Chapter: Six

Fertilizer and Pesticide Industries

By: Biniyam Abera (M.Sc.)

Department of Industrial Chemistry
Block 109
 Outline
01 6.1. Introduction to Fertilizer and Pesticide Industries
02
6.2. Global production trend and consumption of Fertilizer

03 6.3. Production of Nitrogenous fertilizers

6.3.1. Urea 6.3.2. Ammonia Nitrate Production 6.3.3. Urea Ammonium
Nitrate (UAN) 6.3.4. Ammonium Sulphate

04 6.4. Phosphate Fertilizers

05 6.5. Potash Fertilizer Processing Industries and its process technol-

ogy
6.6. Pesticides and Agricultural Chemicals
06 6.6.1. Herbicides 6.6.2. Insecticides
6.6.3. Fungicides 6.6.4. Pesticide Formulation
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 Introduction
 Chemical materials developed to assist in the production of food,
feed, fiber and increase the fertility of soil include herbicides,
insecticides, fungicides, and other pesticides, plant growth regulators,
fertilizers, and animal feed supplements.
 Agricultural chemistry often aims at preserving or increasing the
fertility of soil, maintaining or improving the agricultural yield, and
improving the quality of The ideal composition of
the crop.
soil,
 25% Air,
 25 % H2O,
 45% Mineral
3
Matter
 Composition of Soils

 Minerals are solid, inorganic, chemically uniform substance

occurring naturally in the earth.
 Some common minerals for soil formation are
1. Feldspar,
2. Micas,
3. Silica,
4. Iron oxides, and
5. Calcium carbonates.

4
 Essential Nutrients of Plants

 Plants require optimal amounts of available nutrients for normal growth.

 These nutrients can come from several sources, including

 Soil organic matter

 Native soil minerals

 Organic materials that are added to the soil (animal manures,

etc.)
 Air (Example, Fixation of nitrogen by legumes), and

 Commercial fertilizers
 When a soil is not capable of supplying enough nutrients to meet
crop/plant requirements, commercial fertilizers can be added to supply the
needed nutrients.
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 Availability of soil nutrients to plants

 One of the most important functions of soil in supporting plant growth is to

provide essential plant nutrients—macronutrients and micronutrients.
 Macronutrients are those elements that occur in substantial (higher) levels
in plant biomass and fluids.
 Micronutrients are elements that are essential only at very low levels and
generally are required for the functioning of essential enzymes.
 The elements generally recognized as essential macronutrients for plants

are C, H, O, N, P, K, Ca, Mg, and S. Carbon, hydrogen, and oxygen

are obtained from the atmosphere. The other essential macronutrients
must be obtained from soil.
 Of these, N, P, and K are the most likely to be lacking and are commonly
added to soil as fertilizers.

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There are 14 mineral nutrients that have been found to be
essential for growth of most plants:
Type Examples
Macronutrients Nitrogen (N), Phosphorus (P), Potassium (K), Sulfur (S)

Micronutrients Boron (B), Chloride (Cl), Iron (Fe), Copper (Cu),

Calcium (Ca), Manganese (Mn), Magnesium (Mg),
Molybdenum (Mo), Nickel (Ni) Zinc (Zn).

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 Plant nutrient uptake
 Plants obtain nutrients by direct root contact, mass flow
(movement with water), or diffusion (random motion)
 For plants to take up nutrients they need to be:
 in the right form (soluble or weakly bound)
 in soil solution
Available nutrient forms
Positive charge Negative/neutral charge
Ammonium - NH4+ Nitrate - NO3-
Potassium - K+ Phosphate - H2PO4-, HPO4-2
Calcium - Ca+2 Sulfate - SO4-2
Magnesium - Mg+2 Chloride – Cl-
Iron – Fe+2, Fe+3 Borate – H3BO3, H2BO3-, B4O7-2
Zinc – Zn+2 Molybdate – MoO4-2
Manganese – Mn+2, Mn+4
Copper – Cu+2
Nickel – Ni+2 8
 Introduction to Fertilizers
Essential Nutrients of Plants
Chemical Atomic Ionic forms
Approximate dry
Element symbol weight Absorbed by plants_
concentration
Macronutrients
Nitrogen N 14.01
NO3-, NH4+ 4.0 %
Phosphorus P 30.98
PO43-, HPO42-, H2PO4- 0.5 %
Potassium K 39.10
K+ 4.0 %
Magnesium Mg 24.32 Mg2+
0.5 %
Sulfur S 32.07
SO 4
2-

0.5 %
Calcium Ca 40.08 Ca2+
1.0 %
Micronutrients
Iron Fe 55.85
Fe2+, Fe3+ 200 ppm
Manganese Mn 54.94 Mn2+
200 ppm
Zinc Zn 65.38
Zn2+ 30 ppm
Copper Cu 63.54 Cu2+
10 ppm 9
 Manufacture of nitrogenous fertilizers
Introduction:
 Webster defines fertilizer as “any material, as manure, chemicals,
etc., put on or in the soil to improve the quality or quantity of plant
growth”.
 As much as 95% of a plant is made of carbon, hydrogen and
oxygen. These nutrients are obtained from the air (from carbon
dioxide (CO2), and from water. Remaining nutrients are obtained
from the soil.
 Crop fertilizers contain nitrogen, phosphorus, and potassium as
major components. Magnesium, sulfate, and micronutrients may
also be added.
 Fertilizers are designated by numbers, such as 6-12-8, showing the
respective percentages of nitrogen expressed as N (in this case
6%), phosphorus as P2O5 (12%), and potassium as K2O (8%).

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 Farm manure corresponds to an approximately 0.5- 0.24-0.5
fertilizer. The organic fertilizers such as manure must undergo
biodegradation to release the simple inorganic species (NO 3-,

HxPO4x-3, K+) assimilable by plants.

 24–6–12 indicates that this particular grade contains 24% N
(nitrogen compounds), 6% P 2O5 (phosphorus compounds) and

12% K2O (potassium compounds).

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 Types of Fertilizers

 There are two broad categories of fertilizers: straights and compounds.

 Straights are those fertilizers that have only one of the primary
nutrients:
Examples would be
 Urea with 46% N,
 Single superphosphate (SSP) with 16-18% P 2O5,
 Triple Superphosphate (TSP),
 Ammonium Sulphate (AS),
 Calcium Ammonium Nitrate (CAN),
 Ammonium Nitrate (AN), and
 muriate of potash (MOP) with 62% K2O.
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 Compounds are those fertilizers that have two or all three of the
primary nutrients:
Examples would be
 Diammonium phosphate (DAP) with 18% N and 46% P2O5,
 Mono-Ammonium Phosphate (MAP),) and
 other chemically combined or complex fertilizers with various
proportions of N, P and K produced by the phosphoric acid or nitro
phosphate routes.

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 The product name “NPK” is normally followed by three numbers to
indicate the percent of N, P2O5 and K2O which the product contains,
 In addition, the fertilizer may contain magnesium, boron, sulphur,
micro-nutrients, etc.
 The typical content of nutrients (N + P2O5 + K2O) will normally be
in the range of 40-60%
 Grades with no P2O5 or no K2O are also included in the “NPK”
product range but they are normally named NP and NK fertilizers.
These types of fertilizers can normally be produced in NPK plants
and emission levels will typically be within the limits valid for NPK
grades. 14
 Fertilizer quality

 Fertilizer quality is not always easy to assess particularly by farmers

who have to rely on the supplier or on the labelling.
 In some countries there is considerable scope for adulteration of the
product as it passes along the distribution chain and for this reason
most countries have adopted a detailed fertilizer law that precisely
defines each type of fertilizer in terms of its chemical composition and
the method of analysis.
 In addition to the chemical analysis, other quality factors to consider
are:
 Whether the product is powder, pilled or granular. If pilled or granular,
the size distribution of the particles and the amount of dust.
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 Fertilizer quality…
 If the fertilizer is a compound NPK, whether it is a complex or
blended. If blended, whether the blend components have the same size
distribution so as to minimize segregation.
 Whether the product has been treated with a coating agent or not;
coating agents prevent caking and ensure the product is free flowing.
 Finally, if the product is bagged whether the bags meet the
specification: type and strength, whether correctly labelled, whether
pelleted or not, whether shrink-wrapped or not.
 In the export market, the type of bag used is usually a woven
polypropylene outer with a low-density polyethylene liner. These must
meet the specified strength criteria and must be closed correctly.

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 Bulk versus bagged versus liquid
 Fertilizers can be distributed in bags, in intermediate bulk
containers (IBCs or so-called big bags), in bulk or in liquid.
 There is no best system. Each situation is unique and
depends on the way the distribution pattern has developed
over the years, the size and level of mechanization of the
farms, and the size and pattern of the dealers

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 Environmental and regulatory issues

 Environmental problems can be divided broadly into those occurring

1. At the factory and
2. Along the distribution chain
3. Occur on the farm.
 The two most important problems at the factory level are
a) Gypsum disposal and
b) The removal of cadmium and other heavy metals from phosphate
fertilizers.
 At the farm level the most important problem is the possible
contamination of drinking and sea water by run-off from excessive
fertilizer use.
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 Overview of manufacturing processes
1. Nitrogen fertilizers
Ammonia synthesis
 Apart from small quantities of naturally occurring fertilizers
such as Chile nitrate, all nitrogenous fertilizers are derived
from ammonia.
 Ammonia production is second only to sulphuric acid as a
major base chemical for the world chemical industry.
 Roughly 85% of all ammonia is used for fertilizers while the
remaining 15% is used for industrial uses such as
explosives, dyestuffs, fibers, urea-formaldehyde resins and
melamine.

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 Nitric acid

 Along with ammonia, nitric acid is a key building block for

nitrogenous fertilizers such as ammonium nitrate and nitro
phosphate although the growth in nitric acid production is now
virtually static because of the rapid growth in the use of
alternative fertilizers such as urea.

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 Urea
 Urea – high efficiency nitrogen fertilizer with 46. 2% nitrogen content.
 Two urea grades are produced: grade A and grade B.

Urea
application

Chemical Agriculture
industry (Grade А) Grade A and B

Raw material for urea- aldehyde Animal farming (grade А)

resins
Used in the synthesis of  Natural alternative to protein in livestock feeds
melamine, hydrazine and other
pharmaceuticals Plant cultivation (grade B)
 used in the petroleum for
Universal fertilizer suitable for practically all kinds
purification of oils and motor
fuels from paraffin of soils and crops

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 Urea [CO(NH2)2]:
 Fertilizer grade: 46-0-0.
 Soluble, readily available source of N.
 Termed as Dry fertilizer product.
 Produced by reacting ammonia (NH 3) with carbon dioxide
under pressure at an elevated temperature.
2NH3 + CO2  CO(NH2)2 + H2O
 Contains the highest percentage of N of all dry fertilizers.
 Applying too much near germinating seeds can kill seedlings
due to NH3 release.
 Rapid hydrolysis to ammonium carbonate can cause
significant N losses as NH3 gas when urea is applied to the
surface of soil:
CO(NH2)2 + H2O  2(NH3)(gas) + CO2
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Urea [CO(NH2)2]: production
 The process has two main steps: the first uses ammonia
and carbon dioxide (conveniently, this is a by-product from
ammonia synthesis) to produce ammonium carbamate.
 The second step is the dehydration of ammonium
carbamate to give urea and water. This step must be
controlled effectively so as to reduce the production of
harmful biuret.
 The production of 1 ton of urea requires about 0.57 tons of
ammonia and 0.74 tons of carbon dioxide.

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 Ammonium nitrate

 There are two main types of ammonium nitrate - fertilizer grade and
explosive grade (EGAN), which is a more porous type.
 Both are made essentially in the same way by reacting nitric acid with
additional ammonia.
 The final product (33-34.5% N) is pilled or granulated and, like urea,
treated with a coating agent.
 Because ammonium nitrate is an oxidizing agent and can be explosive
under certain conditions there are very tight regulations controlling storage
and distribution.
 In some markets, such as Germany and the Netherlands, admixtures with
finely divided calcium carbonate are preferred. This type of product is
referred to as calcium ammonium nitrate (CAN, usually 26% N) or Nitro
chalk in the UK.
 CAN has a lower fire risk and is less prone to absorb moisture in humid
conditions.

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 Phosphate fertilizers

 The starting point for phosphate fertilizers is phosphate rock of

which there are essentially two broad types - igneous and
sedimentary.
 Igneous rock tends to be harder and less reactive in comparison
with sedimentary rock.
 Indeed certain plants are only readily suitable for processing
rock from one or a limited number of sources. Particular
problems include: high fluoride, chloride or Sulphide content, all
of which are corrosive, excessive foaming which requires a
defoamer, excessive hardness making the rock hard and
expensive to grind, slower rates of filtration, sludge and scale
formation.

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 Phosphate fertilizers…
 The main quality measure of phosphate rock is the amount of
phosphate, normally measured as % Bone Phosphate of Lime (BPL) or
% P 2O5.
 The quality of rock on the market is steadily declining as most of the
high-grade material has been used.
 In addition, other factors to consider include:
 The chemical composition: amounts of other materials such as
organics, calcium oxide, aluminum, magnesium, chloride, strontium
and cadmium;
 The ease of filtration when producing phosphoric acid; and the
level of sludge formation in phosphoric acid.
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 Single superphosphate (SSP)

 SSP is one of the simplest fertilizers and involves the reaction of ground
phosphate rock with (diluted) sulphuric acid in a so-called 'den';
 The resulting mixture is a slurry which quickly solidifies. The product is
tipped or cut out of the den and sent to storage where it is normally pile-
cured.
 The production of 1 ton of SSP requires about 0.64 tons of phosphate rock
and 0.37 tons of 100% sulphuric acid.
Triple superphosphate (TSP)
 The TSP process is similar to SSP except that the reagent is phosphoric acid
rather than sulphuric acid and the end-product has a much higher P 2O5
content.
 The production of 1 ton of TSP requires about 0.4 tons of phosphate rock and
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 Monoammonium phosphate (MAP)
 MAP and DAP are produced by reacting phosphoric acid with
ammonia.
 1 ton of MAP requires 0.15 tons of ammonia and 0.54 tons P2O5 as
phosphoric acid
Diammonium phosphate (DAP)

 While 1 ton of DAP requires 0.23 tons of ammonia and 0.47 tons
P2O5 as phosphoric acid.

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 Potash fertilizers

Potassium chloride
 The most widely used potash salt is potassium chloride, often
referred to as muriate of potash (MOP), which makes up over 90%
of total potash consumption.
 This is derived from naturally occurring potash deposits and these
are either deep-mined as, for example, in Canada, Russia, Germany
and the UK or
 harvested from solar evaporation ponds as in Jordan and Israel using
brines from the Dead Sea.

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 Basic Forms of Fertilizer

 Granular – designed to be scratched into soil, may also be water

soluble
 Powdered – designed to be dissolved in water for liquid feeding to
soil or foliage
 Liquid – usually a concentrated form to be mixed with water
 Solid – usually ‘spikes’ to push into soil around plant, very slow to
dissolve

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 Organic fertilizer
 Organic means: carbon / hydrogen based fertilizer

1 Naturally occurring organic fertilisers:

 Manure, urine, faeces, worm castings, peat, seaweed and
guano
2 Manufactured organic fertilizers:
 Compost, dried blood, bone meal and seaweed extracts, struvite
from urine, composted faeces.

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 Organic vs Inorganic

 There are some significant differences between the two types

and some of the key features of natural products are that:
 They are bulky and difficult to handle; farmyard manure
(FYM) and slurry, in particular, has a high water content
and low nutrient content.
 They provide organic matter which aids soil structure.
 They are slow-release fertilizers and contain micro-
nutrients.
 They are usually expensive per unit of plant food if
delivered off farm.

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 6. Pesticides
 According to reliable estimates, biotic factors, i.e., animal pests,
microorganisms and weeds, diminish the yield of agricultural produce
by 35%.
 Pesticides are widely used in present agriculture to control pests,
diseases, and weeds, which may affect crops and decrease their quality
and yield.
 Pesticide is any substance or mixture of substances intended for
preventing, destroying, repelling or mitigating any insects, rodents,
nematodes, fungi or weeds or any other forms of life declared to be
pests; any substance or mixture of substances intended for use as a plant
regulator, defoliant or desiccant.
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 The need for pest management:
• Increased population
• less land available for agriculture
• Land in agriculture must be very productive
• Must also be sustainable
• By their very nature, most pesticides create some risk to humans,
animals, or the environment because the are:
• designed to kill
• or otherwise adversely affect living organisms.
• At the same time, pesticides are useful to society because of their
ability to:
• kill potential disease-causing organisms
• Control insects, weeds and other pests.
34
 A bit of history…
• Sulfur
• Chinese - 1000BC
• Europe - 1800s
 Arsenic-containing
 Strychnine
 Nicotine (tobacco leaves extracts - 1690)
 Pyrethrum (chrysanthemum extract)
 Bordeaux mix: copper, lime (Ca(OH)2), water

35
 Pesticides pollution

What Happens after Application?

 When pesticides are applied the goal is that they will remain in the target area
long enough to control a specific pest and then degrade into harmless compounds
without contaminating the environment.
 Once applied, many pesticides are mobile in the environment (air, soil, water).
 This movement can be beneficial (moving pesticide to target area, such as roots)
but can also reduce the effect on the target pest and injure non-target plants and
animals.
 Air, soil, water, plants, animals, people, in/outside buildings

 Beneficial organisms, endangered species

 There is public concern about the effect of pesticides on the environment

36
 WHO has developed a classification system that group pesticides
according to the potential risks to human health caused by accidental
contact to human being and they are grouped into the following
classes;
 Class Ia = extremely hazardous
 Class Ib = highly hazardous
 Class II = moderately hazardous
 Class III = slightly hazardous
 Class IV = products unlikely to present acute hazard in
normal use

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Pathways of pesticide movement

 Runoff
 Chemical degradation
 Volatilize (gas vapor)
 Leaching and breakdown in soil
 Leaching and degradation by microbes
 Photo degradation (sun)
Factors influencing a pesticide’s fate
 Properties of the pesticide
 Conditions where & when applied
 Application method

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 Properties of the pesticide
 Vapor Pressure (volatility) – pesticides with a high vp are more likely to
change to a gas and escape into the atmosphere.
 Sorption – attraction to soil surfaces, pesticides with higher sorption values
have reduced leaching
 Water Solubility/dissolvability - more soluble pesticides have lower
sorption and are more mobile in the environment as they are leached or
moved with runoff.
 Persistence – the amount of time a pesticide remains in the environment,
measured by half-life. Pesticides with longer half-lives pose a greater threat
to the environment.
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 Conditions where & when applied

To maximize pesticide effectiveness and minimize negative environmental

impacts, the pesticide must be compatible with the physical, chemical, and
biological conditions of the application site.
 For pesticides use in crop or plant pest control consider the following
conditions:
 Soil: physical and chemical properties (texture, amount of organic matter, pH).
 Geology – depth to water table (larger distances give more soil to act as filter)
 Surrounding water sources – nearby water is more susceptible to contamination
when pesticides are applied to highly erodible soils, over-irrigated, or rain-
soaked soils. Managing crop residues and maintaining grass waterways and
filter strips help to protect surface waters from sediment and pesticide pollution

40
 Conditions where & when applied…

 Environmental conditions – heavy or sustained rainfall or irrigation

shortly after pesticide application can increase runoff, leaching, and
volatilization.
 Soil temperatures (extremely high or low) can interfere with
pesticide performance. Pesticides generally become more volatile in
high temperatures and windy weather.
 Pesticides can be incorporated (disked in) or applied directly into the
soil to decrease the potential for drift and volatilization.

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 Product labels

 The pesticide label is a binding, legal document. Compliance is

required by state and federal regulations.
 Label directions must be carefully followed – from purchase to
container disposal.
 High risk pesticides may only be purchased and applied by certified
persons.

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 Understanding the Label
Read before you
buy to be sure
you are buying
Very important!
the right
Understand the
product for the
potential dangers and
job.
keep out of the reach
of children.

It is important to keep
products in the
original container in
Buy the proper case of accidental
amount so you poisoning so you can
can avoid follow the first aid
storage, and instructions and have
dispose of the list of ingredients
container and left- available to give to
over product poison control.
properly.

43
Classification of Pesticides
 Pesticides can be classified based on their origin and the pests they
control.
Classification based on their origin
 Pesticides are classified based on their origin into chemical
pesticides and bio pesticides.
1. Chemical Pesticides
Further divided into four types:
 Carbamates
 Organophosphate pesticides
 Organochlorine pesticides
 Pyrethroid pesticides

06/07/2024 44
2. Bio pesticides

• These are derived naturally from living organisms or their metabolites

like bacteria, fungi, plants etc.

• They are classified into three major groups:

 Microbial pesticides
 Biochemical pesticides
 Plant incorporated protectants

06/07/2024 45
 Classification of pesticides based on how biodegradable they are:

i) Biodegradable pesticides: The biodegradable kind is those which can

be broken down by microbes and other living organisms into harmless
compounds’

ii) Persistent pesticides: These are pesticides which may take months
or years to break down.

06/07/2024 46
• Another way to classify pesticides is the consideration of their chemical
forms or those derived from a common source or production method.

• Chemically related pesticides

i) Organophosphates: Most organophosphates are insecticides; they

affect then nervous system by disrupting the enzyme that regulates a
neurotransmitter.

ii) Carbonates: Similar to the organophosphorus pesticides, the carbonate

pesticides also affect the nervous system by disrupting an enzyme that
regulates the neurotransmitter. However, the enzyme effects are usually
reversible

06/07/2024 47
iii) Organochlorine insecticides: They were commonly used in the past
but now many countries have removed organochlorine insecticides
from their market due to health and environmental effect and their
persistent nature, eg DDT, Chloradane and Toxaphene

iv) Prethroid: These are a synthetic version of pyrethroin, a naturally

occurring pesticides found in chrysanthemums (flower). They were
developed in a way so as to maximize their stability in the
environment.

v) Sulfonyl urea herbicides: These have been commercialized for

weed control such as pyrethrobac-sodium, cyclo sulfamtron etc.

06/07/2024 48
 Pesticide Types
 Acaracides
 Kills mites, ticks and spiders.

 Algaecides
 Control algae in lakes, canals, swimming pools, water tanks, and other sites.

 Antifouling agents
 Kill or repel organisms that attach to underwater surfaces, such as boat bottoms.

 Antimicrobials
 Kill microorganisms (such as bacteria and viruses).

 Antitranspirant
 Reduces loss of water from plant tissues

 Attractants
 Attract pests (for example, to lure an insect or rodent to a trap - however, food is

not considered a pesticide when used as an attractant.)

 Avicide
 Kills birds.

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 Pesticide Types…
 Bactericide
 Kills bacteria.
 Bio pesticides
 Pesticides derived from such natural materials as animals, plants, bacteria,
and certain minerals.
 Biocides
 Kill living organisms.
 Defoliants
 Remove unwanted plant growth without killing the whole plant.
 Fungicides
 Kill fungi (including blights, mildews, molds, and rusts).
 Fumigants
 Produce gas or vapor intended to destroy pests in buildings or soil.
 Herbicides
 Kill weeds and other plants that grow where they are not wanted.

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 Pesticide Types…
 Insecticides
 Kill insects and other arthropods.
 Insect growth regulators
 Disrupt the molting, maturity from pupal stage to adult, or other life
processes of insects.
 Miticides
 Kill mites that feed on plants and animals.
 Microbial pesticides
 Microorganisms that kill, inhibit, or out compete pests, including insects
or other microorganisms.
 Molluscicides
 Kill snails and slugs.
 Nematicides
 Kill nematodes (microscopic, worm-like organisms that feed on plant
roots).
 Ovicides
 Kill eggs of insects and mites

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 Pesticide Types…
 Pheromones
 Biochemical used to disrupt the mating behavior of insects.
 Predacide
 Kills vertebrate pests
 Repellents
 Repel pests, including insects (such as mosquitoes) and birds.
 Rodenticides
 Control mice and other rodents.

The term pesticide also includes these substances:

 Desiccants
 Dry up plant leaves and stems, also insects.
 Disinfectants and sanitizers
 Kill or inactivate disease-producing microorganisms on inanimate
objects.
 Plant growth regulators
 Substances (excluding fertilizers or other plant nutrients) that alter the
expected growth, flowering, or reproduction rate of plants.

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 Pesticide Formulation
 A Pesticide product consists of two parts:
 Active ingredients
 Inert ingredients
 Active ingredients are chemicals which actually control the
pest.
 Inert ingredients are primarily solvents and carriers that help
deliver the active ingredients to the target pest; they serve
to enhance the utility of the product.
 Inert ingredients may be liquids into which the active
ingredient is dissolved, chemicals that keep the product
from separating or settling, and even compounds that help
secure the pesticide to its target after application.
 The combination of an active ingredient with the compatible
inert is referred to as a formulation.

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 A Pesticide active ingredient in a relatively pure form,
ready for manufacturer’s use, rarely is suitable for field
application.
 An active ingredient usually must be formulated in a
manner that
 Increases pesticide effectiveness in the field
 Improves safety features
 Enhances handling qualities
 The formulation gives the product its unique physical form
and specific characteristics, enabling it to fill a market
niche.
 There are approximately 860 pesticide active ingredients
formulated into 21,000 pesticide products sold and used in
USA.

54
 The active ingredients in pesticide products come from many sources.
 Some, such as nicotine, pyrethrum and rotenone, are extracted from plants
 Others have a mineral origin, while a few are derived from microbes
 The vast majority of active ingredients are synthesized in the laboratory.
 These synthetic active ingredients may have been designed by an organic
chemists or discovered through a screening process of chemicals generated
by various industries.
 Regardless of their source, pesticide active ingredients have different solubility.
 Some dissolve in water, others only in oils.
 Some may be relatively insoluble in either water or oils.
 These different solubility nature, coupled with the intended use of pesticide
define the types of formulations in which the active ingredient may be delivered.

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Pesticide Formulation…

56
 Types of Formulations
• Dry • Liquid
• Dust (D) • Water soluble concentrate (WS)
• Bait (B) • Emulsifiable concentrate (E or EC)
• Granule (G) • Oil-soluble amine concentrates
• Wettable powder (WP OR W) • Ultra-low volume concentrate (ULV)
• Soluble powder (SP or WSP) • Flowable (F or L)
• Water dispersible granule or dry • Liquefied gas (Fumigants)
flowable (DF) • Aerosols (A)
• Pellet (P)
• Microencapsulated (M)

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 58
Dust
Granules

59
Pellets
60
Wettable powders
before mixing Wettable powders after
mixing

61
Dry flowables before mixing

Dry flowables after mixing

62
Soluble powders
before mixing

Soluble powders after mixing

63
 Types of Formulations…
Liquid Formulations
 Four common liquid formulations that are mixed with a
carrier are known:
 Liquid flowables
 Microencapsulates
 Emulsifiable concentrates and
 Solutions
 The carrier will generally be water, but in some instances
labels may permit the use of crop oil, diesel fuel, kerosene, or
some other light fuel oil as a carrier.

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 Anti-insect agents
Insecticides of natural origin

 Applied long time before the synthetic insectides.

 Applied as early as 1690 in Europe.
 In the period between 1900 and the 1940s – nicotine,
anabasine, pyrethrins, rotenone and quassia were used in
addition to inorganic insecticides.
 Application virtually ceased on the discovery and large-
scale economic production of synthetic insecticides.
 In recent years the importance of certain of this group has
increased again because of their advantageous properties
from the point of view of toxicology and environmental
protection.

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 Anti-insect agents…
Nicotine, anabasine and related derivatives

 The various Nicotiana species, particularly N. rustica,

N. tahacum. N. sylvestris and N . glauca, contain
different Nicotiana alkaloids in various proportions. The
most important of these alkaloids are nicotine (l),
nornicotine (2) and anabasine (3).

2 . nornicotine 3. anabasine
1. nicotine

Oxidation Quaternisation,
methylation and
subsequent oxidation
into N-methylpyrrolidine
-2- carboxylic acid 66
 Pyrethrins and synthetic pyrethroids
 Pyrethrum, the dried flower of Chrysanthemum
cinerariaefolium, or its solvent extract, has been used
for centuries in order to kill insects.
 The plant, originally native to the Near East, was
introduced into Europe and America in the nineteenth
century, and later into Japan and Africa. Its main regions
of culture are Kenya and other African countries,
Equador and Japan.
 The active substances of pyrethrum (rethrins) are
pyrethrin I (9), pyrethrin II (l0), cinerin I (11), cinerin II
(12), as well as jasmolin I (13) and jasmolin II (14).
 The esters are optically active, their absolute
configuration being lR, 3R, 4's.
 The double bond in the alcoholic part possesses Z,
while that in the carbonic acid part E-configuration.
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68
Pyrethrins and synthetic pyrethroids…

pyrethrin I pyrethrin II

cinerin II
cinerin I

jasmolin II
jasmolin I

69
 Pyretbrins and synthetic pyrethroids…
 The synthesis of chrysanthemic acid (15), the acid
component of the esters 9,11 and 13, was first solved by
Staudinger et al. (1924). Starting from 2,5-dimethylhexa-
2,4-diene (16) and ethyl diazoacetate, they obtained ( ± )-
(Z)-chrysanthemic acid (15).
 By modifying this process, Harper et al. (1 95 1) obtained a
mixture of the esters of the Z and E modifications, from
which the active E-isomer could be recovered by
crystallization. According to the findings of Matsumoto et al.
(1963), using the t-butyl ester of diazoacetic acid in the
presence of copper dust, (8- chrysanthemic acid is formed
stereoselectively.

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71
 Synthetic Pyrethroids
 Pyrethroids are acknowledged of their fast nocking down
effect against insect pests, low mammalian toxicity and
facile biodegradation.
 Although the naturally occurring pyrethrins are effective
insecticides, their photochemical degradation is so rapid
that their uses as agricultural insecticides become
impractical.
 The synthetic analogues of the naturally occurring
pyrethrins (pyrethroids) were developed by the
modification of pyrethrin structure by introducing a
biphenoxy moiety and substituting some hydrogens with
halogens in order to confer stability at the same time
retaining the basic properties of pyrethrins.
 The most widely used synthetic pyrethroids include
permethrin, cypermethrin and deltamethrin.

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 Synthetic organic Pesticides
1. Organochlorines pesticides

 Organochlorines pesticides are organic compounds with five or more chlorine

atoms.
 Organochlorines were the first synthetic organic pesticides to be used in
agriculture and in public health. Majority of them were banned from agricultural
use
 Most of them were widely used as insecticides for the control of a wide range of
insects, and they have a long-term residual effect in the environment since they
are resistant to most chemical and microbial degradations.
 Organochlorine insecticides act as nervous system disruptors leading to
convulsions and paralysis of the insect and its eventual death. Some of the
commonly used representative examples of organochlorine pesticides are DDT,
lindane, endosulfan, aldrin, dieldrin, Hexachlorocyclohexane, and chlordane and
73
 Hexachlorocyclohexane
(Benzenehexachloride,
BHC)
Cl

P-Dichlorobenzene (p-DCB)

Cl 74
Cyclodiene Derivatives

Chlordane

β-Chlordane
α-Chlordane

75
heptachlor
Heptachlor epoxide
Aldrin,

Dieldrin,

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 Carbamates

Carbamates are organic pesticides derived from carbamic

acid with the general formula

Where, R1 is an alcohol group, R2 is a methyl group and R3 is

usually hydrogen.
 Both oxime and aryl carbamates have fairly high insect and
mammalian toxicities as cholinesterase inhibitors.
 Some of the widely used insecticides under this group include
carbaryl, carbofuran and aminocarb.

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 Organophosphorus compounds
 Organophosphorous insecticides on the other hand contain
a phosphate group as their basic structural framework as
defined by Schrader's formula:

Where, R1 and R2 are usually methyl or ethyl groups, the O in the OX group
can be replaced with S in some compounds, whereas the X group can take a
wide diversity of forms.
 Organophosphorous insecticides are generally more toxic to vertebrates and
invertebrates as cholinesterase inhibitors leading to a permanent overlay of
acetylcholine neurotransmitter across a synapse.
 As a result, nervous impulses fail to move across the synapse causing a
rapid twitching of voluntary muscles and hence paralysis and death.
 organophosphorous insecticides are not persistent in the environment

78
 Organophosphorus compounds…
 Some of the widely used organophosphorous insecticides
include parathion, malathion, diaznon, Dimethoate and
glyphosate

Dimethoate

79
 Rodenticides

 For many centuries the eradication of rodents has been a grave

problem to humanity. In addition to the hygienic aspects, it was
important for stock protection, while exterminating them from
crops is one of the tasks of plant protection.
 Initially, poisons of vegetable origin and inorganic compounds
with toxic properties were used to kill rodents. These active
substances were added to ground cereals, or possibly to
unground seeds, as the basic substance of the bait.
 Of the plant poisons, scilliroside, a glucoside of red squill
(Urginea maririma), a plant of the family of the Liliaceae, and
strychnine, an alkaloid extracted from the seeds of Strychnos
nux vomica and a number of other species of the family of the
Loganiaceae, were initially used for the eradication of rodents.

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Rodenticides

Scilliroside Strychnine
 Of the inorganic compounds, not only the compounds of
arsenic (As2O3,Na3AsO3,) and phosphorus, but in
particular barium carbonate (BaCO3,) and thallium sulfate
(Tl2SO4,) were noted for their more specific rodenticidal
action.

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 Fungicides
 Fungicides are pesticides that are used for the control of
fungal infections in crops.
 There are inorganic and organic fungicides.
 Inorganic fungicides include Bordeaux mixture,
Cu(OH)2.CaSO4 and malachite, Cu(HO)2.CuCO3.
 Organic fungicides on the other hand include among
others, benomyl and oxime copper

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 Fungicides
 The fungitoxic properties of various metal salts:
Ag> Hg> Cu> Cd > Ni > Pb> Co > Zn > Fe> Ca.
 Copper compounds are protective fungicides with a broad
range of action and long residual activity.
 In the treatment of seeds they have proved most effective
against bunt. They do not, however, give adequate protection
against Fusarium diseases or covered smut and leaf stripe of
barley.
 Sulfur and its inorganic compounds: The biocidal effect of
sulfur has been known since antiquity.
 Organo-mercury compounds
 The chlorinated and nitrated derivatives of aromatic
hydrocarbons, primarily of benzene are used for the
prevention of fungal infections from the soil by seed or soil
treatment. Their action in the soil is enhanced by their
medium volatility.
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 Fumigants
• Very volatile - inhalation exposure
• Non-selective, highly reactive and cytotoxic
• Examples
• acrylonitrile
• carbon disulfide
• carbon tetrachloride
• ethylene dibromide (gastric carcinomas, sterility)
• ethylene oxide (carcinogen, developmental tox.)

• phosphine (PH3) released from aluminum phosphide (AlP) in moist

conditions (grain storage)

84