruit and vegetable crops, but

114 AgriMoon.Com
Manures Fertilizers & Agrochemicals

application in forest crops and cotton is wide. Under the name of lacutin it serves in
veterinary medicine for control of ectoparasites such as ticks and mange mites.
Toxicicology. The acute mammalian toxicity of lindane is somewhat greater than
that of DDT (LD50 rat 76-200 mg/kg). After administration, lindane is found in the milk,
body fat and kidneys, but is excreted quickly. The danger of accumulation is very slight.
In the technical product, hexachlorocyclohexane, the high chronic and cumulative
toxicity of β-hexachlorocyclohexcane (present to about 5-14%) make the use of the
technical product very undesirable.
Lindane has a similar insecticidal spectrum to DDT but its physical properties are
more suitable than DDT for use as soil insecticides because of its greater volability and
water solubility.
Mode of Action of Lindane
Lindane, like DDT, rapidly penetrates the insect cuticle and can exert a
significant fungiant action in a dry atmosphere.
Uses
It is stable to heat and is useful as a soil dressing against soil insects. As sprays
lindane is valuable against many sucking and chewing pests and as smokes for control
of pests in grain stores.

The crude material has an impleasant musty odour and taste which tends to taint
foodstuffs. This is due to the presence of other isomers because γ-HCH has no smell,
but is more expensive.
The symptoms of insect poisoning superficially resemble those of DDT and γ-
HCH is known to be a neurotoxicant. A concentration of 10 µm increase the frequency
of spontaneous discharges in the cockroach nerve cord and extends the synaptic cleft
after discharge. Lindane rapidly penetrates the cuticle of cockroaches and accumulates
in the peripheral regions of the central nervous system quickly causing tremors, loss of
bodily co-ordination, convulsions and prostration. Like DDT, lindane probably kills
insects by bringing about sodium potassium imbalance in nerve membranes.
One of the initial products of metabolism of lindane in houseflies was the
monodehydrochlorinated compound pentachlorocyclohexane, isolated from lindane –
resistant houseflies and the resistance to γ-HCH observed in houseflies is due to this.

B) ENDOSULFAN

115 AgriMoon.Com
Manures Fertilizers & Agrochemicals

(6, 7, 8, 9, 10, 10-hexachloro-1, 5, 5a, 6, 9, 9a-hexahydro-6, 9, methano-2, 4, 3,

benzodioxathiepin-3-oxide).
Other Names
Thiodan, Mallx, Cyclodan, Thimul, Thifur.
The insecticidal properties were first described by W. Finkenbrink. Since 1950
endosulfan has been on the market under the name Thiodan.
Synthesis
Thiodandiol (obtained by saponification of the Diels-Alder adduct from HCCP and
Cisl-4-diacetoxybutene) is converted into technical Endosulfan by heating with thionyl
chloride in xylene.
Technical material is a brownish solid (m.p. 70-100°C). It is a mixture of two
isomers differing in the position of the sulfite group. α-endosulfan (70%) and β -
endosulfan (30%). Both isomers yield the corresponding cyclic sulfate upon oxidation.
The α - endosulfan is slowly converted to more stable isomer at high
temperature. Both the isoemers are slowly oxidized in air and biological systems by
provides or permanganate to endosulfan sulfate. Endosulfan is slowly hydrolysed back
to the thiodandiol by the action of aquous acid or base.
Endosulfan has a similar spectrum of insecticidal activity to aldrin, except that it is
also acaricidal. Endosulfan, unlike most organochlorines is degraded in the environment
and does not accumulate. It is the only organochlorine insecticide permitted in USA.

116 AgriMoon.Com
Manures Fertilizers & Agrochemicals

23.ORGANOPHOSPHATES – CHARACTERISTICS, PREPARATION AND USE OF

MONOCROTOPHOS, PHOSPHAMIDAN, MALATHION AND CHLORPYRIPHOS
a) Monocrotophos (Azodrin)
Derivative of phosphoric acid
Monocrotophos (Dimethyl-1 methyl-2-methyl carbamoyl-venyl phosphate)

(Monocrotophos)

LD50: 21 mg/g

b) Phosphamidon (Dimecron)
(2-chloro-2diethyl carbamyl-1-methylvinyl dimethyl phosphate)

1. Derivative of Phosphoric Acid

Phosphamidon is produced by reacting equimolecular quantities of trimethyl
phosphite with boiling solution of diethylamide of dichloroacetic acid in chlorobenzene.

O CH3
| |
(CH3O)3P+CH3CO C Cl2 CON(C2H5)2(CH3O)2-P-O-C=CCl-CON-(C2H2)2+CH3Cl

Phosphamidon is very similar to mevinphos in toxicity has a broad spectrum of activity

against biting and sucking pests and spider mites.

LD50: 10 mg
Pure phosphamidon is colourless. Commercial product is bright violet due to the
presence of a dye. B.P. 70°C, with a faint pleasant odour.

117 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Highly soluble in water, alcohol, acetone, slightly soluble in saturated

bydrocarbons like hexane and insoluble in kerosene. Does not clogg the nozzles and
hence suited to ultra low volume and low volume sprays.

• Phosphamidon is stable in neutral and weak acidic aqueous solutions.

• It is rapidly hydrolysed in alkaline medium.
• Stable for 2 years when stored in closed containers.
• It is compatible with most pesticides except alkaline ones.
• When mixed with captan it is synergistic. Toxicity is reduced when mixed
with copper oxychloride.
• When insects feed on this, the choline esterase is inhibited and the insect
gets killed.
• Used as a systemic to control sucking pests in cotton.

c) Malathion
(0, 0-dimethyl S-(1, 2, dicarbethoxy) ethyl phosphorus dithioate)
Derivatives of Dithiophosphoric acid
Dithiophosphoric acid + Maleic acid  Malathion
Malathion is obtained by addition of dimethyl dithiophosphoric acid to maleic acid
ester in the presence of basic catalyts.
Malathion was introduced in 1950 by the American Cyanamid company. It is an
important and widely used contact insecticide and acaricide for the control of aphids, red
spidermites, leafhoppers and thrips on a wide range of vegetable and other crops. It
was important in the history of development of OP insecticides since it was the first
member with a broad spectrum of contact insecticidal activity combined with the
remarkably low mammalian toxicity (LD50: 1300 mg/kg rats). Malathion is also valuable
to control insect vectors eg. Mosquitoes and can be used as a substitute for
organochlorine insecticides.
Pure malathion is a colourless liquid boiling at 120°C. It is sparingly soluble in
water but highly soluble in most of the organic solvents except in saturated
bydrocarbons.
Malathion on prolonged heating at 150°C is isomerised and goes over to thiolo
isomers.

d) Chlorpyriphos (Dursban)

118 AgriMoon.Com
Manures Fertilizers & Agrochemicals

(0, 0-diethyl 0-(3, 5, 6 trichlorophyridine-2 yl phosphorothioate)

Derivative of Thiophosphoric acid
Chlorpyrifos is used for mosquito control but may also be employed against
ectoparasites on domestic animals.
LD50: 135-163 mg/kg rat oral.
Metallic ions in soils often interact with organophosphorus insecticides; the cupric
ion is a very effective calalyst for the degradation of some organophosphorus esters,
such as diazinon and chlorpyrifos.
Chlorpyrifos has low acute mammalian toxicity in the 2000-5000 mg/kg range.
Many organophosphorus insecticides contain heterocyclic moieties with nitrogen
heterocycles. The only important pyridine derivatives are chlorpyrifos and chlorpyrifos
methyl. Chlorpyrifos is a very valuable contact insecticide some 3500 tonnes were used
in USA in 1982. It has a wide spectrum of activity, by contact, ingestion and vapour
action. It is moderately persistant and retains its activity in soil for 2-4 months and is
valuable against mosquito and fly larvae, cabbage root fly, aphids and codling and winter
moths on fruit trees.
Chlorpyrifos has become one of the most widely applied insecticides in homes
and restaurants against cockroaches, and other domestic pests. It is a comparatively
safe insecticide. Chlorpyrifos methyl (R=CH3) is quite volatile and is used to control
insects in grain stores.

119 AgriMoon.Com
Manures Fertilizers & Agrochemicals

24. ORGANOPHOSPHATES – CHARACTERISTICS, PREPARATION AND USE OF

PHORATE, PHOSALONE, DIMETHOATE AND QUINALPHOS

a) Phorate (Thimet)
(0, 0-diethyl-S-2-ethylthiomethyl phosphoro dithioate)
Derivative of Dithiophosphoric acid.
Phorate is produced by reacting dimethyl dithiophosphoric acid with
formaldehyde and ethyl mercaptan at room temperature.
The second method is by condensation of chloromethyl sulphide with sodium
dithiophosphoric acid.
Phorate is a clear liquid. B.P. 100°C, highly soluble in most organic solvents. It
is unstable to hydrolysis. In acid medium it is more stable. It is easily oxidized to the
corresponding sulphoxide which is resistant to hydrolysis and hence persists on plants
for long time providing insecticidal action.
Phorate has both systemic and contact insecticidal action and is a very toxic
compound. Phorate is absorbed and translocated in plants. It is oxidatively
metabolized. Phorate is employed for control of aphids, carrot fly, fruit fly and wire worm
in potatoes.

b) Phosalone (Zolone)
(0, 0-diethy-S-(6-chloro-2, 3-dihydro-2 oxobenzoxazol-3-yl) methyl
phosphorodithioate).
Derivative of Dithiophosphoric acid
Phosalone is a systemic insecticide and acaricide used in citrus and orchard
fruits. It is also used to control aphids in cereals, oilseed, rape and brassicas. It is also
used for testing seeds to protect the seedling from insect damage. LD50: 135 mg/kg.
Phosalone is produced by condensation of sodium or ammonium
diethyldithiophosphoate with 6-chloro-3 chloromethyl benzoxazolone.
It is practically insoluble in water. It is a white crystalline substance, m.p. 45-
17°C. It is relatively stable in acid medium but in alkaline medium it is rapidly hydrolyzed
to the 6-chloro-benzenehexazolone diethyl thiophosphoric acid and formaldehyde.
c) Dimethoate (Rogor, phosphamide, cygon)
(0, 0-dimethyl-S-methyl carbamoylmethyl phosphoro dithioate).
Derivative of Dithiophosphoric acid

120 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Dimethoate is a systemic and contact insecticides and acaricide, produced by

reacting salts of dimethyldithiophosphoric acid with N-methylchloroacetamide in aqueous
medium in the presence of some organic solvents.
It is also produced by reacting dithiophosphate with aqueous methylamine at low
temperature.
Pure dimethoate is a white crysatalline substance with camphor like odour. The
technical material is a yellowish brown (amber) coloured oily liquid with sulphurous acid
smell. It is highly soluble in water and most organic solvents. Dimethoate is thermally
unstable and on heating it decomposes.
d) Quinalphos (Ekalux) or (Bayrusil)
Derivative of Thiophosphoric acid.
Quinalphos (0, 0diethyl-0- (2-quinoxalinyl) phosphorothioate) is obtained by
condensation of 0-phenylenediamine with the hemi-acetal of glyoxylate.
The compound is highly active against biting and sucking insects and has an
LD50: 70 mg/kg rat (oral).
Quinalphos developed by Bayer AG (1969) is prepared by reaction of 0-
phenylenediamine, chloroacetic acid and 0, 0-diethyl phosphorochloride thioate.
Quinalphos is a broad-spectrum contact and systemic insecticides, applied as
spray to control pests in cereals, brassicas and other vegetables. The mammalian
toxicity is quite high (LD50: 70 mg/kg) but the compound is degraded in plants within a
few days of application.

121 AgriMoon.Com
Manures Fertilizers & Agrochemicals

25.CARBAMATES – CHARACTERISTICS, PREPARATION AND USE OF –

CARBARYL, CARBOFURAN, CARBOSULFAN AND ALDICARB

Carbamates
Mode of action – carbaryl, carbofuran, methomyl, aldicarb and bendiocarb
characteristics and use persistence in plant, soil and water.
Carbamates are derivatives (esters) of carbamic acid. Several carbamates are
systemic, transported in the xylem. It is possible to control pests on shoots and roots
which are otherwise difficult to reach. Hence, they are used as soil insecticides and
nematicides (aldicarb, carbofuran, oxamyl etc.). Commercial products available are
grouped into three groups.
1. N, N-dimethyl carbamates of enols and hydroxy heterocycles
2. Phosphocarbomates
3. Oxinecarbomate

Mechanism of action
The mechanism of action of the insecticidal carbamates is identical to that of the
organophosphates, viz., inhibition of the enzyme cholinesterase. This enzyme has the
function of hydrolyzing the pod synaptic effector, acetylcholine into chlolire and acetic
acid.
Inhibition of acetylchlinesterase (ACHE) leads to a buildup of acelylcholine in the
post synaptic membrane and hence to a permanent nerve stimulation with lethal results.
This stimulation of insects manifests itself in uncountrolled movements and paralysis.
A) Carbaryl (Sevin, Hexavin, Ravyon)
(Naphthyl carbamate, 1-Naphthyl-N-methyl carbamate)
LD50: 850 mg.
Broad spectrum contact insecticide, non-systemic used in cotton, fruits,
vegetables, forage crops etc. Also to control of earth worms.
Carbaryl, introduced by American Union Carbide Company in 1956 was the first
successful commercial carbamate. Carbaryl is produced by any of the general methods
of preparation of carbamates, like reacting 1-naphthol with methyl carbamoyl chloride at
room temperature.
The rate of reaction is increased by removing the HCl that is formed with a strem
of air or nitrogen.

122 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Pure compound of carbaryl is obtained by reacting 1-naphthol with methyl

isocyanate.
Carbaryl is also synthesized by reacting 1-naphthylchlorocarbonate with
methylamine in the presence of HCl acceptors.
Carbaryl is a white crystalline compound with M.P. 142° C. it is highly soluble in
organic solvents; resistant to the action of water at room temperature and also to light
and oxygen of air.
In alkaline medium, it is rapidly hydrolysed and so it is not compatible with
compounds of alkaline nature like Brodeaux Mixture.
B) Carbofuran (Furadan)
(2, 3, dihydro 2, 2 dimethyl 7, benzofuranyl)
Broad spectrum insecticide, nematicide and miticide.
LD50: 8-14 mg/kg rat.
Can be incorporated in soil at 6-10 kg/ha for control of soil insects and nematodes. It
has high mammalian toxicity but is rapidly metabolized to non-toxic products in plants
and animals.
It is a systemic carbamate, broad spectrum insecticide. It is stable in acid and
neutral media but unstable in alkaline medium. Sparingly soluble in water; but soluble in
organic solvents. It is compatible with non-alkaline pesticides and fertilizers. It is not
phytotoxic to rice. Carbofuran when applied to soil is absorbed by plant roots and
distributed to stems and leaves and metabolized to non-toxic compounds in 30 days.
Carbofuran present in soil is degraded by hydrolysis depending on soil pH and clay
content. Toxic residues do not remain in the soil for long.
C) Carbosulfan
Carbosulfan, a sulphanylated derivative of carbofuran acts as a contact and
systemic insecticide. It can be applied to the foliage or soil as a nematicide. It has a
lower mammalian toxicity.
LD50: 209 mg
The carbomates, carbofuran, carbosulfan and aidicarb are valuable
nematicidesss. Carbosulfan formulated as granules is used in vegetables. eg.
brassicas, carrots and turnips.
D) Aldicarb (Temik)
2-Methyl-2-(methylthio) propanol 0-Methylamino carbonyl oxime)
Systemic insecticide, acaricide, nematicide for soil use; only available as
granules to reduce handling hazards.

123 AgriMoon.Com
Manures Fertilizers & Agrochemicals

LD50: 0.93 mg/kg rat.

Used for cotton, sugarbeet and ornamentals. Aldicarb is extremely toxic and is
absorbed through skin. It is therefore marketed as a granular formulation.
White crystalline substance m.p. 100°C. Sparingly soluble in water prepared by
reacting corresponding oxime with methyl isocyanate.
Aldicarb is a carbamate of carbamoyl oxime group. It is effective for control of
aphids, nematodes, flies beetles, leaf miners, thrips and white flies on a wide range of
crops. Aldicarb is readily translocated in plants after soil applicatikon where it is
metabolized to the sulphoxide and the sulphore which are also active.

124 AgriMoon.Com
Manures Fertilizers & Agrochemicals

26.BOTANICALS – CHARACTERISTICS, PREPARATION AND USE OF NEEM

PRODUCTS, NICOTINE AND PYRETHRUM
Botanical insecticides
Toxicants derived from plants are used in insect control and among them neem
products, nicotine and pyrethrum are well known.
Insecticidal butylamides
Several members of the Compositae and Rutaceae groups of
plants contain insecticidal unsaturated butylamides. Example: Pellitorine
and Fagaramide. These compounds like several of the pyrethrins, have a
rapid knock down effect of flying insects; their practical application as
insecticides is unfortunately, limited by chemical instability. However a
number of synthetic analogues have been examined and several show
promise as insecticides.
Azadirachtin
Neem – derived from Persian word Asad-dilakt-I-hind, which means free
tree of India - Azadirachta indica A. Juss.
In India 14 million trees (1959 survey) of which 50 % in UP. Though not a
forest tree it grows wild I the forests of AP, Tamil Nadu and Karnataka.
Full-grown neem tree yields 50 kg fruit annually and 350 kg of leaves.
India probably produces 0.7 million tones of fruits and 5 million tones of
leaves every year.
Almost every part of the tree is bitter and finds its application in
indigenous medicine. Oil and cosmetic industries are the users of neem.
The refined and purified neem seed oil has many therapeutic properties.
Considerable quantities of oil are used in cosmetic preparations. The
neem cake after oil recovery is used for slow release of nitrogenous
fertilizers.
Neem oil contains limonoids, a class of compounds that act as
antifeedants or growth regulators in insects. They do not kill instantly but
wipe out a whole generation of insects by preventing the young ones from
maturing and the adults from reproducing.
The most effective of the limonoids is a compound called azadirachtin.

125 AgriMoon.Com
Manures Fertilizers & Agrochemicals

It is similar to the insect hormone ecdysone, which is needed for moulting

during insect development. It works at a concentration of 1-10 ppm by
blocking ecdysone’s action, thereby preventing the larvae from shedding
their external skeletons and maturing. It also prevents feeding in about
200 insects at a concentration of 10-100 ppm.
The knowledge about neem in India is at least a few centuries ago. Indian
scientists had been studying neem for about 70 years and isolated some
active compounds by 1960’s.
A number of neem formulations are being produced by small-scale
formulators and marketed as insecticides. (Neemguard, Margocode,
Nimbicidine, Neemplus, Sukrina, Achook etc.).
Neem oil has some of the less known antifeedants like., salanin, nimbin
and epoxyazadiradione.(4 International conferences were held discussing
regarding production, structure elucidation, isolation of ai, residue
analysis).

Nicotine (C10 H14 N2).

Its chemical name is I-methyl-2,3 (pyridyl) pyrrolidine. It is the principal alkaloid in

tobacco (An alkaloid may be defined in general as a naturally occuring heterocyclic,
optically active nitrogenous base of relatively high molecular weight and having marked
physiological activity). Nicotine is found in the leaves of Nicotinana tabacam and N.
rustic a in the range of 2 to 14 per cent. Among the twelve alkaloids present in tobacco
nicotine is the most important one contributing about 97 per cent and the other two of
insecticidal value are (i) Nornicotine (C9 H12 N2) 2-(3-pyridyl pyrrolidine) (ii) Anabusine
(Neonicotine, 3-(2-piperdyl) pyridine.
Pyrethrum
The insecticidal principle in pyrethrum is found in the flower heads of certain plants
of chrysanthemum genus, family compositeae. Only a few species like c.roseum,

126 AgriMoon.Com
Manures Fertilizers & Agrochemicals

c.cineravieflium, c.marshalli and C.tamrutene have been found t<' be valuable sources
of this insecticide. It is used as dusts and sprays.

The flowers are dried at 54.4°C. These flowers are ground to a fine powder and
extracted with the solvents. The solvent is repeatedly percolated through the ground
flowers and the weak extracts. are evaporated in a vacuum still to recover the solvent.
The extracted powder (pyrethrum) containing traces of pyrethrins is sometimes used as
carriers in dust preparations. Dust concentrates are made from concentrated pyrethrum
extracts with a non-volatile solvent and a suitable absorbent carrier and then diluted
before use with an inert diluent. Antioxidants such as tannic acid or hydroquinone are
used to stabilise the pyrethrins in dust preparations. Concentrated extracts of pyrethrum
in aectone, alcohol or a hydrocarbon solvent together with an emulsifier is sold ill the
market.
Miscellaneous compounds
Picrotoxinin (PTX) has been isolated from the seeds of Anamirta
cocculus and is moderately toxic to Insects. E.g. Cockroaches, but is more
toxic to mice. PTX, like avermectins act on GABA regulated chloride ion
channels and functions as a GABA receptor antagonist.
Other compounds with a similar mode of action include the
trioxabicyclooctanes. Eg. The phosphorus ester and
bicycloorthocarboxylates: all are nerve poisons, which are not
cholinesterase inhibitors. The compounds were generally more toxic to
mammals than insects; the bicycloorthocarboxylates, however, can
sometimes show selective activity to house flies and cockroaches and
consequently, have potential for development as novel insecticides.
Insect neurapeptides (INPs) generally containing 5 – 10 amino acid
residues play vital role as circulating neurohormones and
neurotransmitters. They control many aspects of insect’s growth,
development and reproduction together with important physiological and
metabolic processes. Twenty five such processes are thought to be
mediated via these neuropeptides. By 1988, some 27 INPs have been
identified and their structures elucidated. For instance, in the locust, the
adipokinetic hormones AKH I and II, stimulate lipid metabolism during
periods of sustained activity. Eg. Migratory flight. Increased knowledge of
the structures and physiology of INPs should provide new potential target

127 AgriMoon.Com
Manures Fertilizers & Agrochemicals

sites for the design of novel insecticides. Peptide synthesis is one possible
area of exploitation – if certain physiologically active peptides were
introduced to the insect at the wrong time. Severe disruptive effects would
result.
If the gene coding for INPs could be introduced into crop plants,
then insects attacking the crop could be killed. Another promising line of
research would be the design of novel peptides and other molecules to
block the INP receptors.

128 AgriMoon.Com
Manures Fertilizers & Agrochemicals

27. CHARACTERISTICS, PREPARATION AND USE OF SYNTHETIC

PYRETHROIDS-FENVALERATE AND CYPERMETHRIN
Synthetic pyrethriods
Pyrethrum is derived from the dried flowers of the plant Chrysanthemum
cineariaefolium. The name given to the active insecticidal components of the dried
flowers is known as pyrethrins. Chemically pyrethrins are organic esters formed by the
combination of two carboxylic acids and three keto alcohols.
The synthesis of chrysanthemic acids and of cyclopentenolones
opened up the possibility of obtaining synthetic pyrethroids, a remarkable
class of insecticides.
The outstanding properties of pyrethrins are
 Rapid action
 Low mammalian toxicity
 Broad spectrum activity
 Lack of persistence
 Repellency
Allethrin is the first of its kind prepared by esterification of synthetic
chrysanthemic acid with the alcohol allethrolone.
Allethrin had strong insecticidal activity (0.1 µg / insect) and
removal of keto group gave another synthetic pyrethroid known as
bioallethrin (0.02 µg / insect).
Bioresmethrin is an extremely active insecticide (0.005 µg /
insect). This is photosensitive and consequently was not persistent.
However when the isobutenyl group of bioresmethrin was replaced by the
dichlorovinyl group, the resultant compound is NRDC134 which was more
toxic to house flies and mustard beetles than the most known
insecticides.
Permethrin was active against houseflies and mustard beetles and
showed much greater photostability and consequently was a moderately
persistent insecticide. It was the first synthetic pyrethroid effective as a
seed treatment against wheat bulb fly.
Decamethrin was prepared by replacement of chlorine atoms by
bromine and the introduction of ∝ cyano group from permethrin. This was
discovered in 1974 is a potent insecticide known. (0.0003 µg / insect) 50

129 AgriMoon.Com
Manures Fertilizers & Agrochemicals

times more active than Pyrethrin I. This has reasonable photostability and
very low mammalian toxicity.
The corresponding chloro derivative as the cis – trans mixture is
known as cypermethrin which is a broad spectrum insecticide (dose 20-
80 g /ha) with good residual activity on plants.
A survey of the esters of furylmethanol led to the discovery of
insecticidal activity in a group of phenyl acetic acid esters and Japanese
chemists at Sumitoma company introduced fenvalerate in 1974.
Fenvalerate is a mixture of 4 isomers and is used at 20-150 g ai/ha
against a wide range of pests and relatively stable in light.
American Cynamid introduced another phenyl acetic acid esters
viz., flucythrinate and fluvalinate.
Bromination of the double bonds on decamethrin and cypermethrin
gave tralomethrin and tralocythrin. Both are highly active – activity may be
due to the in vivo conversion in to parent compounds.
Lambda Cyhalothrin has a comparatively high mammalian toxicity
(LD 50 (Oral) 60 mg /kg). It is effective at very low doses (5-30 g ai/ha)
against major insect pests in many crops. Little hazard to honey bees and
this represents an important advantage over OP insecticides which are
highly toxic to honey bees. At normal rates cyhalothrin shows low toxicity
to birds with no accumulation in eggs or tissues and no effect on
earthworms. The half life in soil is 3-12 weeks; in aerobic soils it
undergoes extensive mineralization to CO2. In flooded soil degradation
was slower and only hydrolysis products were detected. No phytotoxicity
towards major crops and controls a wide spectrum of lepidopteran pests.
This is valuable for the control of plant virus vectors.
Tefluthrin is the first pyrethroid effective as a soil insecticide at
doses of 12-150 g ai/ha. It is formulated as granules and may also be
applied as foliar spray or seed dressing. Tefluthrin kills insects that are
resistant to OP and carbamate insecticides. Low mam. toxicity LD50
=1500mg/kg.Little hazard to earthworms and birds but highly toxic to fish.
Half life in soil is 4-12 weeks and there is no danger of residue
accumulation.
Mode of action of pyrethroids

130 AgriMoon.Com
Manures Fertilizers & Agrochemicals

 The symptoms of insects poisoned by pyrethroids clearly show that

the chemical attacks the insect’s nervous systems.

 Pyrethroids cause hyper excitation followed by convulsions and

death in arthropods.

 The rate and mechanism of metabolism has a major influence on

the toxicology of a compound.

 In (rats) mammals pyrethroids are very rapidly metabolized by ester

cleavage, oxidation hydroxylation.

 The synthetic pyrethriods are very expensive to prepare on a tonnage basis.

 The high insecticidal activity and low mammalian toxicity of pyrethroids are
especially significant now that compounds stable to light and oxygen are
potentially available.
 Their toxicity to fish is high. They are rapidly degraded in soil and have no
detectable illeffects on soil microflora and microfauna. They are not active
against mites.

 The major symptoms of pyrethroid poisoning in insects may be accounted by

effects on the kinetics of nerve membrane sodium channels.

 The mean open times of these channels are prolonged with consequent
hyperactivity of nerves.

 The synthetic pyrethroids have been found to be useful as early season sprays to
control the variety of insects that occur on cotton including boll worms, leaf
worms, jassids, thrips and whitefly. They are used in combination with an organo
phosphorus insecticide as an ultra-low volume spray.

 They are non toxic to humans and animals. LD50 to rats is around 8000 mg/kg.
They are used at only 50 g/ha. The cost/of treatment per hectare is low.

131 AgriMoon.Com
Manures Fertilizers & Agrochemicals

28. HERBICIDES – MODE OF ACTION – CLASSIFICATION OF ORGANIC

HERBICIDES CHARACTERISTICS –
Introduction
A herbicide in the broadest sense is any compound that is capable of killing or
severely injuring plants and may be used for elimination of plant growth.
A weed is an plant, wild or cultivated that is undesired in that particular place. In
Agriculture and horticulture weeds are thus any ant other than the specific crop being
grown. On railway tracks, industrial sites, air port paths, open spaces and the like the
entire vegetation can be regarded as weeds.
Weeds are conveniently divided into dicotyledonous plants, termed broad leaf
weeds and monocotyledonous plants, termed grass weeds. Weeds completed with
plants for water, light, food and above and below the surface. The yield loss due to
weeds is estimated to be 9-10%. Also herbicide economies or helps in crop production
by reducing the cultural operations.
Herbicides may be classified based on one or more common characteristics such
as chemical composition or mode of action or time of application etc.
----------------------------- Organic

Chemical
----------------------------- Inorganic

Contact

Mode Of Action

Systemic

Pre-Sowing
Time of application.................... Pre-emergence
Post-emergence of Crops
Pre-emergence or post-emergence is with respect to the
emergence of crop and not of the weed

Soil herbicides - root absorption systemic

132 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Manner of absorption
Foliage herbicide - contact
Total - unspecified vegetation
Range of application
Selective

Aromatic-Carboxylic
a) 2, 4-D : 2,4-Dichlorphenoxy acetic acid
LD50: 375
2, 4-D can be used for destruction of dictotyledonous plants and it is well tolerated
by many monocotyledonous crop plants.

2, 4-D is used as a selective herbicide particularly in cereals. The great advantages

are cheap manufacture and relatively low mammalian toxicity. It is a systemic herbicide.
b) 2,4,5, T : 2,4,5, Trichlorophenoxy acetic acid
LD50: 500
2,4,5, T has particularly high activity against woody plants and usually used in
combination with other herbicides for control of trees, shrubs and control of otherwise
intractable broad leaf weeds.
Structural analogues of IAA such as NAA or 2,4-0 promote growth in lower doses
but have a herbeidal effect at higher concentrations. 2,4,5, T is more persistent in soil
than 2,4-D or MCP A (2-methyl-4-chlorophenoxy acetic acid).
Mode of Action
• Interference with nucleic acid metabolism
• Disruption of translocation system

Anilides
The type of activity and the range of weed control vary greatly within
this group some being used post-emergence while others are active
through the soil.
In 1965, 1966 and 1969 Monsanto introduced three anilides for pre-
emergence control of annual weeds.
(1) (α-chloro-N-isopropyl acetanilide) as 'Ramrod' which shows a
high degree of specificity for annual grass weeds and certain
133 AgriMoon.Com
Manures Fertilizers & Agrochemicals

broad- leaved weeds in maize, soybeans, sugarcane, peanuts and

certain vegetables. (ii) Alachlor (α-chloro-2'6'-diethyl-
Nimethoxy methyl acetamide) as 'Lasso’ for use in maize, cotton,
soybeans, sugarcane, peanuts and certain vegetable crops where it
shows very good activity against annual grasses, particularly
Echinochloa crus-galli, Setaria Spp. and Digitaria Spp. (iii)
Butachlor (N-[butoxymethyl]-chloro-2',6'-diethyl acetanilide) as
'Machete' for the control of most annual grasses, certain broad-
leaved species in transplanted rice. In 1974, Ciba Geigy
introduced metolachlor (2-chloro-6'-ethyl-N- [2-methoxy-l-
methylethyl] acet-o-toluidide) as 'Dual', a pre- emergence
germination inhibitor, active mainly on grasses for use in maize,
soybeans and groundnut.

Butachlor
oxyfluorfen
Thiocarbamates
EPTC (S-ethyl-N.N-dipropylthiocarbamate).'Eptam', was introduced
by Stauffer in 1954. It kills germinating seeds, a number of annuals and
inhibits bud development in the underground organs of perennial weeds
such as couch grass (Agropyron repens) and sedges (Cyperus Sp.). It may
be used soil incorporated 3 weeks before planting potatoes, field beans,
sugar beet and others. Monsanto introduced di-allate as 'Avadex’ (S-
2,3-dichloroallyl-N,N-di-isopropyl (thiocarbamate)), a volatile herbicide
for pre-plant control of Avena fatua and Alopecurus myosuroides in
brassica and beet crops in 1960; and tri-allate (S-[2,3,3’- trichloroallyl]-di-

134 AgriMoon.Com
Manures Fertilizers & Agrochemicals

isopropyl (thiocarbamate)) in for the control of these grasses and others in

cereals and peas.
In 1970 thiobencarb (S-4-chlorobenzyl diethyl thiocarbamate) was
introduced It is an important herbicide for the control of weeds in rice
showing very high selectivity between rice and barnyard grass
(Echinochloa crus-galli). In addition it controls many other grass
cyperaceous and broadleaved weeds.
Thiobencarb

Substituted Ureas
Diuron (3-[3,4-dichlorophenyl]-1,1-dimethylurea) as 'Karmex’, was
introduced by Du Pont in 1954 and Fenuron (I,I-dimethyl-3- phenyl urea)
as 'Dybar' was introduced in 1957 and is used for the control of woody
plants by basal application.
Fluometuron (1, I –dimethyl-3-[α-trifluoro-m-tolyllurea) as 'Cotoran'. was
introduced by Ciba Geigy and is used for the control of weeds in cotton.
Another very important herbicide for the control of annual, grasses
including Alopecurus myosuroldes, Avena fatua and Poa annua and many
annual broadleaved weeds in cereals was isoproturon (3-[4-isopropyl-
phenyl]- 1, I –dimethyl urea) marketed by three companies - Hoechst (as
'Arelon'), Ciba Geigy (as 'Graminon') and Rhone-Poulenc (as 'Tolkan') in
1972.

Diuron lsoproturon

135 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Heterocyclic Nitrogen Compounds

Triazines
In general triazines have little effect on germination and they are
taken up by the roots or leaves. Due to an inhibition of the Hill reaction of
photosynthesis, affected plants turn yellow and necrotic symptoms
develop. With a few exceptions, the symmetrical triazines have got
substituted amino groups at two of the carbon atoms while the third carbon
has a chloro, a thioether or a methoxy function. The chloro compounds
(CI) end in azine, the thioethers (-S-) end in tryne (e) and the methoxy
ones (CH30) in ton. In the list of herbicides which follows all were
introduced by Ciba Geigy unless stated otherwise. The first
commercial triazine, simazine (2 – chloro - 4, 6 - bis [ethyl -amino] - I,3,5
-triazine) was introduced as 'Gesatop' in 1956 for the selective residual
pre-emergence control of a great many annual grass and broadleaved
weeds in a variety of deep-rooted crops (including citrus fruits, coffee, tea
and cocoa), due to its low solubility in water (3.5 mg I-1 at 20°C). It is also
used for the control of most annual and perennial weeds in non-crop areas.
It is remarkably selective for use on maize because of the ability of this
crop to degrade it non-enzymically to the non-active hydroxy derivative.

Simazine
The second introduction atrazine (2-chloro-4-ethylamino-6-
isopropylamino-1,3,5-triazine), introduced as 'Gesaprin’ and 'Primatol in
1958, is both foliar and soil acting being taken up both by leaves of
emerged weeds and by the roots of weed seedlings emerging after
spraying. In maize, where it is also degraded in, a manner similar to

136 AgriMoon.Com
Manures Fertilizers & Agrochemicals

simazine, it is preferred to the latter especially in dry years. Being more

water soluble (30mg I-1 at 20°C) it is more suitable for the dry soils on
which this crop is grown where it will effectively control couch grass
(Agropyron repens) and other perennial grasses. It is also used in roses,
for selective use in coniferous forests and for non- selective use on non-
crop land and industrial sites.

Atrazine
Pyridines
In 1957 and 1958 I.C.I. introduced two very important bipyridillium
quaternary herbicides. Both are broad spectrum, rapidly acting causing
wilt and desiccation, and are translocated to a certain extent. Diquat (1,
I'-ethylene-2,2'-bipyridillium ion formulated as dibromide) under various
trade names 'Reglone', Weedol', 'Path clear' is used for potato haulm
desiccation, for seed crop desiccation and for aquatic weed control. The
Chapman Chemical markets it as 'Aquacide’. Paraquat (1,1'-dimethyl-
4,4'-bipyridilium ion formulated as dichloride) as 'Gramoxone' destroys
photosynthetic tissues and Is used for a variety of purposes Including
stubble cleaning, inter-row weed control, desiccation of various crops and
killing out of old pastures which can then be resown without ploughing.
It is very fast acting, the first effects being noticeable after a few hours
and kill is usually completed in 3-4 days. It is quickly absorbed on to soil
(particularly clay) particles so that sowing can follow soon after
application.

137 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Diquat Paraquat
The Dow chemical has Introduced three foliar-applied, selective,
growth-regulatory herbicides which produce symptoms on susceptible
plants very similar to those produced by the auxin type herbicides, namely
tissue proliferation, epinasty, leaf curling and production of adventitious
roots.

Organophosphorus Compounds
The organophosphorus compounds include: (1) bensulide (0,0-
diisopropyl-S-2-phenyl-sulphanylaminoethyl phosphorodithioate) which
was introduced by Stauffer in 1964 as 'Prefair' for pre-plant pre-emergence
use on cucurbits, brassicas, lettuce and cotton, and as 'Betasan' for pre-
emergence control of annual grasses and broad-leaved weeds in lawns. (2)
Piperophos (S-2-methylpiperidino-carbonyl methyl-0,0-dipropyl
phosphorodithioate) was introduced by Ciba Geigy in 1969. It can be used
pre-emergence in rice, maize, cotton, soybeans and groundnuts for the
control of many monocotyledonous weeds including Cyperus Sp.,
Echinochloa Sp., Trianthema portulacastrum and Monochoria
vaginallis.Glyphosate (N-[phosphonomethyl] glycine) a derivative of the
amino acid, glycine, was introduced by Monsanto as 'roundup' in 1971. It
is used post-emergence and is rapidly absorbed by the leaves and
translocated from vegetative parts to underground parts, rhizomes or

138 AgriMoon.Com
Manures Fertilizers & Agrochemicals

stolens of perennial grass and broad-leaved weed species giving good

control of both above-ground and underground organs Agropyron repens
is very sensitive. Glyphosate is inactivated on contact with the soil. It
provides excellent weed control in pre-tillage of post-harvest treatments of
annual crops or when applied as a direct spray in woody crops such as
vineyards, deciduous fruit, rubber, coffee, citrus, tea and oil palm.It can
also be used in non-agricultural areas and for bush control in forestry.

Piperophos Glyphosate

139 AgriMoon.Com
Manures Fertilizers & Agrochemicals

29. Fungicides - Classification - Inorganics - characteristics, preparation

and use of sulfur and copper - Mode of action - Bordeaux mixture and
copper oxychloride
Fungicides are chemicals that have the ability to reduce or prevent
the damage caused by fungi in plants and their products. Fungicides are
classified based on mode of action as protective, curative and eradicant
fungicides.
Protective fungicides prevent fungal infection by sporicidal activity.
These arrest the germination of spores or kill the fungal hypae as they
penetrate the leaf or prevent their penetration. E.g. Sulphur
Curative fungicides penetrate cuticle and kill young fungal mycelium
growing in the epidermis and this prevents further development of fungal
growth. E.g. Organomercurials.
Eradicant fungicides are agents that make control of fungus even after
the symptoms become visible and that kill both newly developed spores
and the mycelium. E.g. Systemic fungicides.
The early fungicides were inorganic materials like sulphur, lime sulphur,
copper and mercury compounds.
Sulphur compounds
Elemental Sulphur is available in dust, wettable powder and colloidal
forms. The efficiency of S dust increases with fineness of the particle size.
A high proportion should pass through 200 – 300 mesh sieve. Colloidal
sulphur is formulated with kaolin (diluent) with 40 per cent S and a particle
size of < 6 µ. Sulphur is a contact and protectant fungicide used to control
powdery mildew in fruits, vegetables, flowers and tobacco. It is also
effective against apple scab and rust of field crops. Lime sulphur: It is
aqueous solution of calcium poly sulphides. It is prepared by sulphur
solution in calcium hydroxide suspensions under pressure in the presence
of air. Calcium penta sulphide and calcium tetra sulphide found in the
mixture are the active materials of fungicidal value which on exposure to
air release elemental S.
Mode of action: At first it was observed that S could not be the toxic
agent. Sempio (1932) reported that the action was due to the production
of various S derivatives. Another theory was that the fungal spores reduce
S to H2S which has shown to be toxic to the spores. However in 1953 this
140 AgriMoon.Com
Manures Fertilizers & Agrochemicals

theory was disproved as colloidal S was more effective than H2S. Another
hypothesis ascribed to various oxidation products such as SO2, H2SO4
and thiosulphuric acid. Then no S derivative is responsible and came to
Sempio and finally that S itself is fungi toxic.
Among the heavy metals only Cu and Hg have been widely used as
fungicides although silver is most toxic metal cation. The relative toxicity
is in the order of
Ag > Hg > Cu > Cd > Cr > Ni > Pb > Co > Zn > Fe > Ca
Copper compounds
Copper sulphate has been used since 18th century as seed treatment
against cereal bunt later replaced by organomercurials. Cu ions in
solution are toxic to all plant life. Selective fungicidal action can therefore
be achieved by application of insoluble Cu compound on the foliage.
E.g. COC, Copper carbonate, Copper hydroxide, Bordeaux mixture etc.
Bordeaux mixture
Millardet in 1882 discovered the Bordeaux mixture effective against
powdery mildew. A mixture of copper sulphate and lime was initially applied as a
paste and thus gained wide recognition as “Bovillie Bordelaise” (Bordeaux Mixture). As
the initial mixture continuing 8 kg of blue stone dissolved in 100 litres of water and 30
litres of lime suspension prepared with 15 kg lime was found to cause foliar injury.
Various combination were tried. Now a 4-4-50 mixture (copper sulphate in 1 b; lime in 1
b; water in gallons), is used but the concentration of the ingredients is varied depending
on the purpose. However, the proportion of copper sulphate to lime usually remains
constant. In India Bordeaux mixture is being made by preparing a solution of copper
sulphate and quick like (or hydrated lime) in finely ground form in separate containers
and then mixing them simultaneously into a third container with copper sulphate like
copper, wooden and earthern vessels. Wide variation in the composition of the resulting
mixture will be observed due to chemical reactions between calcium hydroxide and
copper sulphate in solution when the ratio between the components is changed.
Bordeaux mixture named from the locality of its origin consists of Cu SO4
(4.5 kg) and Ca (OH) 2 (5.5 kg) in 454 litres of water. It is prepared under
a wide range of formulae. Once the mixture has been prepared it should
be sprayed immediately on the crop since the toxicity decreases on
standing. It is rather difficult to apply because the precipitate tends to
block the nozzles. Jaggary or sugar is added to prevent crystallisation.

141 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Mode of action is complex. The ai is probably not Cu (OH) 2 but rather

basic Cu SO4 approximately to the formula [Cu SO4. 3 Cu (OH) 2].

Bordeaux mixture is almost insoluble in water. So how is Cu mobilized in

plants to kill the fungus? The exudates both from the surface of leaf and
from the fungal spores can dissolve sufficient quantities of Cu from the
dried deposits due to the presence of certain compounds like amino and
hydroxy acids which can form chelates with copper.
B) Copper oxychloride
(Blue copper 50: Fytolan) Cupramar, Blimix 4%, Blitox 50%.
Copper oxychloride is one of the low soluble copper fungicides produced by the
action of air on cupric chloride solution or scrap copper.
4Cu + O2  2Cu2O
Cu2O+2HCl  2CuCl + H2O
2 CuCl + O + 2 HCl  2CuCl2 + H2O
CuCl2 + Cu  2 CuCl
4CuCl2 + 3CaCo3 + 3H2O  3Cu(OH)2 CuCl2 + 3Cl2
It is marketed in the form of wettable powder containing 50 and 90% copper
oxychloride and dusts containing 4 to 12% metallic copper. The 50% formulation
contains a diluent (Kaolin) and a surface active agent.
Burgandy mixture
This was introduced by Mason in 1887 by mixing copper sulphate (1 part)
with sodium carbonate crystals (1 part) and is less effective than
Bordeaux mixture.
Cheshnut compound
This is suggested by Bewley in 1921 consists of 2 parts of Cu SO4 and 11
parts of (NH4)2 CO3. The two compounds are well powdered thoroughly
mixed and stored in air tight containers for 24 hours before use.
Chaubattia paste
This was developed at Government Fruit Research Station, Chaubattia,
Almora district, UP. It is prepared by mixing copper carbonate (800 g) and
red lead (800 g) in 1 litre of linolin or raw linseed oil. It is used as wound
dressing agent on pruned parts.
Copper oxy chloride approximately Cu Cl 2. 3 Cu (OH) 2 is marketed as
colloid and wettable powder. It is a protective fungicide used to control

142 AgriMoon.Com
Manures Fertilizers & Agrochemicals

potato blight, several leaf spots and effective against several diseases of
horticultural crops.
COPPER HYDROXIDE Cu (OH)2 IS A NEW FORMULATION
INTRODUCED.
Mode of action is the denature of proteins by free copper ions. Since
enzymes are made up of proteins, the Cu inactivates the enzymes. The
Cu kills the fungal spores by combining with the sulphohydril groups of
certain enzymes.

143 AgriMoon.Com
Manures Fertilizers & Agrochemicals

30. Organic fungicides – Mode of action-. Dithiocarbamates- characteristics and

use of Zineb and Maneb

Dithiocarbamates (Organic sulphur compounds)

Investigations of the DuPont Company (USA) showed that some of the
derivatives of dithiocarbamic acid H2N ,CSH had insecticidal and fungicidal properties.
However dithiocarbamic acid itself is not known to exist in the free state. When the
primary and secondary aliphatic and aromatic amines are treated with carbon-di-
sulphide in alcoholic solutions, dithiochrbamates are produced.
The hydrogen attached to S dissociates and may be replaced by a metal or other
radicals producing a variety of derivatives. The group > NCS is considered to be
essential for insecticidal and fungicidal action. By reacting dimethylamine and CS2
under alkaline conditions, Thiram and salts of Na, Fe and Cd were prepared. Nabam
was produced by reacting ethylene diamine and CS2. Subsequently the heavy metal
complexes of dithiocarbamates like Ziram and Ferbam and complexes of
bisdithiocarbamates like maneb and zineb were developed.
A large number of derivatives of dithiocarbamic acid possess fungicidal
properties. They can be classified as follows.
1. Metalic dithiocarbamates – Ziram and Ferbam
2. Thiuram disulphide (Thiram) –S-Slinkage
3. Bis dithiocarbamates – Manels, Nabam, Zineb
A) Zineb (Dithane-A 78)
Dithane-Z 78 is a white crystalline substance insoluble in water and most organic
solvents; moderately soluble in pyridine. It is unstable in the presence of moister, heat,
light and alkali. Moist compound under unfavourable storage conditions may
decompose to 50% in a year. To reduce the chance of explosive evolution of CS2, Zineb
has to be stored in a well ventilated place at low temperatures. It is compatible with
most insecticides like Ferbam.
It is formulated as wettable powder. Its residual effect depends on weather and
season. Zineb can be of great use on Zn deficient soils.
B) Maneb (Dithane-M 45, Manzate)
It is the manganese salt of ethyulene bisdithiocarbamic acid; is similar to zineb, in
most physical and chemical properties. Decomposes rapidly under high temperature
and moisture. It is a yellow crystalline substance insoluble in water and organic
solvents. Compatibility is similar to Ferbam. When stored in bulk, Maneb is capable of
144 AgriMoon.Com
Manures Fertilizers & Agrochemicals

spontaneous decomposition with charring which can be avoided by diluting with an inert
material. Other analogues are Dithane C-31, Propineb, Thioneb (carbathene).
Thiram as tetra methyl thiuram disulphide was the first compound to be
applied as a fungicide and is still used, especially against moulds and as
a seed dressing against soil fungi causing damping off. Thiram is
prepared by the interaction of carbon disulphide and dimethylamine in the
presence of NaOH which is subsequently oxidized to thiram.
Later work resulted in the discovery of the fungicidal activity of zinc and
ferric salts of dimethyl dithiocarbamates known as ziram and ferbam
respectively. Disodium ethylene bis dithiocarbamate or nabum is also
fungicidal and is used to control stem rots. Nabum is the insoluble zinc
and manganese salts known as zineb and maneb which are produced by
reaction with an aqueous solution of zinc and manganese sulphate have
largely replaced water soluble. These are used as protectant fungicides
and are applied for the control of wide range of phyto pathogenic fungi
such as downy mildews. They have very low mammalian toxicities (LD 50
-1
> 7000 mg kg ).
Metham-sodium (N- methyl dithiocarbamate) is a valuable soil sterilant
for the control of damping off diseases.
Mancozeb, a coordinated complex of zinc and manganous salts was
introduced in 1962. Maneb and mancozeb are formulated with synthetic
fungicides to reduce development of resistance.
The dithiocarbamates owe their fungicidal activity due to their ability to
chelate with metal cations such as copper. The dithiocarbamates get
metabolized to isothio cyanates which react with vital thiol compounds
with in the fungal cell.
Heterocyclic N compounds
Captan (N-(trichloromethylthio)-4-cyclohexane-1,2-dicarboximide) is a
very effective and persistent foliage fungicide against many soil and seed
borne diseases. Analogues that have been subsequently developed as
foliar fungicides include folpet and difolatan, which are most active
against potato blight. These are some of the safest fungicides (LD 50 >
10000 mg kg-1).
Captan interacts with cellular thiols to produce thiophosgene which poison
the fungus.

145 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Dichlofluanid, introduced by Bayer is a broad spectrum protective

fungicide which is less sensitive than captan.
Phenols
The majority of phenols, especially those containing chlorine, are toxic to
microorganisms, their bacterial action has been known for along time and
many phenols are also fungicidal. However many are phytotoxic.
Shirlan or salicylanilide is used to inhibit the growth of moulds on cotton
and against a number of laef diseases as tomato mould.
Dinocap is a non systemic aphicide and contact fungicide which is
effective for the control of powdery of mildew on many horticultural crops.
Low mammalian toxicity LD 50 > 980 mg kg-1.
Binapacryl is closely related to dinocap and is used for the control of
powdery mildew on apples.
Oxine α-hydroxy quinoline is a protectant fungicide, when suitably
formulated, appears to possess limited systemic action. Oxine has a
striking capacity to form chelates with metals (Cu) which is effective
against a range of phytopathogenic fungi.
Chlorobenzenes and related compounds
2,6-dichloro-4-nitro aniline was marketed in 1959 by Boots Ltd. Especially
valuable for the control of Botrytis in tomatoes and against fungal
organisms causing post harvest decay of fruits.
Penta chloro nitro benzene (PCNB) called quintazene is a widely used
soil fungicide for damping off diseases. Chloroneb is used to control soil
borne fungi as seed dressings or by soil application.
Chlorothalonil is a broad spectrum foliar or soil applied fungicide used in
many crops. Sandoz kavach.

Chlorothalonil

146 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Quinones
A number of quinines occur in plants and are also products of fungal
metabolism.
Dichlone is more stable in light has been used as a seed dressing agent
and a foliage spray against powdery mildew.
Dodine (N-dodecyl guanidine acetate) has been known asa bactericide
(1941) and more recently has been shown to have fungicidal activity.
Dodine is a cationic surfactant is generally formulated as wettable
powder. Low mammalian Toxicity (LD 50 > 1500 mg kg-1).
Guazatine is mainly used as seed dressing agent for cereals at 0.6 –0.8
g ai kg-1 of seed and against post harvest diseases. (LD 50 > 500 mg kg-1).
The fungicidal activity of these compounds probably depend on their
ability to alter the permeability of the fungal cell wall, causing loss of vital
cellular components such as amino acids and P compounds.
Dicarboximides
All members contain the 3,5-dichlorophenyl moiety and the fungicidal
activity depends on the presence of the two chlorine atoms in 3, 5
positions.
Procymidone, hydantoin, iporodione and vinclozolin have been
extensively used for the control of Botrytis and Scelrotinia sp in cereals,
fruits and vegetables but their use is restricted due to the development of
resistance.
More recently metomedan, chlozolinate and myclozoline have been
introduced.
Drazoxolon (ICI,1960) is a valuable seed dressing agent against
damping off diseases.
The dicarboximides have low mammalian toxicities (LD 50 > 3500 mg kg-.

147 AgriMoon.Com
Manures Fertilizers & Agrochemicals

31. SYSTEMIC FUNGICIDES – Benomyl, carboxin, oxycarboxin,

Metalaxyl, Carbendazim,- characteristics and use
The idea is earlier but 1960 only commercial systemic fungicides
have come to market. A systemic fungicide is a compound that is taken
up by a plant and is then translocated with in the plant, thus protecting the
plant from attack by pathogenic fungi or limiting an established fungal
infection.
If a candidate chemical is to be an effective systemic fungicide the
following criteria must be satisfied. It must be fungicidal or to be converted
in to an active fungitoxicant with in the host plant.It must possess very low
phytotoxicity. It must be capable of being absorbed by the roots, seeds or
leaves of the plant and then translocated, at least locally, within the plant.
The earlier protectant fungicides applied as foliar sprays formed dried
deposits on the leaves of the host plant, protecting it from fungal attack.
However the deposits are of course gradually removed by the effects of
weathering and cannot protect new plant growth formed after spraying or
any part of the plant not covered by spraying. These disadvantages can
be overcome by the use of systemic fungicides which since penetrates
the plant cuticle. They also offer the possibility of controlling an
established fungal infection. There fore systemic fungicides should exhibit
both protectant and eradicant activity.
Benzimidazoles
These represent a new era in fungicide use when they were introduced in
late 1960s.

148 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Benomyl Carbendazim

The most important members of this group are benomyl [methyl –1-
(butyl carbamoyl) benzimidazole-2- carbamates] TN: Benlate and
thiobendazole. Both are wide spectrum systemic fungicides effective
against many pathogenic fungi including powdery mildews and soil borne
pathogens. These fungicides may persist in plants for several months.
Benomyl was introduced in 1967. It was synthesized from cyanide and
methylchloroformate. Benomyl and thiabendazole are both wide spectrum systemic
fungicides active against many pathogenic fingi including powdery mildews and soil-
borne pathogens, Verticillium alboatrum on cotton and black spot on roses.
Du-pont; Benlate LD50: > 9590
Foliar fungicide in wine grape fruits, vegetables, citrus, cereal seed dressing.
Benomyl is the more active compound and is widely applied as a foliar spray,
seed dressing or to the soil for control of grey mould (Botrytis cinerea), apple scab
(Venturia inequalis) canker and powdery mildew (Podosphaera leucotricha), leaf spot
(Cercospora beticola), major fungal diseases of soft fruits and some pathogens of
tomato and cucumber.In aqueous solution benomyl is rapidly hydrolysed to
methyl benzimidazole – 2 – carbamate and this is probably the active
fungitoxicant carbendazim which is used as a wide spectrum systemic
fungicide formulated as 50 per cent WP.
Metalaxyl
Metalaxyl is included in the phenylamides group of systemic fungicides.
The compounds of this group show protective and systemic activity against
Oomyceles causing foliar, root and crown diseases in wide range of crops eg. downy
mildews and late blight. The first members of this group Metalaxyl and Furalaxyl
were introduction by Ciba-Geigy in 1977 (Metalaxyl = Ridomil). With a high activity at
low rates of foliar or soil application metalaxyl controls diseases caused by air or soil
borne comycetes in crops like potatoes, grapes, tobacco, cereals, hops and vegetables.
A wettable powder formulation with mancozeb, (a complex of Zn and Mn salts
fungicides) is widely used as a foliar spray against hlight on potatoes. Metalaxyl has the
broadest spectrum of fungicidal activity of this group of fungicides; it is good against
downy mildew on vines, lettuce, maize and Pythium diseases and can be formulated as
a seed dressing.
E) Carbendazim (Bavistin, Derosol)

149 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Foliar fungicide in grapes, fruits, vegetables, cereals, cereal seed dressing

LD50: 15.000 Carbenda in methylbenzimidazole-2-carbamate is used as a wide
spectrum systemic fungicide and may be formulated as a 50% w.p. for control of
Botrytis, Gloeosporium rots, powdery mildews and apple scab. Carbendazim is
absorbed by the roots and foliage of plants and is quicker acting than Benomyl.
The activity of the benzimidazole fungicides (Benomyl, thiabendazole and
carbendazim) is due to the inhibition of nuclear division due to their action on the
microtubule assembly and the resistance developed in fungi is the result of mutant
strains possessing an altered microtubule assembly.
Carboxin and related compounds (Oxathiins)
Oxathiins are another group of heterocyclic compounds with interesting
systemic fungicidal properties. Carboxin and the sulphone analogue
known as oxycarboxin are primarily effective against basidomycetes
class of fungi which includes such economically important group of fungal
pathogens rusts, smuts and bunts of cereals and the soil fungus
Rhizactonia solani.

The fungitoxicity is due to inhibition of glucose and acetate oxidative

metabolism and RNA and DNA synthesis.
Carboxin and Oxycarboxin
Oxathins are another group of heterocyclic compounds with systemic fungicidal
properties. Examples are Carboxin (5, 6 dihydro-2-methyl-1, 4 oxathin-3-carboxanilisde)
(Vitavax) and the sulphone analogue known as Oxycarboxin (Plantvax).

LD50: 3820 LD50: 2000

Seed dressing: cereals, cotton Sol and foliar fungicide

smuts & Rests Rusts

150 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Carboxin is prepared by reaction of α-chloroacetoacetanilide and 2-thiothanol

followed by cyclization. Oxycarboxin is obtained by subsequent oxidation of
carboxin with hydrogen peroxide. Both are fairly water soluble and are not phytotoxic.
They are active against Basicdiomycetes class of fungi causing rusts, smuts and bunts
of cereals and soil fungi Rhizoctonia solani. Carboxin can be formulated with other
fungicides like thiram, copper oxine.
C) Oxycarboxin
Oxycarboxin has systemic action against rusts of cerals, and vegetables and
seed treatment or soil application can be done. Carboxin is absorbed and
translocated by plant roots. In water, soil and plants; the compound is oxidiseds to
sulphozide but further oxidation to sulphone was not observed. The sulphoxide is much
less fungicidal and so oxidation causes loss of activity. The primary mode of action
of carboxin and related compounds probably involves the blocking of succinate oxidation
in the mitochondria of sensitive fungi.

Antibiotics
Antibiotics are chemicals produced by living organisms that are
selectively toxic to other organisms. The first successful antibiotic against
human diseases was penicillin discovered by Fleming (1929) but it has
never achieved commercial significance as a systemic fungicide.
Glitoxin, an antifungal antibiotic produced by the soil fungus Tricoderma
viride inhibited the growth of Botrytis and Fusarium spores at 2-4 ppm
concentration but the compound was too unstable for use as a soil
fungicide.
Streptomycin and cycloheximide are antibiotics obtained from the
culture filtrates of Streptomyces griseus is used for the control of bacterial
pathogens of plants.
Griseofulvin isolated in 1939 from Penicillium griseofulvum is an
important antifungal antibiotic showing a wide spectrum of activity
especially against Botrytis in lettuce and Alternaria solani on tomato.
Blasticidin, a pyrimidine derivative isolated from Streptomyces
griseochromogenes give excellent control of rice blast and also inhibits
certain bacteria. The antibiotic polyoxin D is another pyrimidine
derivative which is toxic towards several fungi including rice blast. The
fungi toxicity is due to interference with chitin synthesis.

151 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Melanin Biosynthesis Inhibitors (MBI s) act on the pathogen to

prevent it penetrating the plant epidermis; these compounds block
melanin synthesis in a variety of Ascomycetes and fungi imperfecti. They
provide practical control of rice blast and experimental control of some
Colleotricum species. Tricyclozole prevents the rigidity of penetration by
Pyricularia oryzae. Validamycin is an aminoglucoside antibiotic active
mainly against Rhizactonia diseases and has been widely used to control
rice sheath blight. Probenazole related to saccharin is effective by root
application against rice blast and bacterial leaf disease Xanthomonas
oryzae. It is not fungi toxic Invitro and probably acts indirectly by
enhancing the resistance response of the host plant.
Aminopyrimidines
Some 30 years ago there is a series of 2-amino-4-hydroxypyrimidines had
specific systemic activity against powdery mildews. These structure
activity studies led to development of dimethrinol and ethrinol.
Dimethrinol discovered in 1965, showed outstanding systemic activity by
root application against certain powdery mildews in vegetables and some
ornamentals.

Piperazine, pyridine, pyrimidine, imidazole and triazole

fungicides
These fungicides are considered together because they all show a
common biochemical target, namely synthesis of ergosterol; they are
methylation inhibitors.
Triforine is the only piperazine derivative showing systemic activity
against powdery mildews on cereals and vegetables.

Buthiobate and pyrifenox are pyridine fungicides. Buthiobate is used

mainly in Japan against powdery mildews while pyrifenox controls a wide
range of leaf spot pathogens of fruits and vegetables.

152 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Triarimol, fenarimol and nunarimol are pyrimidine derivatives

introduced by Eli Lilly in the late 1960s. Triarimol has been withdrawn due
to its undesirable toxicological properties. Fenarimol, a systemic and
protective fungicide is used as a foliar spray to control a broad spectrum
of powdery mildews, scabs, rusts and leaf spots. Nuarimol is used against
powdery mildews in cereals.

Fenarimol Nunarimol
Imazalil, the first imidazole agricultural fungicide (1960) is now used as
seed dressing in cereals.

Prochloraz Imazalil

Prochloraz (Boots, 1973) is a broad spectrum fungicide with good activity

against ascomycetes and fungi imperfecti but rather less activity against
basidamycetes.
Triflumizole controls a wide range of pathogens Viz., powdery mildews
and scabs.
Triadimefon [(1-(4-chlorophenoxy) 3,3-dimethyl –1-(1,2-triazol –1yl)
butan-1-one)] TN: Bayleton has systemic activity against a broad range of
plant pathogens effective at rates of 0.1 – 2.0 ppm. This discovery led to
the introduction of several 1,2,4- triazole fungicides.

153 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Triadimefon
These fungicides owe their fungitoxicity due to their ability to inhibit
ergosterol biosynthesis. Ergosterol is a major sterol in many fungi where it
plays a major role in membrane structure and function.
Morpholine fungicides
Dodemorph (roses) and tridemorph (cereals) are systemic foliar
-1
fungicides effective against powdery mildews at 0.75 litres ha .

Dedemorph Tridemorph

Organo phosphorus fungicides

Today more than 100 OP compounds show fungicidal action. However
relatively few compounds are of practical use as fungicides, Many are
phytotoxic and very specific against fungal species.
One of the first Op fungicides was triamiphos claimed to be the first
systemic commercial fungicide. Since then many compounds were
derived. Pyrazophos TN: Afugan is a foliar systemic fungicide effective
against apple powdery mildew.
Triclophos – methyl is effective against Rhizactonia and other soil borne
diseases as a drench in vegetables and against black scarf and canker in
seed potatoes.
Iprofenfos TN: Kitazin P introduced in 1968, is a systemic rice fungicide
applied as granules in paddy water to control rice blast and it inhibits
mycelial growth in tissues.
Edifenphos is also very effective against rice blast.

154 AgriMoon.Com
Manures Fertilizers & Agrochemicals

OP fungicides have shown to block the synthesis of phospholipids. The

reduction in phospholipids alters the membrane structure, increasing the
permeability and consequent loss of vital cellular components and
eventually killing the fungus.
Phenyamides and related compounds
 Metaloxyl – broad spectrum
 Furalaxyl – soil drenching
 Benalaxyl – potato blight
 Oxadixyl –with mancozeb to control potato blight
Carbamates
 Prothiocarb – ornamentals
 Propamocarb – Fruits and vegetables
 Cymaxanil – Potatoes and vines
Miscellaneous compounds
Isoprothiolane – systemic fungicide against rice blast
Dithiolane
Formaldehyde (Formalin 40 %) is used as seed dressing and soil
sterilant
Substituted
azepenes – systemic fungicidal activity against leaf spot, powdery mildew
and rust diseases.
Recent potent fungicides for future use
Chlorooximes
Very effective broad spectrum fungicide. Substitutients in the oxime moiety plays a key
role in the biological activity.
Cyano-oximes : The most active compound in this group is Cymoxanil which controls
grape vine downy mildew disease. The analogous compound a propargyll derivative, is

155 AgriMoon.Com
Manures Fertilizers & Agrochemicals

equally effective. After isosteric replacement of the acetylenic triple bond by the cyanide
triple bond the resulting compound showed enhanced activity against downy mildew
Aryl sulfonylallyl trichloromethyl sulfoxides : A series of 2-aryl sulfonylallyl
trichloromethyl sulfoxides , have been found effective as broad spectrum fungicides with
residual activity against grape downy mildew
CH2 0
II

ArSO2C - CH2 - S – CCl3

β methoxyacrylates with oxime ether side chain:

Azoxystrobin, is a well known broad spectrum fungicide which facilitates the control
of a wide range of major plant pathogens. If the central pyrimidine ring is replaced with
an oxime ether moiety, it yields a highly effective fungicide.Analogous compounds
containing a heterocyclic moiety instead of phenyl ring were also prepared to ascertain
the fungicidal activity.
Pyrimidine derivatives: A series of novel 2-anilinopyrimidine compounds, based on
lead compound were synthesized and introduced to the market in 1994. The synthetic
compound mepanipyrim, exhibited excellent activity against grey mould of vine and veg-
etables, scab of apple and pear and brown rot of peach.
Biofungicides

These comprise of antibiotics and a few microbes such as Pseudomonas cepacia,

Peniophora gigantea and Trichoderma viride which control a number of fungi associated
with major crops
Mode of action of fungicides
Non systemic

The toxic action of sulphur in the cell is still not clear, however, several theories have
been proposed from time to time. The theory accepted at present is that sulphur acts as
hydrogen acceptor in metabolic systems to form H2S, and in doing so disrupts the
normal hydrogenation and dehydrogenation reactions in the cell. But in case of Cu-
fungicides, the Cu ions precipitate or inactivate the proteins (enzymes of sulphydryl
group) and thus kill the spores.
The mercury fungicides also act either as vapour or in ionic form and destroy

156 AgriMoon.Com
Manures Fertilizers & Agrochemicals

sulphydryl group of (.SH) enzymes. Organomercurials are more toxic than the inorganic
mercuric ones due to enhanced lipid solubility facilitating diffusion through the spore
membrane to the site of action.
The mode of action of quinone derivatives may be due to binding of the quinone
nucleus to .SH and -NH2 groups in the cell leading to disturbance in the electronic
transport systems. The activity of captan and related analogues may thus involve the
role of CI and S atoms of the molecule leading to inactivation of sulphydryl group of
enzymes.
b) Systemic

The general mode of action of systemic fungicides is associated with a) interference

with the electron transport chain influencing the energy budget of the cell, b)
reduction in the biosynthesis of new cell material required for growth and development of
the organism, and c) disruption of cell structure and permeability of cell membrane.
Benomyl and its related compounds interfere with mitosis in cell division in
angiosperms and fungi. Benzimidazoles, thiophanates, oxathins, phenylamides
(metalaxyl derivatives) influence DNA synthesis and are also mitosis inhibitors. The
triazole group of fungicides interfere with the biosynthesis of fungal steroids and
ergosterol which are important constitutents of the cell wall. Pyrimidine derivatives
inhibit purine biosynthesis and several pyridoxal dependent enzymes. The mode of

R4Sn - R3SnX - R2SnX2 - RSnX3 - SnX.

action of morpho lines is still not well understood but appears to be inhibition of sterol
biosynthesis. The mode of action of organ phosphorus fungicides is different from
insecticides due to the absence of cholinesterase enzyme in fungi. The widely
accepted theory is that it inhibits permeation through cytoplasmic membrane of the
substrates for chitin synthesis.
The thiono compounds appear to be inactive against fungi and this may be due to
fungus being unable to activate the thiono group to the ox on form by oxidation. The
effect of penetration into the fungal hyphae depends on the polarity of the P=O group
and needs to be balanced by a larger liphophilic group such as, the second thiophenyl
group in case of edifenphos, cyclohexyl group in case of cerezin, benzyl mercaptan in
case of kitazin or kitazin-P and the phenyl radical in the case of inezin.
Metabolism
The stability of fungicides in soil depends on chemical structure, nature of soil and
climatic conditions. In general, the fungicides are not as stable as organochlorine

157 AgriMoon.Com
Manures Fertilizers & Agrochemicals

insecticides. The most versatile dithiocarbamate group of compounds, decompose in

acidic soils to give non-toxic amines and carbon disulfide. Metabolism of alkyltin
compounds in liver microsomal monooxygenase system and in mammals leads to the
following sequence of detannylation (carbon-tin cleavage) reaction
The first step reaction product possessed increased toxicity and potency as inhibitors
to mitochondrial respiration whereas in the subsequent steps the reaction product
possesses less potency and has altered nature of biocidal activity.
The carboximides such as captan, folpet, captafol are hydrolysed under neutral and
alkaline conditions. Chloroneb degrades to the phenolic derivative but reconversion to
parent molecule is a microbial process and this might be the probable reason for long
term effectiveness of chloroneb in soil.
Benzimidazole systemic fungicides like benomyl, thiabendazole and thiophanate
methyl are first converted to carbendazim, an active ingredient at the site of action.
These are finally degraded to non toxic compounds such as aniline, phenyl diamine and
cyanoaniline. The breakdown of benomyl into MBC occurs by intramolecular process in
slightly acidic or neutral media. A hydrogen bond is formed between the free electron
pair of the N atom of the benzimidazole ring and hydrogen on the nitrogen of the
butylcarbamoyl side chain, forming an unstable four membered ring which opens up to
yield MBC and butylisocyanate. The cyanate rapidly forms butylcarbamic acid with water
which in turn decomposes into CO2 and butylamine. The major metabolites of
dimethirimol are ethirimol and 2-amino derivative.

Benomyl and thiophanate-methyl, in plants decomposes first to MBC which then

gives photoproducts) like carbomethoxyguanidine (i), carbomethoxyurea (ii) and
guanidine (iii)other minor compounds depending on the nature of the solvents used
Piperazine, a metabolite of the fungicide triforine in barley degraded to non toxic
products such as iminodiacetic acid, glycine, and oxalic acid on the surface of the plants
by photodecomposition Chlorthalonil, 2,4,5,6-tetrachloroisophthalonitrile, in benzene
solvent was photodegraded to amonophenyl adduct 3,5,6-trichlorobiphenyl-2, 4-
dicarbonitrile, (i) as major photoproduct and disulfides. chlorophenyl methyl carbonate
and an unknown product.
R
.
S
n

158 ~ AgriMoon.Com

R
Manures Fertilizers & Agrochemicals

32.Insecticide act-Compatibility of pesticides with fertilizers and other

Agrochemicals.

Agrochemicals combinations and their significance

Fertilizer-herbicide combinations are extremely popular because they combine two

operations. Combinations with pre emergence chemicals are generally effective since
both fertilizer and herbicide action are dependent on contact with the soil (requiring
rainfall or irrigation). Post emergence herbicide action depends more on absorption by
leaves, and granules in such combinations do not adhere well to smooth-surfaced
leaves. They will stick better if applied when weed leaves are damp, perhaps with
morning dew. “Weed and feed” materials present a conflict in desirable actions. Proper
time for weed control often does not coincide with the most desirable time and rates for
fertilizing. If used for follow-up fertilizations, there is danger of herbicide overdose.

HERBICIDE - INSECTICIDE COMBINATIONS

Emulsifiable concentrate formulations of insecticides can act like oil adjuvants when
applied in combination with a herbicide. Past research has demonstrated that Lorsban in
combination with Betanex or Betamix can cause more sugar beet injury than Betanex or
Betamix alone. Lorsban should not be applied in combination with normal rates of
Betanex, Betamix or Betamix Progress in situations where sugarbeet injury is a concern.
The micro rate of Betanex or Betamix + UpBeet + Stinger + methylated seed oil at 0.5
pt/A + 1/8 oz/A + 1.3 fl oz/A + 1.5% v/v already has an oil adjuvant as a part of the
system. Therefore, the addition of Lorsban to the micro rate would not be expected to
cause an increase in sugarbeet injury.

While Lorsban act like oil adjuvants, the insecticides are not as effective as
commercial oil adjuvants and the insecticides should not be substituted for oil adjuvants
in herbicide treatments where oil adjuvants are needed for optimum weed control.
Adjuvants for enhancing herbicide performance
An adjuvant is any substance in a herbicide formulation or added to the spray tank to
improve herbicidal activity or application characteristics.
Adjuvant selection: should be primarily based on herbicide label._ should consider
percent active ingredient as well as cost.

159 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Adjuvants are commonly used in agriculture to improve the performance of pesticides.

Broadly defined, “an adjuvant is an ingredient that aids or modifies the action of the
principal a ctive ingredient.” The use of adjuvants with agricultural chemicals generally
falls into two categories: (1) formulation adjuvants are present in the container when
purchased by the dealer or grower; and
(2) spray adjuvants are added alongwith the formulated product to a carrier such as
water. The liquid that is sprayed over the top of a crop, weeds, or insect pest often will
contain both formulation and spray adjuvants.
Formulation adjuvants are added to the active ingredient fora number of reasons
including better mixing and handling,increased effectiveness and safety, better
distribution, and drift reduction. These traits are accomplished by altering the solubility,
volatility, specific gravity, corrosiveness, shelflife, compatibility, or spreading and
penetration characteristics .With the large number of formulation options
available(solutions, emulsions, wettable powders, flowables, granules,and encapsulated
materials), adjuvants become even morei mportant in assuring consistent performance.
Spray adjuvants are added to the tank to improve pesticide performance. Literally
hundreds of chemical additives are now available that fall into this category. Spray
additives canbe grouped into two broad categories:
Activator Adjuvant s include surfactants, wetting agents, stickers-spreaders, and
penetrants; special purpose or utility modifiers such asemulsifiers, dispersants,
stabilizing agents, coupling agents,co-solvents, compatibility agents, buffering agents,
antifoamagents, drift control agents, and nutritionals.
SPECIAL PURPOSE ADJUVANTS
Compatibility agents allow simultaneous application of two
or more ingredients. They are most often used when herbicides are applied in liquid
fertilizer solutions. Unless the pesticide label states that it can be mixed with liquid
fertilizers,a compatibility agent should be included.
Buffering agents usually contain a phosphate salt or more
recently citric acid, which maintains a slightly acid pH whenadded to alkaline waters.
These are added to higher pHsolutions to prevent alkaline hydrolysis (a chemical
reaction)of some organophosphate (OP) and carbamate insecticides.Some acidifying
agents are also sold to enhance herbicideuptake and performance. However, there is
little evidence tosupport the need for these acidifying agents for this purposewith most
herbicides. Some buffering agents are also “water softening” agents that are used to

160 AgriMoon.Com
Manures Fertilizers & Agrochemicals

reduce problems with hardwater. In particular, calcium and magnesium salts

mayinterfere with the performance of certain pesticides. Ammonium
sulfate (AMS) is sometimes added to reduce hard water
problems. Examine the specific pesticide and water source todetermine the need for a
buffering agent.
Antifoam agents usually are added to suppress surface foamand minimize air
entrapment that can cause pump and sprayproblems. Defoamers often contain silicone.
Drift control agents (thickeners) modify spray characteristicsto reduce spray drift,
usually by minimizing small dropletformation. Drift inhibitors are generally polyacrylamide
orpolyvinyl polymers to increase droplet size.
Surfactants
The primary purpose of a surfactant or “surface active agent”is to reduce the surface
tension of the spray solution to allow more intimate contact between the spray droplet
and the plant surface. Any substance that brings a pesticide into closer contact with the
leaf surface has the potential to aid absorption. Surface tension is a measure of the
surface
energy in terms of force measured in dynes/cm. Water has asurface tension of 73
dynes/cm. Surfactants lower the surfacetension of water to that of an oil or solvent,
which spreadsmore readily than water on plant surfaces. Surfactants typically lower the
surface tension of a solution to between30 and 50 dynes/cm.The interaction between
surfactant, herbicide, and plant surface is far more complex than simply lowering the
surface tension of the pesticide solution. Surfactant molecules maya lso alter the
permeability of the cuticle. Surfactants form abridge between unlike chemicals such as
oil and water or
water and the wax on a leaf surface. Although there are manyd ifferent types of
surfactants, in general, they are constructed of a long chain hydrocarbon group on one
end that is considered lipophilic (fat loving) and a more hydrophilic(water loving) group of
atoms on the other end.
Surfactants are classified as nonionic, anionic, or cationic.
Nonionic surfactants have no electrical charge and are
generally compatible with most pesticides. Nonionic
surfactants are most commonly used because of their
universal fit. An anionic surfactant possesses a negatively
charged functional group and is most often used with acids
or salts. Anionic surfactants are more specialized and

161 AgriMoon.Com
Manures Fertilizers & Agrochemicals

sometimes used as dispersants or compatibility agents.

Cationic surfactants are used less frequently, but one group
(ethoxylated fatty amines) has been frequently used with theherbicide Roundup.
The organosilicone-based materials are another group of
surfactants more recently introduced. These surfactants are
used in place of or in addition to more traditional nonionic
surfactants. Proponents of these surfactants stress low
surface tension, greater rain fastness, and possible stomatal
penetration characteristics. Several silicone-based products
are currently available for use with postemergence herbicides
Oils
Adjuvants that are primarily oil based are very popular with
pesticide applicators. Crop oils are probably the oldest groupwithin this category.Crop oil
is a misnomer because the material actually is from petroleum (paraffin or naphtha base,
not vegetable derivative),a phytobland onphytotoxic), . Crop oils are believed to promote
the penetration of pesticide spray through waxy cuticle or the tough chitinous shell of
insects. Traditional crop oils are more commonly used in insect and disease control than
with herbicides. Crop oils are typically used at 1 to 2 gallons peracre.
Crop oil concentrate contains 80 to 85 percent phytobland
emulsifiable crop oil (petroleum based) plus 15 to 20 percent nonionic surfactant. The
purpose of the surfactant in this mixture is to emulsify the oil in the spray solution and
lower the surface tension of the overall spray solution. Crop oil concentrates attempt to
provide the penetration characteristics of the oil, while capturing the surface tension
reduction qualities of a surfactant. Crop oil concentrates are also important in helping
solubilize less water-soluble herbicides such as Assure, Poast, Fusilade, Select, and
atrazine on the leaf surface.
Vegetable oil concentrates have performed less consistently than their petroleum-
based counterparts. However, manufacturers are attempting to improve plant or
vegetable-based oils by increasing their non polar or lipophilic characteristics. The most
common method has been through esterification ofcommon seed oils such as
methylated sunflower, soybean,cotton, and linseed oils. The methylated forms of these
seed oil concentrates are comparable in performance to traditional(petroleum) crop oil
concentrates so their importance has increased. In taking it one step further,
organosilicone-basedmethylated vegetable oil concentrates are also available. These
adjuvants boast the surface tension-reducing properties

162 AgriMoon.Com
Manures Fertilizers & Agrochemicals

of silicone but have the advantages of a methylated

vegetable oil concentrate.
Nitrogen Fertilizer
Within the last 15 years, nitrogen fertilizers have been more
frequently added to the spray solution as an adjuvant to
increase herbicide activity. Ammonium salts (NH4+) appear to be the active component
of these fertilizer solutions and have improved the performance consistency on some
weeds. It is still unclear how ammonium salts improve herbicide performance.
Herbicides that appear to benefit from the addition of ammonium are the relatively polar,
weak acid herbicides such as Basagran, the sulfonylureas (Accent,Beacon, Classic, and
Pinnacle, etc.), and the imidazolinones(Pursuit and Raptor). Nitrogen fertilizers may
replace surfactant or crop oil concentrate with some of the contact type herbicides, but
are usually added in addition to surfactant or crop oil concentrate with systemic
products. Velvetleaf and some grassy annual weeds in particular have been responsive
to the addition of nitrogen fertilizer in the spray mix. In general, velvetleaf control has
improved by as much as 10 to 25 percent by the addition of an ammonium based fluid
fertilizer compared to crop oil concentrate or surfactant. Some broadleaves and grasses
show little or no response with the inclusion of ammonium fertilizer solutions.
Ammonium-based fertilizers and, in particular, ammonium sulfate (AMS) are also being
promoted to reduce potential antagonism with hard water or antagonism with other
pesticides. Both hard water antagonism and pesticide antagonism can occur with some
herbicides. Roundup(glyphosate) is one product that specifically recommends omits
label the addition of ammonium sulfate (or a higher rateof Roundup) for hard water, cool
air temperatures, or drought conditions. Examine the specific pesticide label,water
source, and environmental conditions to determine the need for AMS or other adjuvants.

Foliar fertilizers

Many of these products are being used extensively in combination with herbicides. It is
important to know the facts before mixing them unregistered with herbicides.

• Certain fertilisers do work effectively with certain herbicides for very specific
reasons. It is however highly improbable that it is as a result of more actively
growing plants.

163 AgriMoon.Com
Manures Fertilizers & Agrochemicals

• Foliar fertilisers could sometimes even be antagonistic to herbicide activity!

Certain companies even warn farmers not to mix these products with their
herbicides.
• If you mix unregistered combinations, please keep in mind that it becomes your
problem and that the herbicide company will not take responsibility for poor weed
control or crop damage. Unregistered combinations are a risk that you take. We
don't think it worthwhile to take such a risk.

Tank mixtures

Unregistered tank mixtures are one of the main reasons for poor herbicide efficacy. It is
important to keep the following in mind.

• Always stick to label recommendations

• If in doubt, contact the manufacturer for advice

Conditions during and just after spraying

Climatic conditions during application could make or break a herbicide.

• Remember that once the spray solution droplet hits the target, it is exposed to
the forces of nature. Try to protect it in every way possible.
• Try to avoid herbicide-limiting factors such as low humidity and other
environmental constraints.
• Always include the registered adjuvant as it can compensate somewhat for lower
humidity and other environmental limitations.

Retention and absorption

It is important for spray solution droplets to firstly be retained on the leaf surface and
then to be absorbed in adequate amounts.

• Remember that both retention and absorption are equally as important. Good
wetting and spreading is useless if conditions for absorption are unfavourable.
• Try to avoid herbicide-limiting factors such as low humidity and other
environmental constraints as this could detrimentally influence both retention and
absorption.

164 AgriMoon.Com
Manures Fertilizers & Agrochemicals

• Always include the registered adjuvant as it ensures adequate retention and

absorption.
• Don't follow unregistered practices as this could decrease both retention and
absorption.

HERBICIDEMIXTURES AND PROBLEMS IN

MIXING HERBICIDES
The use of herbicide combinations is not new, but it has
not received the attention and input that is necessary to fully understand and implement
the practice. Although the number of herbicides available is continually increasing, we
have to realize that in most cases herbicides are quite specific in their activity toward
either grass or broadleaf weeds and even other species within these broad categories.
Excellent herbicides have limitations that might be alleviated with the proper addition of
another herbicide.
There are several advantages that may be gained from
the combination of herbicides over a single herbicide.
Some of these are:
1. Control of a broader spectrum of weeds.
2. More consistent control over a wide range of climatic
conditions.
3. Reduced potential of herbicide residue in crops and soils.
4. Lower rates of application resulting in decreased crop
injury and lower costs.
5. Unexpected synergistic effects (increased herbicidal
effectiveness beyond that expected).
There have been limitations and concern in the past
concerning the legal use of herbicide combinations. At no
time has the University of Wyoming recommended
chemical mixtures unless the herbicides, herbicide-fertilizer
mixtures, and other pesticides were registered by the
Environmental Protection Agency (EPA) and the state of
Wyoming.
EPA's policy on herbicides and herbicide-fertilizer
mixtures is as follows:
1. An herbicide or mixture of herbicides may be mixed

165 AgriMoon.Com
Manures Fertilizers & Agrochemicals

with other pesticides and/or with fertilizers if the mixture is

not prohibited by the labeling.
2. Two or more herbicides and/or pesticides may be mixed
if all the dosages are at or below the recommended label
rate.
When making such mixtures it must kept in mind that
these pesticide mixtures are applied at the applicator's own
risk with respect to effects on crops, application equipment,
applicator safety, environmental effects and residue tolerance.
MIXING HERBICIDES
Always be sure the sprayer has been properlycalibrated. Calculate the amount herbicide
to add to thesprayer tank based on the active material in each gallon ofherbicide
concentrate, or the percentage of active ingredientof dry herbicide formulation. Always
read and follow the instructions on the manufacture's label pertaining to
personal hazards in handling.
The following steps should be taken when mixing
herbicides:
1. Fill the sprayer tank with at least half the volume of wateror fertilizer solution you will
ultimately need.
2. Start continuous moderate agitation.
3. Add compatibility agents if needed. For maximum
benefit, they must be in solution before herbicides are
added.
4. Add, mix, and disperse dry herbicides (wettable powders,dry flowables, or water
dispersible granules). Theseformulations contain wetting and dispersing agents that
aidin mixing.
5. Add liquid flowables and allow thorough mixing. These
also contain wetting and dispersing agents.
6. Add emulsifiable concentrates (EC's) and allow thorough
mixing.
7. Finish by adding water soluble formulations (2,4-D
amine, etc.).
8. Add any surfactants, crop oil concentrates, etc. last.
Crop oils, especially, do not mix and disperse well if added
first.

166 AgriMoon.Com
Manures Fertilizers & Agrochemicals

9. Add remainder of water or liquid fertilizer and maintain

agitation while spraying until tank is empty.
Never pour concentrated herbicides into an empty tank.
Never allow a sprayer containing mixed chemicals to stand
without agitation, as heavy wettable powders may clog
nozzles or settle into corners of the spray tank. Wettable powder herbicides should be
pre-slurried before addition to a spray tank. Adding the wettable
powder directly to the spray tank can result in globs or
unwetted material in the tank where it can clog spray
equipment. This is particularly a problem with the more
finely ground wettable powders.
Tank mixtures of a wettable powder and an emulsifiable concentrate can cause
problems if not properly
mixed. The proper procedure is to first pre-slurry the
wettable powder and add it to the tank 3/4 full of water.
The emulsifiable concentrate should then be added followed by the necessary water to
fill the tank. If the sequence is reversed with the wettable powder added last, problems
can arise.
FERTILIZER AND HERBICIDEMIXTURES
The mixing of liquid fertilizers and pesticides and applying at the same time has several
advantages. The mixture can save time, labor, fuel, and may help reduce soil
compaction.
There could be mixtures of a herbicide + fertilizer =
"weed + feed"; fertilizer + insecticide = "feed and worm";
herbicide + insecticide = "weed + worm". The following
material will only be concerned with the "weed + feed"
concept of mixing herbicides with liquid fertilizers.
Even before checking the compatibility of herbicide +
fertilizer mixtures, other factors of importance must be
taken into consideration.
1. Do you have the right equipment for application?
Fertilizer application is not as exacting as for applying
herbicides.
Uniform application covering every square inch
is essential for the effectiveness of herbicides.

167 AgriMoon.Com
Manures Fertilizers & Agrochemicals

The equipment ordinarily used for applying fertilizers does not give the uniform
distribution pattern that equipment used for herbicide application provides.
Some fertilizer application equipment does not have the
agitation necessary to keep herbicides uniformly dispersed.
Herbicide application equipment may not be able to
withstand the weight and corrosiveness of liquid fertilizers
nor apply the necessary volume of liquid fertilizer.
2. Are mixtures of herbicides and fertilizer practical? The
applicator must determine if the timing of application,
placement and distribution of each component in the
mixture are similar enough to be applied as a mixture.
Several herbicides and fertilizers can be applied at the
same time. For example, AAtrex (atrazine) can be tank
mixed with liquid fertilizer and applied to corn either
preplant incorporated or broadcast on the soil surface after
the corn is planted but before the crop emerges. Placement
of the mixture may raise a question of practicality. Suppose
a farm operator sprays the herbicide and fertilizer mix over
the corn row, in a band, at planting time. By using a
nitrogen solution as a carrier for the herbicide the nitrate
form of nitrogen will be incorporated by rainfall. If the
ammonium (NH4) form of nitrogen is used as a carrier and
soil surface applied, it will react with the soil particles and
be held in the top 1/4 inch of soil. This nitrogen will move
downward only after being converted to the nitrate form. If
the fertilizer carrier for the herbicide is a solution
containing nitrogen and phosphorus it will have to be
positioned in the soil near the roots for plants to adequately
utilize it as phosphorus does not move readily in most soils.
If the nitrogen and phosphorus fertilizer solution is banded
over the corn at planting time, the corn will not benefit fromthe phosphorus as a starter in
early plant growth. Thus, thiscombination would not be practical from a placement
standpoint.
3. Distribution of the mixture. Liquid fertilizers are usually
broadcast over the entire field. Applying the herbicide in

168 AgriMoon.Com
Manures Fertilizers & Agrochemicals

with the fertilizer means broadcasting of the herbicide also.

Many herbicides can be band applied, a practice which
reduces the total cost of the herbicide per acre in proportion
to the row-spacing and width of the band treated.
Therefore, the total benefits and economics of mixing
should be taken into consideration.
4. Is the fertilizer-herbicide mixture compatible?
Herbicides may not always mix evenly throughout the liquid fertilizer or the components
may separate making their use impractical. A simple test should be used before mixing
large quantities.
COMPATIBILITY
Even though guidelines have been presented with respect to tank mixes there still
remains the question of compatibility when mixing two or more chemicals,especially,
when directions for mixing and application are not included on the label.
Both chemical and physical incompatibility are possible. With chemical incompatibility
the chemical maybe completely deactivated, resulting in no weed control, or
the chemical might be made highly phytotoxic resulting in
damage to the crop. It is also possible to change the
mammalian toxicity making a normally safe chemical highlytoxic.
Physical incompatibility is most commonly evidenced
by precipitation in the spray solution which takes the form
of crystalline solids, formation of a gelatinous mass, or
separation of components which takes the form of layering.
Lack of compatibility may only result in the formation of a
substance that plugs up screens and nozzles, however,
extreme incompatibility may produce a settling out of
material that can harden like concrete in the bottom of a
tank and in hoses, pumps, and other internal parts of the
sprayer. The result may be total loss of the pesticide and
use of the sprayer.
Chemical compatibility of a mixture is impossible to
determine without extensive research being conducted,
whereas physical compatibility can easily be checked.
You should use only labeled tank mixtures or mixtures
recommended by experienced scientists whose

169 AgriMoon.Com
Manures Fertilizers & Agrochemicals

recommendations are backed by research. For all unlabeled

tank mixtures, a jar test is strongly recommended to test for
the compatibility of herbicide-herbicide mixtures,
herbicide-insecticide mixtures, herbicide -fertilizer mixtures,or any combinations
involving pesticides and/or fertilizers.
In some cases, adding a compatibility agent (Complex, Unite, or comparable
surfactants) may aid in maintaining
component dispersion.
JAR TEST FOR COMPATIBILITY
The jar test may be used to test the compatibility
of herbicides with each other or herbicides and other
pesticides with liquid fertilizers.
1. Add 1 pint of carrier (water, liquid fertilizer) each to two
quart jars. Mark the jars with an identifiable letter, number
or other means. Usually "with" and "without" is the most
practical (representing with and without compatibility
agent).
2. Add 1/4 teaspoon or 1.2 ml of compatibility agent to one
jar (equivalent to 2 pints per 100 gallons of spray solution).
3. To each jar add the required amount of pesticide in the
order suggested in the section on mixing herbicides Shake well after each pesticide
addition to simulate continuous agitation.
4. When all ingredients are added, shake both jars for 15
seconds and let stand for 30 minutes or longer. Then
inspect the mixture for flakes, sludge, gels, or non dispersible oils, all of which may
indicate incompatibility.
If, after standing 30 minutes, the components in the jar
with no compatibility agent are dispersed, the herbicides are compatible and no
compatibility agent is needed.
If the components are dispersed only in the jar
containing the compatibility agent, the herbicide is
compatible only if a compatibility agent is added.
If the components are not dispersed in either jar, the
herbicide-carrier mixture is not compatible and should not
be used.

170 AgriMoon.Com
Manures Fertilizers & Agrochemicals

33. Fate of pesticides in soil and plant.

What Happens to Pesticides

When a pesticide is released into the environment many things happen to it. Sometimes
what happens is beneficial. For example, the leaching of some herbicides into the root
zone can give you better weed control.

Sometimes, releasing pesticides into the environment can be harmful, as not all of the
applied chemical reaches the target site. For example, runoff can move a herbicide away
from target weeds. The chemical is wasted, weed control is reduced, and there is more
chance of damaging other plants and polluting soil and water. Or some of the pesticide
may drift downwind and outside of the intended application site.

Many processes affect what happens to pesticides in the environment. These processes
include adsorption, transfer, breakdown and degradation. Transfer includes processes
that move the pesticide away from the target site. These include volatilization, spray drift,
runoff, leaching, absorption and crop removal.

Each of these processes is explained in the following sections.

Transfer Processes

Adsorption is the binding of pesticides to soil particles. The amount a pesticide

is adsorbed to the soil varies with the type of pesticide, soil, moisture, soil pH,
and soil texture. Pesticides are strongly adsorbed to soils that are high in clay or
organic matter. They are not as strongly adsorbed to sandy soils.

Most soil-bound pesticides are less likely to give off vapours or leach through the
soil. They are also less easily taken up by plants. For this reason you may
require the higher rate listed on the pesticide label for soils high in clay or organic
matter.

171 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Volatilization is the process of solids or liquids converting into a gas, which can
move away from the initial application site. This movement is called vapour drift.
Vapour drift from some herbicides can damage nearby crops.

Pesticides volatize most readily from sandy and wet soils. Hot, dry, or windy
weather and small spray drops increase volatilization.

Where recommended, incorporating the pesticide into the soil can help reduce
volatilization.

Spray Drift is the airborne movement of spray droplets away from a treatment
site during application.

Spray drift is affected by:

 spray droplet size - the smaller the droplets, the more likely they will drift
 wind speed - the stronger the wind, the more pesticide spray will drift
 distance between nozzle and target plant or ground - the greater the
distance, the more the wind can affect the spray

Drift can damage nearby sensitive crops or can contaminate crops ready to
harvest. Drift may also be a hazard to people, domestic animals, or pollinating
insects. Drift can contaminate water in ponds, streams, and ditches and harm
fish or other aquatic plants and animals. Excessive drift also reduces the
pesticide applied to the target and can reduce the effectiveness of a treatment.

Runoff is the movement of pesticides in water over a sloping surface. The

pesticides are either mixed in the water or bound to eroding soil. Runoff can also
occur when water is added to a field faster than it can be absorbed into the soil.
Pesticides may move with runoff as compounds dissolved in the water or
attached to soil particles.

The amount of pesticide runoff depends on:

 the slope
 the texture of the soil
 the soil moisture content
 the amount and timing of a rain-event (irrigation or rainfall)
 the type of pesticide used

Runoff from areas treated with pesticides can pollute streams, ponds, lakes, and
wells. Pesticide residues in surface water can harm plants and animals and
contaminate groundwater. Water contamination can affect livestock and crops
downstream.

Pesticide runoff can be reduced by:

172 AgriMoon.Com
Manures Fertilizers & Agrochemicals

 using minimum tillage techniques to reduce soil erosion

 grading surface to reduce slopes
 diking to contain runoff
 leaving border vegetation and plant cover to contain runoff

Pesticide losses from runoff are greatest when it rains heavily right after you
spray. Reduce the chances of runoff by watching the weather forecast. If heavy
rain is expected, delay spraying to avoid runoff. Irrigate according to label
instructions.

Leaching is the movement of pesticides in water through the soil. Leaching

occurs downward, upward, or sideways. The factors influencing whether
pesticides will be leached into groundwater include characteristics of the soil and
pesticide, and their interaction with water from a rain-event such as irrigation or
rainfall. These factors are summarized in the table below.

Leaching can be increased when:

 the pesticide is water soluble

 the soil is sandy
 a rain-event occurs shortly after spraying
 the pesticide is not strongly adsorbed to the soil

Groundwater may be contaminated if pesticides leach from treated fields, mixing

sites, washing sites, or waste disposal areas.

Summary of Groundwater Contamination Potential as Influenced

by Water, Pesticide and Soil Characteristics

Risk of Groundwater Contamination

Low risk High risk

Pesticide characteristics

Water solubility low high

Soil adsorption high low

Persistence low high

Soil characteristics

Texture fine clay coarse sand

Organic matter high low

173 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Macropores few, small many, large

Depth to groundwater deep shallow

(100 ft or more) (20 ft or less)

Water volume

Rain/irrigation small volumes at infrequent large volumes at frequent

intervals intervals

Based on: McBride, D. K. 1989. Managing pesticides to prevent groundwater

contamination. North Dakota State University Extension Service, Publication E-979.

Similar factors influence pesticide movement in surface runoff, except that

pesticides with low water solubility may move with surface runoff if they are
strongly adsorbed to soil particles and have some degree of persistence.

Soil characteristics are important to pesticide movement. Clay soils have a high
capacity to adsorb many chemicals including pesticides and soil nutrients. Sandy
soils have a much lower capacity to adsorb pesticides. Organic matter in the soil
also can adsorb pesticides. Soil structure influences the movement of water and
pesticides. Coarse textured sandy soils with large air spaces allow more rapid
movement of water than fine textured or compacted soils with fewer air spaces.
Other characteristics of the site, such as depth to groundwater, or distance to
surface water, are important. Finally, the pattern of water falling on the soil
through irrigation or rainfall is significant. Small volumes of water at infrequent
intervals are less likely to move pesticides than large volumes of water at more
frequent intervals.

Absorption is the uptake of pesticides and other chemicals into plants or

microorganisms. Most pesticides break down once they are absorbed. Pesticide
residues may be broken down or remain inside the plant or animal and be
released back into the environment when the animal dies or as the plant decays.

Some pesticides stay in the soil long enough to be absorbed by plants grown in a
field years later. They may damage or leave residues in future crops.

Crop Removal through harvest or grazing may remove pesticide residues.

Degradation or Breakdown Processes

Degradation is the process of pesticide breakdown after application. Pesticides

are broken down by microbes, chemical reactions, and light or photodegradation.
This process may take anywhere from hours or days to years, depending on
environmental conditions and the chemical characteristics of the pesticide.
Pesticides that break down quickly generally do not persist in the environment or
on the crop. However pesticides that break down too rapidly may only provide
short-term control.

174 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Microbial breakdown is the breakdown of chemicals by microorganisms such

as fungi and bacteria.

Microbial breakdown tends to increase when:

 temperatures are warm

 soil pH is favourable
 soil moisture and oxygen are adequate
 soil fertility is good

Chemical breakdown is the breakdown of pesticides by chemical reactions in

the soil. The rate and type of chemical reactions that occur are influenced by:

 the binding of pesticides to the soil

 soil temperatures
 pH levels - Many pesticides, especially the organophosphate insecticides,
break down more rapidly in alkaline soils or in spray tank water with a high
pH level.
 moisture

Photodegradation is the breakdown of pesticides by sunlight. All pesticides are

susceptible to photodegradation to some extent. The rate of breakdown is
influenced by the intensity and spectrum of sunlight, length of exposure, and the
properties of the pesticide. Pesticides applied to foliage are more exposed to
sunlight than pesticides that are incorporated into the soil. Pesticides may break
down faster inside plastic-covered greenhouses than inside glass greenhouses,
since glass filters out much of the ultraviolet light that degrades pesticides.

Top
Pesticide Characteristics

From University of Nebraska NebGuide G1182

Pesticide characteristics are also important in determining the fate of the chemicals in
the environment. These characteristics include:

1. solubility in water (water solubility)

2. tendency to adsorb to the soil (soil adsorption)
3. pesticide persistence in the environment (half-life)

Pesticides with high water solubility, low tendency to adsorb to soil particles and long
persistence or half-life have the highest potential to move into water. These three
factors, soil adsorption, water solubility and persistence, are commonly used to rate
pesticides for their potential to leach or move with surface runoff after application.

175 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Soil adsorption is measured by Koc, which is the tendency of pesticides to be attached to

soil particles. Higher values (greater than 1000) indicate a pesticide that is very strongly
attached to soil and is less likely to move unless soil erosion occurs. Lower values (less
than 300-500) indicate pesticides that tend to move with water and have the potential to
leach or move with surface runoff.

Water solubility is measured in parts per million (ppm) and measures how easily a
pesticide may be washed off the crop, leach into the soil or move with surface runoff.
Pesticides with solubilities of less than 1 ppm tend to remain on the soil surface. They
tend not to be leached, but may move with soil sediment in surface runoff if soil erosion
occurs. Pesticides with solubilities greater than 30 ppm are more likely to move with
water.

Pesticide persistence is measured in terms of the half-life, or the time in days required
for a pesticide to degrade in soil to one-half its original amount. For example, if a
pesticide has a half-life of 15 days, 50 percent of the pesticide applied will still be present
15 days after application and half of that amount (25 percent of the original) will be
present after 30 days. In general, the longer the half-life, the greater the potential for
pesticide movement. A pesticide with a half-life greater than 21 days may persist long
enough to leach or move with surface runoff before it degrades.

No one factor--adsorption, water solubility, or persistence--can be used to predict

pesticide behavior. It is the interaction of these factors and their interaction with the
particular soil type and environmental conditions that determines pesticide behavior in
the field.

Top
Ways to Minimize Pesticide Impact

The following are several practices which reduce the potential for pesticides to cause
environmental damage or water contamination. Consider applying these practices to
your farm.

Integrated Pest Management

Follow integrated pest management (IPM) principals. IPM doesn't rely solely on
chemicals for pest control. Biological control, cultural practices, and timely
chemical applications are used to obtain the necessary level of control.
Pesticides are the last line of defense and are used only when pest levels are
causing sufficient damage to offset the expense of the application. IPM also
requires the following actions:

• Scout or monitor crops regularly to check the levels of pest populations and
their damage.
• Implement available non-chemical control practices, including mechanical,
cultural and biological controls, sanitation, and plant resistance. For
example, use crop rotation to manage corn rootworms and cut alfalfa early
to manage weevils (cultural controls); select resistant varieties (plant

176 AgriMoon.Com
Manures Fertilizers & Agrochemicals

resistance); thoroughly clean combines between fields to reduce weed seed

introductions (sanitation); and use cultivation to control weeds (mechanical
control).
• Maximize the benefits of naturally occurring biological controls by using
pesticides only when necessary and selecting pesticides which are the least
harmful to beneficials. For example, some insecticides and fungicides kill
predatory mites, which can cause a mite outbreaks later in the season.
Prevent backsiphoning and spills

Never allow a hose used for filling a spray tank to extend below the level of the
water in the tank. Contain all spills as quickly as possible and handle according
to label directions. Use anti-siphon devices in the water line. They are
inexpensive and effective. (See the Emergencies section of this website for
further spill information.)

Consider weather and irrigation plans

Application just before rainfall or irrigation may result in reduced efficacy if the
pesticide is washed off the target crop, resulting in the need to reapply the
pesticide.

Heavy rainfall may also cause pesticide-contaminated runoff at the application

site.

Pesticide use and storage

Always read and follow the label directions on the pesticide container. Use
pesticides only when economic thresholds are reached and buy only what you
need. Use appropriate protective equipment and clothing according to label
instructions. Avoid mixing pesticides near wells or other sources of water. Store
all pesticides safely, and according to legal requirements (see the Storage and
Shelf Life section of this website).

Dispose of pesticide and chemical wastes safely

Dispose of excess chemical and pesticide containers in accordance with label

directions. Triple-rinse empty pesticide containers (use this water in the spray
tank), punch holes in containers, and dispose of them at approved waste
disposal sites. (See the Pesticide and Container Disposal section of this website
for further information).

Leave buffer zones around sensitive areas

Read the pesticide label for guidance on required buffer zones around water,
buildings, wetlands, wildlife habitats and other sensitive areas.

177 AgriMoon.Com
Manures Fertilizers & Agrochemicals

Reduce off-target drift

Never begin an application when wind or temperature favors pesticide drift to an

off target area. Use appropriate spray pressure and nozzle selection to minimize
drift.

Application equipment

Maintain all application equipment in good working order and calibrate it

regularly.

Top
Summary

Many pesticides have the potential to cause harm to the environment if they are not
used safely. Minimize the potential for environmental issues by following label directions,
storing pesticides safely, and using them properly. Help keep groundwater free of
contaminants; safeguard the health of your family, neighbors, and livestock; and ensure
a clean, healthy environment by:

 Practicing Integrated Pest Management (IPM).

 Only using pesticides that are labeled for the intended crop and pest.
 Considering application site characteristics (soil texture, slope, organic matter).
 Considering the location of wells, ponds and other water bodies.
 Measuring accurately.
 Maintaining application equipment and calibrating accurately.
 Mixing and loading carefully.
 Preventing backsiphoning and spills.
 Considering the impact of weather and irrigation.
 Storing pesticides safely and securely.
 Disposing of wastes safely.
 Leaving buffer zones around sensitive areas.
 Reducing off-target drift.

178 AgriMoon.Com
Manures Fertilizers & Agrochemicals

34. Plant growth regulators

Plant hormones (phytohormones) are physiological intercellular messengers that are

needed to control the complete plant lifecycle, including germination, rooting, growth,
flowering, fruit ripening, foliage and death. In addition, plant hormones are secreted in
response to environmental factors such as abundance of nutrients, drought conditions,
light, temperature, chemical or physical stress. Hence, levels of hormones will change
over the lifespan of a plant and are dependent upon season and environment.

The term “plant growth factor” is usually employed for plant hormones or substances of
similar effect that are administered to plants. Growth factors are widely used in
industrialized agriculture to improve productivity. The application of growth factors allows
synchronization of plant development to occur. For instance, ripening tomatoes can be
controlled by setting desired atmospheric ethylene levels. Using this method, fruits that
are separated from their parent plant will still respond to growth factors; allowing
commercial plants to be ripened in storage during and after transportation. This way the
process of harvesting can be run much more efficiently. Other applications include
rooting of seedlings or the suppression of rooting with the simultaneous promotion of cell
division as required by plant cell cultures. Just like with animal hormones, plant growth
factors come in a wide variety, producing different and often antagonistic effects. In
short, the right combination of hormones is vital to achieve the desired behavioral
characteristics of cells and the productive development of plants as a whole.

Traditionally five major classes of plant hormones are listed: auxins, cytokinins,
gibberellins, abscisic acid and ethylene. However as research progresses, more active
molecules are being found and new families of regulators are emerging; one example
being polyamines such as putrescine or spermidine.
Note that this classification is based partially on the chemical structure and partially on
the commonalities of plant physiological effects that certain substances exhibit.
Members of one class may not relate from a structural point of view to another. Auxins
for instance include not only many indole 3-carboxylic acid derivatives but numerous
phenylacetic acids as well. Most cytokinins (such as zeatins) are derivatives from
adenine but still differ widely in their chemical structure. Hence, the mechanism driving
action may be different in each case and likewise each specific activity will differ also.

179 AgriMoon.Com
Manures Fertilizers & Agrochemicals

This is demonstrated by the range of optimal concentrations required for different factors
which spans many decimals (0.001 – 100 mg/L).
Auxins

Auxin is the active ingredient in most rooting mixtures. These products help the
vegetative propagation of plants. On a cellular level auxins influence cell elongation, cell
division and the formation of adventitious roots. Some auxins are active at extremely low
concentrations. Typical auxin concentration range from 0.01 to 10 mg/L.

Cytokinins
Cytokinins promote cell division, stimulate shoot proliferation, activate gene expression
and metabolic activity in general. At the same time, cytokinins inhibit root formation. This
makes cytokinins useful in culturing plant cell tissue where strong growth without root
formation is desirable. Natural cytokinin hormone levels are high during maximum
growth periods of mature plants. In addition, cytokinins slow the aging process in plants.
Concentrations of cytokinin used for horticulture vary between 0.1 to 10 mg/L

Gibberellins
Gibberellins are derivatives of gibberellic acid. They are natural plant hormones and
promote flowering, stem elongation and break dormancy of seeds. There are about 100
different gibberellins, but gibberellic acid (GA3) is the most commonly used form.
Gibberellins are fundamental to plant development especially with respect to the growth
of stems. Low levels of gibberellins will prevent plants from reaching their natural height.
Gibberellin synthesis inhibitors are extensively used in grain production to keep stems
artificially short: shorter and thicker stems provide better support and resist weather
conditions better too.
Gibberellins are particularly effective at breaking seed dormancy and at speeding
up germination. Seeds that are difficult to germinate are frequently treated with gibberillic
acid solutions

Abscisic Acid

Abscisic acid (ABA) is a plant growth inhibitor and an antagonist of gibberellins: it

induces dormancy, prevents seeds from germinating and causes abscission of leaves,
fruits, and flowers. High concentrations of abscisic acid can be induced by environmental

180 AgriMoon.Com
Manures Fertilizers & Agrochemicals

stress such as drought. Elevated levels of abscisic acid will eventually induce dormancy,
when all non-essential processes are shut down and only the essential metabolism is
maintained in guard cells

Ethylene
Ethylene is unique in that it is found only in gaseous form. It induces ripening, causes
leaves to abscess and promotes senescence. Plants often increase ethylene production
in response to stress and before death. Ethylene concentrations fluctuate with
the seasons while playing a role in inducing foliage and ripening of fruit.
Polyamines

Polyamines are unique as they are effective (and are applied) in relatively high
concentrations. Typical concentrations range from 5 to 500 mg/L. Polyamines
influence flowering and promote plant regeneration

181 AgriMoon.Com
Manures Fertilizers & Agrochemicals

REFERENCES

Bochech, K.H. 1983. Chemistry of Pesticides. John Wiley and Sons, New York.

Cremlin, R.J 1992. Agrochemicals Preparation and mode of action, Wily

publications, New Delhi.

Edwards, C.A., G.I. Veeresh and K. Kruger. 1980. Pesticide Residues in the
environment in India. University of Agrl. Sciences, Bangalore, India.

Graniti et al. 1989. Phytotoxins and plant pathogens. Springer Verlog, Berling.

Jayakumar, R and R. Jagannathan 2003.Weed Science Principles, Kalyani

Publishers, Ludhiana.

Muirhead - Thompson, R.C. 1973. Pesticides and Fresh water Fauna.

Academic Press. London.

O' Brien and Yanamoto 1983. Biochemical toxicology of insecticides. Academic

Press Inc. New York.

Handa, S.K. 1999. Principles of pesticide chemistry. Agrobios, Jodhpur.

Roy, N.K.2002. Chemistry of pesticides. CBS Publishers & distributors,Newdelhi.

1. Brady, N.C.,2002 The Nature and Properties of Soils (13th Edition) McMillan Co.,
New York. Indian Publisher – Eurasia Publishing House (P) Ltd., Ramnagar, New
Delhi – 55
2. Dilip Kumar Das. 2004. Introductory Soil Science, Kalyani Publishers, NewDelhi
3. Fundamentals of Soil Science.2009 .ISSS Publication, New Delhi.
4. Daji A.J., (1970) A Text Book of Soil Science - Asia Publishing House, Madras.
5. Biswas T.D. and Mukherjee S.K., 1987. Text Book of Soil Science–Tata McGraw
Hill Publishing Co. Ltd., New Delhi.

182 AgriMoon.Com
Manures Fertilizers & Agrochemicals

6. Jenny, H. 1941. Factors of Soil Formation - A System of Quantitative Pedology.

McGraw-Hill Book Company INC. NewYork.
7. Joffe, J.S. 1936. The ABC of Soils. Pedology Publication, New Jersy.
8. John Havlin, James Beaten, Samuel Tisdale, Werner Nelson, 2005.Soil Fertility
and Fertilizers - An Introduction to Nutrient Management. 7th Edition, Prentice
Hall. Upper Saddle River, NJ.
9. Kanwar. J.S. 1976. Soil fertility – Theory and Practice. ICAR- New Delhi.
10. Mengel, K. and E.A. Kirkby. 1987. Principles of Plant Nutrition, 4th ed.
International Potash Institute, Worblaufen-Bern, Switzerland.
11. Horst. 1995. Mineral Nutrition of Higher Plants, 2nd edition. Marschner,
Academic Press Inc. San Diego, CA.
12. Yawalkar, K.S., J.P. Agarwal and S.Bokde.1972. Manures and Fertilizers Third
revised edition Agri Horticultural Publishing House, Nagpur.
13. Cooke G.W., 1972. Fertilizers for maximizing yield, Grenada Publishing Ltd,
London.
14. Russell. E.J.1973.Soil conditions and plant growth, Tenth edition English
Language Book Society, London.
15. Westerman, R.L. (ed.) 1990. Soil Testing and Plant Analysis, 3rd. edition. Soil
Science Society of America, Inc., Madison, WI.
16. Tandon, H.L.S. 1994. Fertilizer, Organic Manures, Recyclable Wastes and
17. Biofertilizers Fertilizer Development and Consultation Organization, New Delhi

183 AgriMoon.Com
Manures Fertilizers & Agrochemicals

****** ☺******
This Book Download From e-course of ICAR
Visit for Other Agriculture books, News,
Recruitment, Information, and Events at
www.agrimoon.com
Give FeedBack & Suggestion at [email protected]

Send a Massage for daily Update of Agriculture on WhatsApp

+91-8148663744
Disclaimer:

The information on this website does not warrant or assume any legal
liability or responsibility for the accuracy, completeness or usefulness of the
courseware contents.

The contents are provided free for noncommercial purpose such as teaching,
training, research, extension and self learning.

******☺******

Connect With Us:

184 AgriMoon.Com