Introduction

• Fungicidal activity of copper sulphate was first identified by Prevost

in 1807 but not used till 1885. Later these fungicides predominated
the field of fungicidal plant disease control for more than 50 years.
They can be classified as follows:

●
● Bordeaux mixture,
●
● e.g: Perenox,etc. Bordeaux paste,
Burgundy mixture,etc.
Cuprous Copper
oxide sulphate
preparatio preparatio
ns ns

●
● e.g; Fytolan, ●
● Chaubattia paste.
Blitox-50,etc.
Copper Sulphate Preparations

Bordeaux mixture : It is a combination of copper

sulphate, lime, and water.
It is an effective fungicide and bactericide that has
been used for decades to control diseases of fruit,
nut trees, vine fruits, and ornamental plants.
These natural minerals, when mixed in the correct
order, provide long-lasting protection to plants
against diseases.
Chemical Reaction:
CuSO4 + Ca(OH)2 Cu(OH)2 +CaSO4
 Background
• It was discovered by Pierre-Marie-Alexis
Millardet in 1882. Originally known as Boullie
Bordelaise.
• In the 19th century, several outbreaks of vine
diseases occurred among the Vitis vinifera vines
of the classicial European wine regions. These
outbreaks were caused by pests. These pests
included not only the Great French Wine Blight
caused by the aphid Phylloxera vastatrix, but
also mildew and other diseases caused by fungi.
 Cont..
• After the downy mildew had struck, botany
professor Millardet of the University of Bordeaux
studied the disease in vineyards of the Bordeaux
region then noted that vines closest to the roads did
not show mildew, while all other vines were
affected. After inquiries, he found out those vines
had been sprayed with a mixture of CuSO4 and lime
to deter passersby from eating the grapes, since
this treatment was both visible and bitter-tasting.
This lead to conduct trials with this treatment.
 Cont…
• Later on Millardet and Gayon tested a
series of formulae and ultimately found that
low concentration of copper sulphate and
lime is more effective as compared to
higher concentration or more oftenly
concentration used was 4lb:4lb:50.gallon.
• In France, the use of Bordeaux mixture
has also been known as the Millardet-
David treatment.
Preparation of Bordeaux mixture
(1 % or 1:1:100)
1. Dissolve 1kg of powdered copper sulphate in
50 litres of water in a plastic bucket.
2. Prepare milk of lime in another plastic bucket
by dissolving 1kg of quick lime in 50 litres of
water.
3. Pour the copper sulphate solution and the milk
of lime from the above two vessels into a third
one by gently stirring the mixture all the while.
This will give a final volume of 100 litres of 1%
strength.
 Cont…
• It should be sprayed while fresh, on standing it
losses its fungicidal properties. By adding sugar or
jaggary @ 0.5 lb in 50gallon of water. The mixture
stabilize by this way will not deteriorate for several
days under normal condition.
Why BM use fresh ?
• BM is hydrogel , highly hydrated, tenacious and on
standing it undergoes crystallization and it colour
changes from bluish to violet which indicates the
formation of copper due to this losses it effectivety .
 Test before use
The mixture is to be tested before use for the
presence of free copper, which is phytotoxic to the
plant.
To test bordeaux mixture for free copper, a few
drops of 10% solution of potassium ferrocyanide are
to small quantity of prepared BM if reddish brown
deposit is formed immediately ,more lime should be
added to the mixture if potassium ferrocyanide is not
available , dip a clean iron blade in the mixture. If the
blade shows a reddish colour, add lime to the mixture
till the blade does not show staining on dipping.
 Solubility of BM
• The inherent solubility of BM is quite low . According to
Goldsworthy and Green , BM in equilibrium with water yields
solution containing about 4 ppm. After this material was
thoroughly dried, as in a spray film, the solubility decreased to 0.2
to 0.3 ppm . But we know that Cu in BM is toxic to fungal spores
at higher concentration.
• Therefore the copper must be solubilize to the extend of toxic
level and now it is achieve by few mechanisms have been
explained :
• Action of the atm CO2 and ammonium salts dissolved in rain
water
• Action of the secretions from fungus
• Secretion from the healthy or wound surface of host plants .
 Mode of action
• Bordeaux mixture achieves its effect by means
of the copper ions (Cu2+) of the mixture. These
ions affect enzymes in the fungal spores in such
a way as to prevent germination. This means
Bordeaux mixture must be used before the
fungal disease has struck.
• Thorough coverage of the spray on the plants is
necessary. The Bordeaux spray continues to
adhere well to the plant during rain, though in
the long term it is washed off by rain.
Merits and Demerits
Merits
• It is having natural tenacity
• It is relatively cheap
• Safe to handle
• Control large number of diseases
Demerits
• Delays ripening
• It is reactive with metal containers
• Phytotoxic to some crops
• Botheration of preperation
Bordeaux Paste And Chestnut
Compound
Bordeaux paste
1:1:10
Dissolve 100 g of Copper sulphate and 100 g of quick lime each
in 500ml of water separately. Mix together to make 1 lt of the
paste. This can be applied to the cut ends of stem or nursery
stock with brush.
Cheshunt compound
The compound contains 60 g of Copper sulphate and 330 g of
diammonium carbonate. These two are well powdered and
thoroughly mixed. The dry mixture is stored in an airtight glass
container for 24 hours before use. About 25 g of this mixture is
dissolved in a little hot water solution is made up 8 liters with
cold water and used for soil drenching.
Cheshunt mixture
Structure:
1:1 mixture of copper sulphate and
diammonium carbonate
Burgundy mixture
• Burgundy mixture, named after the French district where it was
first used to treat grapes and vines, is a mixture of copper
sulphate and sodium carbonate. This mixture, is used as a
fungicidal spray for trees and small fruits.
• Burgundy Mixture, also known as “Sal soda Bordeaux,” is used
as a fungus preventative applicant on plants before fungi have
appeared.

• NaCO3
• CuSO4
Synthesis and composition
 Burgundy Mixture is made by combining
dissolved copper sulphate and dissolved
sodium carbonate.
 Dissolved copper sulphate ratios generally
range from 1:1 to 1:18.
 Sodium carbonate is generally added in
higher quantities and at a dissolved ratio of
1:1.5.
Uses and mode of action
 Burgundy Mixture is used as a prevention for trees and
small fruits. This occurs because the Cu(II) ions are
capable of interfering with enzymes found within the
spores of many fungi, prevent germination from
occurring.
 Unfortunately, the mechanism for copper antifungal
properties is not well understood though it is often
thought that interactions with the copper and negatively
charged portions of the cellular walls of the bacteria,
promoting an altered shape and increasing membrane
permeability, which alters the homeostasis of the cell and
can lead to insufficient uptake and storage of essential
nutrients and ions.
Copper Carbonate Preparations
Chaubattia paste: It is used in apple orchards
for the control of stem black, stem brown and
pink diseases. The paste was developed at
government fruit research station Chaubattia
(Almora) Uttarakhand. This was developed as a
wound dressing fungicide.
Copper carbonate hydroxide
 Cont..
The paste is prepared by mixing copper
carbonate 800 g and red lead 800 g in 1lt of
lanolin or raw linseed oil . These are mixed in
some glass or chinaware pot .
The paste has the advantage that
 it is not washed off easily by rain .
 It is very good antiseptic ,
 It is applied to pruned part of apple ,pear
,peach against many diseases .
Fixed Copper Fungicides

Fixed copper fungicides

Copper oxychloride preparation Cuprous oxide preparation

Copper oxychloride Copper hydroxide

 Copper Oxychloride Preparations

COPPER OXYCHLORIDE:
ClCu2H3O3
• Origin: Cu fungicides since 1880s; 1968, Kennecott
Corp.
• Trade Name: Blitox 50, Blue Copper-50, Cupramar,
Fytolan.
• Description: A protectant copper fungicide and
bactericide .
• Mode of Action: Absorbed copper disrupts the enzyme
systems of pathogens
 Cuprous Oxide Preparations

COPPER HYDROXIDE
• Origin: Cu fungicides since 1880s; 1968, Kennecott Corp.
• Chemical Group: Inorganic.
• Chemical formula: (Cu(OH)2) .
• Trade Names: Kocide3000, Champion WP, etc.
• MOA: Multi-site, non-specific denaturizationof proteins and enzymes [M1].
• ROA: Broad spectrum protectant vs. foliar diseases caused by chromistan
and eumycotan fungi, and bacteria (disease control and frost protection).
• Description: Inorganic copper compound used to protect against a
number of fungal and bacterial diseases .
• Mode of Action: Absorbed copper disrupts the enzyme systems of the
pathogens.
Mechanism Of Fungicidal Action
• Horsfall, Marsh and Martin suggested that cuprous oxide killed
spores by a different mechanism from that of cupric oxide. Martin
(1942) found that cupric chloride has greater inherent toxicity.
• Solubilisation theory: workers who believe in solubilization theory
presume that the fungal cells accumulate through water soluble
complexes which later dissociates to give free copper ions. On the
other hand some workers believe that fungal cells accumulate free
ionic copper from Bordeaux mixture that no solubilisation is required.
• Disruption of cell integrity: Copper as Cu+, is readily accumulated
by sensitive fungi. It forms complexes with enzymes that possess
sulphur hydral, hydroxyl, amino or carboxyl groups, inactivating them
and leading to a general disruption of metabolism and breakdown of
cell integrity. As with all immobile protectants, copper products have
to be used frequently in order to achieve adequate coverage and to
maintain disease control in a growing crop.
 Effect of copper on Oxidation-
Reduction Systems
Copper is known to be strong pro-oxidant. G.
and Villedieu (1923), a French couple, wrote
a series of papers beginning in 1920 to show
that copper fungicides kill spores not by
direct action but rather by catalytic oxidation.
This theory was supported by few workers.
The direct experimental proof of the
argument was so unconvincing that it has
been brushed aside by most researchers.
• Certain workers in the field of fungi toxicity, especially
Horsfall, stress the supposed great difficulty of
penetration of toxicant into the spores.
• Investigation with copper have been extensive and it is
clear that copper penetrate into the interior. After a short
exposure the effect of copper is fungistatic and if the
spores are removed from treating solution and then
treated with the dilute acid, then germination will
proceed.
• If the exposure period is long as an hour the ability to
germinate cannot be restored. Copper thus act as a
fungistat.
Permeation of the cell wall
• The mechanism of permeability is not certainly understood.
Bonder and Terenyi were not able leach out the copper when
it went in as an ammonia complex. This meant to them that
copper had permeated the spore wall into the interior where
it was not accessible to the acid.
• Nageli(1893) showed that the protoplast of copper treated
Spirogyra crumbled presumably because copper entered the
cell. The simplest hypothesis is that the fungicidal reaction of
copper compounds involve the cupric ions.
• As already noted, Prevost(1807) found that the germination of
spores was inhibited by extremely low concentration and
hence arise an idea that the spore was able to remove
copper from solution until a toxic accumulation has been
reached.
• The later worker concluded that copper is
accumulated passively by unspecific reactions with
the cell constituents. And concluded that the
fungicidal, or accurately the fungistatic action of
copper arise through a nonspecific denaturation of
proteins and enzymes. Those workers who believe
in solubilization hypothesis presume that the fungal
cell accumulate the water soluble copper complex
which later on dissociate to give free cupric ions. On
the other hand some workers suggest the evidence
that fungal cell accumulate free ionic copper from
Bordeaux mixture and no solubilization is needed.
These free ions precipitate or denature the proteins.
 Enzyme are protein and it would therefore be
expected that the heavy metal would inactivate
these catalysts.
 The enzyme with free sulphur hydral group
appear to be susceptible to inactivation by ions
of heavy metals. It is therefore quite possible
that copper kills spores by combining with the
sulphur hydral group of certain enzymes.
 In 1905, Ewert suggested that copper has a
deleterious effect inside a leaf by poisoning the
diastase that is active in the starch-sugar
system. This suggests that the copper might
poison still other enzyme systems.
Conclusion
• In summarizing available information available on the
mechanism of the fungicidal action of copper it
appears most likely that exudates, such as, hydroxy
and amino acids, produced from fungus spores react
with the insoluble copper fungicides to form soluble
toxic copper complexes.
• While this is the primary fungicidal action it is
supplemented by the copper brought into solution by
the atmospheric agencies and host plant exudates.
• These two agencies, however, likely play the most
important role in phytotoxicity or host plant injury.
THANKS