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Environmentalist (2008) 28:35–44

DOI 10.1007/s10669-007-9045-4

ORIGINAL PAPER

Recent developments of safer formulations


of agrochemicals
Alan Knowles

Published online: 25 August 2007


 Springer Science+Business Media, LLC 2007

Abstract The primary objectives of formulation tech- Keywords Pesticide formulations  Formulation trends 
nology are to optimise the biological activity of the Conventional formulations  Safer formulations 
pesticide, and to give a product which is safe and con- Seed treatment formulations  Surfactants  Adjuvants 
venient for use. However, because of the wide variety of Bioenhancement
pesticide active ingredients which are available, many
different types of formulations have been developed
depending mainly on the physico-chemical properties of
the active ingredients. In the past most formulations were
based on simple solutions in water (SL), emulsifiable 1 Introduction
concentrates in a petroleum-based solvent (EC), or dusts
(DP) and wettable powders (WP). The presence of petro- Over the last 50 years, farmers and growers in all the main
leum-based solvents in EC formulations and dusty powders agricultural areas of the world have relied substantially
in DP and WP formulations can lead to safety hazards in upon fertilisers and crop protection chemicals to help them
use and a negative impact on the envirnoment generally. meet the ever-increasing demand for food and other
Most government and regulatory authorities are now materials such as natural fibres. To meet these demands
demanding formulations which are cleaner and safer for the simple dusting powders and spray oil formulations have
user, have minimal impact on the environment, and can be been used for many years to protect growing crops from
applied at the lowest dose rate. Developments in for- weeds, pests and diseases. However, since the 1950’s, the
mulation technology and novel formulation types, chemical industry has satisfied consumer demands for
sometimes in special packaging such as water-soluble increased crop yield, quality and variety by the continuous
packs, can also give products a competitive advantage, add development and introduction of more effective crop pro-
value or extend the lif-cycle of active ingredients. There is tection chemicals. During this period the population of the
also a demand from government authorities and consumer world has increased from about 2.5 billion in 1950 to about
groups to use safer formulation additives and adjuvants, 6 billion in 2000. Furthermore, the world’s population is
and to minimise the residues of pesticides on food crops expected to reach about 10 billion by the year 2040,
after spraying. All of these aspects are putting increasing placing an even greater pressure on food security and
pressure on the development of improved formulation and environmental safety.
adjuvant technologies. Pesticide formulations for spray This development has led to a need for a wide range
application and for seed treatment are discussed, along with of product formulation types, additives and process
developments in bioenchancement. technology to enable the formulation of pesticide active
ingredients with various physical and chemical proper-
ties. For example, water soluble active ingredients may
A. Knowles (&)
be prepared as aqueous solutions or soluble powder
FORM-AK Formulation Consultancy Services, Tonbridge,
Kent TN11 0RT, UK formulations, whereas oily liquid active ingredients are
e-mail: alan@form-ak.com usually formulated as hydrocarbon solvent-based

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emulsifiable concentrates. Active ingredients which have 3 Formulation types


very low solubility in either water or hydrocarbon oils,
may be formulated as suspensions, powders or water The most common formulations are still soluble con-
dispersible granules (Valkenburg 1973). Other formula- centrates for water-soluble chemicals, emulsifiable
tion types for special applications are granules for direct concentrates for oil-soluble chemicals, and wettable
application to the soil or the crop and seed treatments for powders and suspension concentrates for insoluble solids.
direct application to the seed. In the 1980’s and 1990’s, Granules and seed treatments for direct application have
pressure from government authorities and consumer or- also been produced for many years. In recent years the
ganisations highlighted a need for products and number of formulation types has increased enormously to
formulations which are safer and more convenient to use, meet the needs of operator and environmental safety or to
more effective at much lower application rates, less toxic improve the activity and persistence of the active ingre-
to non-target species and with lower impact on the dient. An international coding system was, therefore,
environment generally. devised by GIFAP in 1984 (in 1996 GIFAP was renamed
The earliest pesticide formulations were based on simple GCPF - Global Crop Protection Federation, based in
technologies providing dusts, powders, granules, aqueous Brussels, Belgium. This organisation is now known as
solutions and mineral oil-in-water emulsions. Since the CropLife International) listing about 80 different types of
1980’s, there has been a rapid development of more formulation. The major types of formulations and inter-
sophisticated formulations based on the availability of more national codes are shown below:
powerful surfactants and other additives, and a much better
understanding of the principles of colloid and surface
Formulation type Code
chemistry to improve formulation stability and biological
activity. Processing technology has also developed over this Granules GR
period to give much smaller particle size for better stability Solution concentrates SL
and biological activity for water and solvent insoluble active Emulsifiable concentrates EC
ingredients. Adjuvants have also been developed to enhance Wettable powders WP
the activity of the pesticide at the target site. Suspension concentrates SC
O/W emulsions EW
2 Formulation objectives Suspoemulsions SE
Microemulsions ME
The main objectives of formulation can be summarised as Water dispersible granules WG
follows: Microcapsules CS
To provide the user with a convenient, safe product Seed treatments DS,WS,LS,FS
which will not deteriorate over a period of time, and
to obtain the maximum activity inherent in the active
ingredient.
4 Conventional formulations
Formulators need to take into account a number of
interacting factors in the choice of the specific formulation Formulations based on the older technologies are still
type for each active ingredient. The main factors governing available and represent the greatest volume of products
the choice of formulation are: applied to crops. A brief review is given here of the main
types of conventional formulations.
• physico-chemical properties
• biological activity and mode of action
• method of application
4.1 Granules (GR)
• safety in use
• formulation costs
Granular formulations are used for direct broadcasting to
• market preference
the field often as pre-emergence herbicides or as soil
Once these parameters have been determined, proper insecticides. The active ingredient concentration is usually
selection can be made of the final formulation type and the from 1–40% and the granule mesh size is generally
use of inert ingredients including surfactants and other between 250 and 1,000 microns. The granules should be
additives to produce a stable formulation with at least a 2- non-caking, non-dusty, free flowing and should disintegrate
year shelf life during storage under varying climatic in the soil to release the active ingredient. Granules are
conditions. usually made either by coating a fine powder onto a

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substrate, e.g. sand, using a sticker such as PVP solution, or Nonylphenol or tallow amine ethoxylates are often used
by solvent impregnation onto an absorbent carrier. Resins as tank mix wetters for solution concentrate formulations to
or polymers may be sprayed onto the granules to control enhance bioefficacy. Alternatively, the wetting agent may
release rates. Absorbent carriers may be mineral such as be built into the formulation to ensure that the correct rate
clays or silicas, or vegetable such as ground corn cobs or of wetting agent is applied to optimise biological activity.
coconut shells. This is often the case, for example, with paraquat and
The absorptive capacity of the carrier is an important glyphosate formulations. A considerable amount of work is
parameter and is a function of the crystalline structure and being carried out on new surfactant wetting agents for
the available surface area of the carrier particles. Some glyphosate formulations (Foy 1992). In some cases pre-
typical absorptive capacities are shown below: servatives may be necessary to prevent mould growth or
bacterial spoilage during long term storage.
Absorptive capacities of granule carriers
Carrier Oil absorption (g/100g)
4.3 Emulsifiable concentrates (EC)
Silica 200
Attapulgite 100
Emulsifiable concentrate formulations have been very
Montmorillonite 23–70
popular for many years and represent the biggest volume of
Kaolin 20–54 all pesticide formulations in terms of consumption world-
Talc 20–40 wide. Emulsifiable concentrates are made from oily active
Calcium carbonate 5–18 ingredients or from low melting, waxy solid active ingre-
Corn cob grits 60–80 dients which are soluble in non-polar hydrocarbon
Walnut shell 20–40 solvents, such as xylene, C9–C10 solvents, solvent naphtha,
odourless kerosene, or other proprietary hydrocarbon
solvents.
Granules are becoming less popular now because of the Surfactant emulsifiers are added to these formulations to
increasing use of post-emergence herbicides. ensure spontaneous emulsification with good emulsion
stability properties in the spray tank. Careful selection of a
4.2 Solution concentrates (SL) ‘‘balanced pair’’ emulsifier blend is frequently necessary to
ensure emulsion dilution stability is maintained over
The simplest of all formulations to make is the solution widely differing climatic conditions and degrees of water
concentrate, an aqueous solution of the active ingredient hardness. Emulsion droplets of 0.1–5 microns are produced
which merely requires dilution in the spray tank. The when the formulation is mixed with water.
number of pesticides which can be formulated in this way The formulation of emulsifiable concentrates has been
is limited by water solubility and hydrolytic stability of the greatly facilitated by the commercial development over the
active ingredient. last 20 years of non-ionic emulsifying agents in which the
Some solution concentrate formulations contain a sur- hydrophilic portion of the molecule consists of a polyeth-
factant, usually a non-ionic ethylene oxide condensate, to ylene oxide chain. The non-ionic surfactant which is
assist wetting onto the leaf surface. Solution concentrate commonly used is a nonyl phenol hydrophobic chain
formulations are usually very stable and, therefore, present condensed with 12 or more moles of ethylene oxide. The
few storage problems. Some problems do occur occasion- other component of the balanced pair is generally an
ally, such as precipitation during dilution, and corrosion of anionic surfactant such as the oil soluble calcium salt of
metal containers or spray applicators. However, these dodecylbenzene sulphonic acid.
problems can be overcome by the use of suitable additives, Recently, however, nonyl phenol ethoxylates have been
such as co-solvents and corrosion inhibitors. A typical suspected of having endocrine modulating properties from
solution concentrate formulation is shown below: metabolites in effluents which may contaminate rivers and
ground drinking water. Because of this potentially toxic
% w/w effect, alternative ethylene oxide condensates based on
aliphatic alcohol hydrophobes are being introduced.
Active ingredient 20–50
The total concentration of the emulsifier blend is usually
Wetting agent 3–10
5–10% of the formulation. There are no definite rules to
Antifreeze 5–10
determine the ratio of anionic to non-ionic surfactant in the
Water to 100
mixed emulsifiers, but guidance can be obtained from the
Water-miscible solvent
HLB system. HLB stands for hydrophile-lipophile balance

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and the higher the HLB the more hydrophilic (water-sol- kaolin or talc is also needed to prevent the formulated
uble) is the surfactant. The HLB range 8–18 will normally product from caking or aggregating during storage. A
provide good oil-in-water emulsions. The optimum ratio of typical wettable powder formulation is shown below:
anionic and non-ionic surfactants is determined experi-
mentally to give spontaneous emulsification in water, and
% w/w
to give a stable emulsion with very little creaming and no
oil droplet coalescence. Active ingredient 25–80
Emulsifiable concentrates are limited in the number of Wetting agent 1–3
active ingredients for which they are suitable. Many pes- Dispersing agent 2–5
ticides are not soluble enough to be supplied economically Inert filler/carrie to 100
in this form. However, it may be possible to boost the
solubility of the active ingredient by the addition of a more
polar solvent without increasing the risk of crystallisation
in the spray tank. A typicalemulsifiable concentrate for- 4.5 Suspension concentrates (SC)
mulation is shown below:
Suspension concentrate technology has been increasingly
% w/w applied to the formulation of many solid crystalline
Active ingredient 20–70 pesticides since the early 1970’s. Pesticide particles may
Emulsifier blend 5–10 be suspended in an oil phase, but it is much more usual
Solvent to 100
for suspension concentrates to be dispersions in water.
Co-solvent
Considerable attention has been given in recent years to
the production of aqueous suspension concentrates by a
high energy wet grinding processes such as bead milling.
The presence of solvents and emulsifiers in emulsion The use of surfactants as wetting and dispersing agents
concentrate formulations can sometimes give enhanced has also led to a great deal of research on the colloidal
biological efficacy compared with other formulations. and surface chemistry aspects of dispersion and stabili-
Many insecticides, e.g. organo-phosphorous compounds sation of solid/liquid dispersions (Tadros 1987).
and pyrethroids are oil soluble liquids or waxy solids and Water-based suspension concentrate formulations offer
are readily formulated as emulsifiable concentrates, and a many advantages such as
few active ingredients need to be formulated with solvents
for optimum biological activity. • high concentration of insoluble active ingredients
• ease of handling and application
• safety to the operator and environment
4.4 Wettable powders (WP)
• relatively low cost
• enable water-soluble adjuvants to be built-in for
Wettable powder formulations of pesticides have been
enhanced biological activity.
known for many years and are made usually from solid
active ingredients with high melting points which are Farmers generally prefer suspension concentrates to
suitable for dry grinding through a mechanical grinder wettable powders because they are non-dusty and easy to
such as a hammer or pin type mill or by air milling with measure and pour into the spray tank. However, there are
a fluid energy micronizer. Air milling gives much finer some disadvantages, notably the need to produce formu-
particles (5–10 microns) than mechanical milling (20–40 lations which do not separate badly on storage, and also to
microns) and can also be more suitable for active protect the product from freezing which may cause
ingredients with lower melting points. However, care aggregation of the particles.
must be taken to prevent, suppress or contain dust In most cases, suspension concentrates are made by dis-
explosions which may occur if a source of ignition, such persing the active ingredient powder in an aqueous solution
as static energy, is present in both types of mills. Wet- of a wetting and dispersing agent using a high shear mixer to
table powders usually contain dry surfactants as powder give a concentrated premix, followed by a wet grinding
wetting and dispersing agents and inert carriers or fillers. process in a bead mill to give a particle size distribution in
They frequently contain more than 50% active ingredient the range 1–10 microns. The wetting/dispersing agent aids
and the upper limit is usually determined by the amount the wetting of the powder into water and the breaking of
of inert material such as silica required to prevent the aggregates, agglomerates and single crystals into smaller
active ingredient particles fusing together during pro- particles. In addition, the surfactant which becomes adsor-
cessing in the dry grinding mills. An inert filler such as bed onto the freshly formed particle surface during the

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grinding process should prevent re-aggregation of the small formulations which have less impact on the environment
particles and should ensure colloidal stability of the dis- generally (Holden 1992). The main issues which are being
persion. Typical wetting/dispersing agents used in addressed are:
suspension concentrate formulations are:
• safety in manufacture and use
• sodium lignosulphonates • convenience for the user
• sodium naphthalene sulphonate-formaldehyde • ease of pack disposal or re-use
condensates • reduction of the amount of pesticide applied
• aliphatic alcohol ethoxylates • reduction of waste and effluent of all kinds.
• tristyrylphenol ethoxylates and esters
The current trends in the development of pesticide for-
• ethylene oxide/propylene oxide block copolymers.
mulations are :
More recently available are polymeric surfactants, such
• to eliminate solvents wherever possible and use aque-
as ‘‘comb’’ surfactants, which adsorb strongly on particle
ous emulsions or microemulsions
surfaces and may give considerably improved stabilisation
• to replace dusty powders by suspension concentrates or
of suspension concentrates for long term storage (Heath
water dispersible granules
et al. 1984). A typical suspension concentrate formulation
• to develop multiple active ingredient formulations
is shown below:
where appropriate
% w/w • to build into the formulation bioenhancing surfactant
adjuvants
Active ingredient 20–50 • to control release rate and targeting of pesticides by
Wetting/dispersing agent 2–5 encapsulation techniques or seed treatment applications
Propylene glycol antifreeze 5–10 • to develop novel formulations such as tablets or gels
Anti-settling agent 0.2–2 • to develop more effective spray tank adjuvants to
Water to 100 enhance biological activity and reduce pesticide dosage
These complex requirements are being met by technical
The anti-settling agent is added to increase viscosity and advances in surfactants and other formulation additives,
build up a three dimensional network structure to prevent particularly blends of surfactants, more powerful dispersing
separation of particles during long term storage. The anti- agents and a better understanding of the principles of colloid
settling agent is usually a swelling clay such as bentonite and surface chemistry and rheology (Seaman 1990). The
(sodium montmorillonite) and may be mixed with water ideal product would seem to be one which is free from vol-
soluble polymers to give synergistic rheological effects. The atile solvents, gives very low operator exposure hazard, has
water soluble polymers are often cellulose derivatives, nat- the maximum biological activity at the lowest dose level, and
ural gums or other types of polysaccharides, such as xanthan produces the minimum of pack disposal problems. Water-
gum, and they are generally susceptible to microbial attack. dispersible granules or wettable powders in water-soluble
For this reason, preservatives are usually added to suspen- sachets which can be added directly to a spray tank go a long
sion concentrate formulations to prevent degradation of the way towards meeting these requirements, and development
anti-settling agent so that long term stability of the product is work is being carried out on these options by all the major
not impaired (Knowles 1995). agrochemical companies. However, it will never be possible
A great deal of research has been carried out using rheo- to formulate all active ingredients this way and so other
logical techniques to measure the forces acting between options are being evaluated extensively, along with ideas for
particles and polymers to enable storage stability to be pre- more convenient packaging and closed transfer spray tank
dicted. However, it is still necessary to carry out long term application systems.
storage tests over a range of temperatures to ensure that the Aqueous-based formulations are regarded as safe alter-
particles do not aggregate or separate irreversibly under natives to water dispersible granule formulations and these
normal storage conditions in the sales pack (Tadros 1995). options include (additional to suspension concentrates
which have already been discussed):
5 New generation formulations
• suspoemulsions
5.1 General trends • o/w emulsions (concentrated emulsions)
• microemulsions
Over the last few years there has been increasing pressure • multiple emulsions
from government and regulatory authorities to develop • microcapsules (capsule suspensions)

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Other possibilities involving specialised packaging are droplets and extensive storage testing of these formulations
gels (in water soluble sachets) and effervescent tablets (Foy is necessary (Tadros 1988).
and Pritchard 1996).
5.4 Microemulsions (ME)
5.2 O/W Emulsions (EW)
Microemulsions are thermodynamically stable transparent
Oil-in-water emulsions are now receiving considerable
emulsions and are stable over a wide temperature range.
attention because of the need to reduce or eliminate volatile
They have a very fine droplet size of less than 0.05 microns
organic solvents for safer handling. Because they are water
(50 nanometers) and consist of three components, namely:
based, oil-in-water emulsions can have significant advan-
tages over emulsifiable concentrates in terms of cost and • oily liquid or solid dissolved in organic solvent
safety in manufacture, transportation and use. However, • water
they require careful selection of surfactant emulsifiers to • surfactant/co-surfactant system
prevent flocculation, creaming and coalescence of the oil
These components form a single phase containing rel-
droplets. Non-ionic surfactants, block copolymers and
atively large ‘‘swollen micelles’’ in which the non-aqueous
other polymeric surfactants are now being used to produce
phase of the active ingredient and solvent are dissolved or
stable emulsions. In the case of non-ionic surfactants it is
solubilised by the surfactant system.
sometimes useful to combine a low and a high HLB sur-
In the preparation of microemulsions two different types
factant to give an emulsifier mixture with an average HLB
of surfactants are needed; one water soluble and one oil
of 11–16 for optimum emulsion stability (Tadros 1995).
soluble. The water soluble surfactant is usually anionic or
Droplet size is also a good indicator of stability and
non-ionic with a very high HLB value, and the hydro-
should be below 2 microns (volume mean diameter VMD).
phobic part of the molecule should match the oil. The co-
The emulsions are usually thickened with polysaccharides
surfactant should be oil soluble and should have a very low
such as xanthan gum to prevent separation of the oil
HLB value, for example hexanol. The total concentration
droplets. Sometimes polymers such as polyvinyl alcohol
of surfactants for a microemulsion can be as high as 10–
are used as both emulsifier and thickener/stabiliser.
30% or more, compared with about 5% for a typical o/w
emulsion (Tadros 1995). Microemulsions have relatively
5.3 Suspoemulsions (SE)
low active ingredient concentrations, but the high surfac-
tant content and solubilisation of the active ingredient may
Mixed combination formulations are becoming more pop-
give rise to enhanced biological activity.
ular because of their convenience, they ensure that the
farmer applies the correct amount of each component
pesticide and overcome problems of tank mix incompati- 5.5 Multiple emulsions
bility. If one active ingredient is a solid and the other is a
liquid, it is necessary to produce a suspoemulsion formu- Another class of emulsion is the multiple emulsion, which
lation, which consists of three phases: can be water-in-oil-in-water (W/O/W) or oil-in-water-in-oil
(O/W/O). These are complex formulations which require
• solid dispersed particles
very careful selection of surfactant emulsifiers and stabil-
• liquid oil droplets
isers to overcome physical instability problems.
• continuous phase, usually water
Multiple emulsions are still in the research phase and
Suspoemulsions can, therefore, be considered to be mix- could be of interest to reduce the oral toxicity of an active
tures of suspension concentrates and oil-in-water emulsions ingredient by restricting it to the primary internal emulsion
with added surfactants to prevent flocculation and thickeners droplet phase. However, because of the need to form a
to prevent separation of the dispersed phases. Surfactants second emulsion phase, the final product must be of low
used as dispersing agents for the solid phase are similar to active ingredient content.
those already mentioned for suspension concentrates.
Emulsifiers for the oily liquid phase are similar to those used
5.6 Controlled release formulations
for oil-in-water emulsions. As these formulations are aque-
ous based and generally thickened with polysaccharides, it is
Controlled release formulations can have the following
necessary to add a preservative to prevent degradation of the
advantages over conventional formulations:
thickener. Careful selection of the appropriate dispersing and
emulsifying agents is necessary to overcome the problem of • longer residual biological activity
heteroflocculation between the solid particles and the oil • may reduce mammalian toxicity

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• control/reduce evaporation of pesticide Microcapsule suspensions need to be stabilised with


• may reduce phytotoxicity to crop surfactants and thickeners in the same way as suspension
• may improve compatibility in spray tank concentrates and emulsions, and similar additives are used.
• reduce ground water leaching This technology allows the controlled release of pesti-
• reduce fish toxicity cide active ingredients and can reduce product toxicity
• reduce solvent usage in formulation appreciably as well as reducing leaching from the soil.
• may reduce pesticide application rate Despite these clear benefits, commercial development of
microencapsulation technology for pesticides has been
Controlled release pesticide formulations can be divided
somewhat slow. Substantial research and development
into four main types:
resources have been devoted to it by the major agro-
• coated pesticide granules chemical companies over the last 10 years or so, but at
• matrix systems containing physically trapped pesticides present there are only about 20–30 significant herbicides
• polymer systems containing covalently bound and insecticides on the market. The slow progress is partly
pesticides due to the complexity of the formulation and processing, in
• polymer membrane-pesticide reservoir systems, e.g. particular the safe handling of the materials used in pro-
microencapsulation duction and the long-term stability of the formulation.
Another difficulty is product application to crops and
The polymer membrane, or microencapsulation tech-
insects under varying conditions where reliable rates of
nique, has become popular in recent years. A well known
release of the active ingredients must be maintained. This
method of microencapsulation uses the principle of inter-
complexity and the high R&D costs tend to deter the
facial polymerisation. In this process the active ingredient,
smaller agrochemical formulation companies from devel-
usually a liquid or low melting waxy solid, is dissolved in
oping controlled release products.
an aromatic solvent, such as the C9 and C10 solvents used
However, recent patents from Syngenta on ‘‘triggered
for emulsifiable concentrates. An oil-soluble monomer
release’’ formulations (according to pH, temperature and
such as toluene di-isocyanate (TDI) is dissolved in the
other factors) suggest that the technology could become very
solvent mixture. A fine emulsion of the oil phase in water is
important in future. It could also find applications in seed
made by high shear mixing with an aqueous solution of an
treatments, where there might be scope for addition of
emulsifier and a reactive amine, such as ethylene diamine.
selective herbicides to products, particularly with geneti-
An emulsion with droplets of 10–30 lm is formed, and
cally modified crops. Syngenta, Dow AgroSciences and
polymerisation between the isocyanate and the amine
Monsanto appear to be in the lead with microencapsulation
occurs at the oil/water interface giving a polyurea mem-
technology. Syngenta has gained a new lease of life for the
brane around each droplet. Alternatively the interfacial
insecticide, lambda-cyhalothrin, using its patented ‘‘Zeon
polymerisation process may be carried out by allowing the
technology’’ which encapsulates the active ingredient in very
isocyanate to react with water at the interface to form an
small capsules with thin walls. This enables quick ‘‘knock-
amine in situ, which then reacts with more isocyanate to
down’’ of insects coupled with long-term persistence. The
form a polyurea membrane (Scher 1983). The rate of
company has also overcome toxicity problems with the
release of the active ingredient can be controlled by
insecticide tefluthrin by producing a capsule suspension as a
adjusting the droplet size, the thickness of the polymer
seed treatment formulation. In a similar way, Monsanto has
membrane and the degree of cross-linking or porosity of
developed a safer capsule suspension of the maize herbicide
the polymer. The rate of release of the pesticide is, there-
acetochlor. Dow is able to encapsulate chlorpyrifos as an
fore, a diffusion controlled process.
emulsion and then convert this into a water dispersible
A typical microencapsulated suspension (CS) formula-
granule by fluid bed spray granulation. Bayer CropScience
tion is shown below:-
have a new technology for coating solid particles with a
polyurea/urethane coating. DuPont are looking at liquid wax
coating techniques. Further innovations are expected in
% by weight microencapsulation technology over the next few years that
Active ingredient 10–30 will contribute to safer pesticide use.
Emulsifier 1–5
Polymer 10–15
Solvent 5–15
5.7 Water dispersible granules (WG)
Anti-settling agents 1–3
Water dispersible granules, or dry flowables as they are
Water to 100
sometimes known, are a relatively new type of formulation

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and are being developed as safer and more commercially spray drying involve the filtration and containment of large
attractive alternatives to wettable powders and suspension volumes of hot air. Furthermore, the plants tend to be rather
concentrates. They are becoming more popular because of large and expensive. Dry compaction gives a hard product
their convenience in packaging and use, being non-dusty, with very poor dispersion properties in water unless
free-flowing granules which should disperse quickly when effervescing agents are added to the formulation. Extrusion
added to water in the spray tank. They therefore represent a granulation is one of the safest, most versatile and eco-
technological improvement over wettable powders and nomical process and is probably the most favoured process
imitate liquids in their handling characteristics. They can used by agrochemical companies at the present time, fol-
be packed into paper bags or cartons with the minimum of lowed closely by fluid bed spray granulation.
contamination and pack disposal problems. The dispersion time in water is a very important prop-
The technology for water dispersible granules is rather erty and to ensure that no problems occur in the spray tank
complex because they can be formulated using various it is necessary for all the granules to disperse completely
processing techniques, but in each case the resultant within two minutes in varying degrees of water tempera-
product must redisperse in the spray tank to give the same ture and hardness. This can be achieved by optimising the
particle size distribution as the original powder or sus- formulation additives and process parameters (Bell 1990).
pension from which it is made. The most important Water dispersible granules usually contain a wetting
processes for producing water dispersible granules are as agent and a dispersing agent in the same way as a wettable
follows (Capes 1980): powder or a suspension concentrate. They may also contain
a water soluble salt to act as a disintegrant in the spray
• pan granulation
tank. The remainder of the formulation is usually a water
• high speed mixing agglomeration
soluble or a water dispersible filler. A typical WG formu-
• extrusion granulation
lation is shown below:
• fluid bed spray granulation
• spray drying
% w/w
Several factors, such as the physico-chemical properties
of the active ingredient and additives, need to be consid- Active ingredient 50–90
ered when deciding upon which process to use. These Wetting agent 1–5
factors and the various processing techniques used to make Dispersing agent 5–20
water dispersible granules determine the main properties of Disintegrating agent 0–15
the final product in terms of granule shape and size, degree Soluble or insoluble filler to 100
of dustiness and ease of dispersion into water.
A comparison of WG processing techniques is given in
Table 1. It can be seen that skill and experience are A survey of the patent literature shows a major surge in
required to obtain satisfactory products by each type of the number of patent applications for WG formulations
process. Pan granulation has been used for many years since about 1990. This has led to the introduction of a large
particularly in the USA, but can be a dusty operation and is number of WG formulations in developed countries to
now much less popular. Fluid bed spray granulation and satisfy the demands for safer, environmentally friendly

Table 1 Comparison of granulation processes


Method Product Plant Materials Comments

Pan Spherical, usually soft Optional size, some Suitable for heat High operator skill required
2–4 mm dia. recycle. sensitive materials. Dusty operation.
High speed Irregular shapes 1–2 mm dia. Optional size, some Suitable for heat Build-up product of on walls.
mixer recycle. sensitive materials.
Extrusion Compact granules 0.6–1.2 mm Optional size, very Suitable for most Versatile process. Requires
dia. 2–10 mm length. small recycle. materials. efficient powder/water mixing.
Dry compaction Hard granules, tablets, Optional size, some Suitable for most Dispersion poor without
briquettes. recycle. materials. effervescing agents.
Spray drying Small uniform spheres, Large scale only, Care needed for heat High air volumes. Single stage
50–200 microns. small recycle. sensitive materials. process.
Fluidised bed Small uniform spheres, Large scale only, Care needed for heat High air volumes. Single stage
spray drying 150–350 microns. small recycle. sensitive materials. process.

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Environmentalist (2008) 28:35–44 43

formulations in easily disposable packaging. For example, phased out because of operator handling safety problems.
in the USA it is estimated that WG formulations represent Water-based flowable suspensions (FS) are more environ-
about 20% of all formulation types approved for use, mentally friendly than powders or solutions, have good
compared with about 10–15% in Europe and a very low retention on seed and are now the preferred formulation for
number in the rest of the world. seed treatments.
Figure 1 shows the appearance of WG products made by The technology for producing flowable suspensions is
three different processes, and a comparison of their rate of similar to that for producing suspension concentrates and
dispersion in water. the surfactants used are also similar to those used for
suspension concentrate formulations. Extra thickeners/an-
tisettling agents are usually added to prevent separation of
6 Seed treatment formulations the dispersed phase because these products are generally
applied directly to the seed without dilution. Seed treat-
Although most pesticide formulations are applied by ment formulations can be applied to seeds in simple
spraying onto crops or weeds, a significant amount of rotating mixing bowls, auger mixers such as the Plantector,
fungicide and insecticide products are applied directly onto or sprayed into rotating bowls such as the Rotostat or the
seeds prior to planting into the soil. It is estimated that the Centaur (Jeffs 1986). High value seeds such as vegetable
market value of seed treatment formulations currently and horticultural seeds are sometimes coated with poly-
represents about 3–3.5% of the total market for agro- mers to prevent loss of the seed treatment chemical. They
chemical products. Approximately 50% of all seed may also be pelleted with clays and polymers to produce a
treatment products are applied to seeds in Europe. Fungi- spherical seed pellet which is easy to handle and plant.
cides dominate the seed treatment market with about a 70% Because seed treatments are applied directly to the seed,
share. The most important seed treatment applications are there is very little wastage of active ingredient (less than
on small grain cereal seeds, which comprise over 50% of 1% of the area treated, compared with whole area spray
the world market and over 60% of the European market. application). Seed treatments are, therefore, seen as a very
Products for seed treatment fall into four categories: efficient means of targeting pesticides to crops and are
regarded as an environmentally safe way of applying pes-
ticides. They may become more important in the future as a
• powders for dry seed treatment DS
means of protecting and adding value to genetically mod-
• water slurriable powders for seed treatment WS ified seeds.
• non-aqueous solutions for seed treatment LS
• flowable suspensions for seed treatment FS
7 Bioenhancement

The choice of formulation type is usually governed by There is increasing pressure from government regulatory
the physico-chemical properties of the active ingredients, authorities to reduce the application load of active ingre-
the type of application equipment available or market dients on the environment, and this can sometimes be
preference. Powder formulations (DS) are dusty and have achieved by including surfactants and other adjuvants in
poor retention on seed. Water-slurriable formulations (WS) the formulation in order to enhance biological activity. In
are still used to a certain extent, particularly in France. some cases, the regulatory authorities require specific data
Solvent-based formulations (LS) are gradually being on the formulation which includes the biological enhancing
adjuvant. The potential effects of surfactants as built-in-
WATER DISPERSIBLE GRANULES (WG)
wetters to formulations are:
• better foliar wetting and spreading
Extrusion Granulation • better adhesion and retention of the droplets
Faster • reduced droplet size of the spray
dispersion • increased drying time and water retention
in water
Fluid Bed Agglomeration • increased uptake and translocation in plant.
Nonionic surfactants are often used as built-in-wetters to
give the above benefits. They can increase the solubility of
Spray Drying the pesticide in the droplet by micellisation, making it
easier for the active ingredient to enter the target. Built-in-
Fig. 1 WG products made by three processes wetters are useful for hydrophilic active ingredients, such

123
44 Environmentalist (2008) 28:35–44

as paraquat and glyphosate, to enhance their uptake Capes, C. E. (1980). Particle size enlargement (Vol. 1). Amsterdam:
through the leaf surface. They may also improve the Elsevier.
Foy, C. L. (Ed.), (1992). Adjuvants for agrichemicals. Boca Raton,
physical compatibility of spray tank mixtures. Florida: CRC Press.
No universal surfactant wetter exists for all pesticides Foy, C. L., Pritchard, D. W. (Eds.), (1996). Pesticide formulation and
and it is necessary to carry out stability tests and biological adjuvant technology. Boca Raton, Florida: CRC Press.
activity tests with a range of different surfactant wetters to Heath, D., Knott, R. D., Knowles, D. A., Tadros, T. F. (1984).
Stabilisation of aqueous pesticidal suspensions by graft copoly-
find the optimum system. However, surfactants such as mers, In H. B. Scher (Ed.) Advances in pesticide formulation
aliphatic alcohol ethoxylates and aliphatic amine ethoxy- technology, ACS Series 254 (pp. 11–28). Washington, DC:
lates are often used. The mechanism of action of surfactant American Chemical Society.
adjuvants in contact with the target organism is not fully Holden WTC (1992). Future formulation trends—the likely impact of
regulatory and legislative pressures, Brighton crop protection
understood, but it seems that lowering the interfacial ten- conference (Vol. 1, pp. 313–320). Brighton: BCPC.
sion, reducing the contact angle and increasing the Holloway, P. J., Stock, D. (1990). Factors affecting the activation of
movement of pesticide through the leaf surface are all foliar uptake of agrochemicals by surfactants, In Karsa D. R.
important processes (Holloway and Stock 1990). (Ed.), Industrial applications of surfactants II (pp. 303–337).
Cambridge: Royal Society of Chemistry.
More recently there has been a trend towards introduc- Jeffs, K. A. (Ed.), (1986). Seed treatment, second edition. Bracknell:
ing surfactants which are themselves more environmentally BCPC Publications.
friendly in terms of biodegradability and ecotoxicity. For Knowles, D. A. (1995). Trends in the use of surfactants in agricultural
example, surfactants based on sugar ethers, such as alkyl formulations. In Pesticide Outlook, 6(3), 31–34.
Knowles, D. A. (1995). Preservation of agrochemicals In F. F.
polysaccharides, have good biodegradability and low eco- Morpeth (Ed.) Preservation of surfactant formulations (pp. 140–
toxicity especially to fish, and are being used increasingly 145). Glasgow: Blackie.
as biological enhancing adjuvants (Knowles 1995). Knowles, D. A. (Ed.), (1998). Chemistry and technology of
Most of the pesticide formulations, process technology agrochemical formulations. The Netherlands: Kluwer Academic
Publishers.
and surfactant adjuvants mentioned in this paper are dis- Scher, H. B. (1983). Human welfare and the environment. In
cussed more fully in two books which have been published Miyamote J., Kearney P. C. (Eds.), IUPAC pesticide chemistry
in the last few years. The first book covers recent devel- (pp. 295–300). Oxford: Pergamon Press.
opments of pesticide formulations and applications in Seaman, D. (1990). Trends in the formulation of pesticides—an
overview. Journal of Pesticide Science, 29, 437–449.
developing countries (Van Valkenburg et al. 1998). The Tadros, T. F. (Ed.), (1987). Solid/liquid dispersions. London:
second book gives a comprehensive state-of-the-art review Academic Press.
of the chemistry and technology of agrochemical formu- Tadros, T. F. (1988). Proceeding of 2nd world surfactants congress,
lations, packaging and applications worlwide and likely section D. Paris, 271–283: ASPA.
Tadros, T. F. (1995). Surfactants in agrochemicals, surfactant science
future trends, and also discusses recent changes to regula- series Vol. 54. New York: Marcel Dekker.
tory control requirements (Knowles 1998). Valkenburg, W. van (Ed.), (1973). Pesticide formulations. New York:
Marcel Dekker.
Valkenburg, W., van Sugavanam, B., Khetan S. K. (Eds.), (1998).
References Pesticide formulation—recent developments and their applica-
tions in developing countries. New Age International Publishers,
India: UNIDO.
A complete updated list of publications by Alan
Knowles on pesticide formulations, additives and
adjuvants is available on his company website,
www.form-ak.com

Bell, G. (1990). The structure/physical property relationships of a


model water dispersible granule. Journal of Pesticide Science,
29, 467–473.

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