Note: Descriptions are shown in the official language in which they were submitted.
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FUNGICIDAL AND BACTERICIDAL COMPOSITIONS
FOR PLANTS CONTAINING PHOSPHONATE AND PHOSPHATE
SALTS, METAL CHELATES, AND DERIVATIVES THEREOF
RELATED APPLICATIONS
The present patent application is a continuation-in-part of U.S. Patent
Application
Serial No. 09/702,417, filed October 31, 2000, which is a continuation-in-part
of U.S.
Patent Application Serial No. 09/387,100, filed August 31, 1999 now U.S.
Patent No.
6,139,879, which is a continuation-in-part of U.S. Patent Application Serial
No.
08/881,968, filed June 25, 1997 now abandoned and which is a continuation-in-
part of
U.S. Patent Application Serial No. 09/419,127, which is a continuation-in-part
of U.S.
Patent No. 5,997,910, which is a divisional of U.S. Patent No. 5,800,837,
which is a
continuation-in-part of U.S. Patent No. 5,736,164.
FIELD OF THE INVENTION
The present invention is broadly concerned with fungicidal and bactericidal
compositions, and methods of use, which provide improved efficacy in
controlling fungus
and bacterial infections in plants. More particularly, the compositions and
methods relate
to metal chelates, and preferably to a copper chelate in the form of Cu-EDDHA
(copper
ethylenediamine-di-o-hydroxyphenylacetic acid), including an effective amount
of
phosphate (P04) and phosphonate (P03), in aqueous solution.
BACKGROUND OF THE INVENTION
Fungicides, as well as bactericides, are either chemical or biological agents
used to
protect agricultural crops from infectious pathogens which, if left
uncontrolled, result in
the weakening or destruction of a plant. In regards to. agricultural crops,
this is
unacceptable, as economic losses will result. Specific pathogens which tend to
have an
undesired effect on various agricultural crops include Citrus Greasy Spot,
Citrus Melanose,
Oak Leaf Blister, Erwinia, Xanthomonas, and Alternaria. In the interest of
protecting
valuable agricultural crops, it is desired to have a fungicide and bactericide
composition
that readily eliminates or treats these various plant maladies, as well as
other infectious
agents.
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Copper (Cu) compounds that are active as fungicides and bactericides have been
in
agricultural use since the advent of Bordeaux in the grape vineyards of France
in the early
1800s. It has been observed that various types of copper compounds can be used
to
effectively treat various plant pathogens. As such, many different
formulations of
fungicides employing copper compounds, such as wettable powders, water based
flowables, and dry flowables, are commonly used today in modern agricultural
applications. While copper compounds are known to impart desirable fungicidal
and
bactericidal properties, there are associated problems. Specifically, known
copper
compounds are typically either phytotoxic, non-soluble, or ineffective as a
fungicide or
bactericide.
Generally, copper compounds used as fungicides have, for the most part, been
inorganic in form when applied to agricultural uses. The inorganic copper
compounds
have been used because they have been observed to be non-phytotoxic. Organic
forms of
the copper compounds, while beneficially water soluble, have been found to be
generally
phytotoxic, especially in foliar applications.
Water soluble, copper compounds such as CuS04, though effective to inhibit
germination of fungus spores, when used in foliar applications to agricultural
crops can be
phytotoxic. Therefore, relatively insoluble forms of inorganic copper
compounds, such as
cupric hydroxide, have been found to be more effective fungicides. Note,
however, that not
all water insoluble Cu compounds are fungicidal or bactericidal. It is known
that the in-
vitro fungicidal activity is largely dependent on the copper solubility in the
spore exudate
and in the fungal cell. Also, despite the phytotoxicity, certain organic
copper compounds
have some utility as fungicides. An example of a suitable organic copper
compound is
CUTRINE (Cu salt of tri-ethanol amine) which is quite effective as an aquatic
algicide, but
unsuitable for use in other foliar applications.
While inorganic copper compounds are beneficially non-phytotoxic, they
generally
suffer from low water solubility. Modern day agricultural uses of inorganic
copper
compounds as fungicides employ varying forms of copper compounds having
relatively low
water solubility and include, for example, cupric hydroxide, tri basic copper
sulfate, and
tank mix combinations (with heavy metal ethylene-bis-di-thiocarbamate
fungicides to
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enhance the bactericidal activity against certain important agricultural
bacterial such as
Xanthomonas, Pseudomonas, and Erwinia). The lack of solubility of the
inorganic copper
compounds is an undesirable problem. Because known and popular copper
fungicides are
largely water insoluble, they are normally applied in relatively large volume
aqueous
suspensions and, as such, are readily removed by rain after application.
Frequent
applications are, thus, necessary at short intervals -- an application process
which is
expensive and environmentally imprudent.
Inorganic copper compounds alone are also not particularly effective in
treating
certain forms of fungus known as Phytophthora. From 1845 to 1846, the Irish
Potato Famine
occurred, which was one of the most devastating crop failures in the history
of the world.
The potato famine was caused by the disease late blight which resulted in
harvested potatoes
quickly decaying, making them unsuitable for consumption. The disease is also
known to
cause defoliation in infected plants. Late blight is caused by a Phytophthora
infestans
infecting potato and tomato plants. As can be gathered, the Phytophthora
fungus, if not
controlled, can cause major economic damage to agricultural crops, with the
resulting damage
causing the loss of millions of dollars in crop revenues. Additionally, there
is the possibility
of significant reduction of the potato and tomato supply available to
consumers.
To control late blight, it has been recommended that the contaminated potatoes
and/or
tomatoes be buried in deep pits and covered by at least two feet of soil. In
Northern
Latitudes, the potatoes or tomatoes can be spread on the soil surface and
allowed to freeze
during the winter. These methods temporarily prevent the spread of the
disease, but do not
prevent infection and attack by the Phytophthora infestans. The treatment only
addresses
plants and crops after they have been destroyed. For this reason, it is
desired to have a
composition or method that can be administered to potato and tomato fields to
actively
control and prevent the spread of the Phytophthora infestans infestation.
Some species of the Phytophthora genus can be controlled, such as Phytophthora
parasitica. In particular, fosetyl-al (ethyl phosphonate) can be administered
to plants to
control diseases such as root rot caused by Phytophthora parasitica. As such,
it is known
that many phosphonate (P03) compositions are highly effective in combating the
disease root
rot and, in particular, some of the species of the genus Phytophthora.
Unfortunately, fosetyl-
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al and other phosphonates, alone, do not control late blight and similar
Phytophthora diseases
caused by the species Phytophthora sojae. Thus, it is desired to have a method
or
composition that readily inhibits infection by and proliferation of
Phytophthora infestans.
Phosphorus is an essential element in plant nutrition because it governs the
energy
producing reactions, including those that are oxidative and photo
phosphorylative.
Phosphorous is essential to the production of adenosine diphosphate (ADP) and
adenosine
triphosphate (ATP). Energy-rich phosphate bonds of ADP and ATP provide the
energy for
many of the physiological reactions that occur in plants. As such, various
forms of
phosphorous are absorbed by plants for use as part of the photosynthetic
process.
The element phosphorous appears in numerous general forms, including
phosphonate
(P03) and phosphate (P04). The term "phosphonate," sometimes also referred to
as
"phosphite," means the salts (organic or inorganic) of either phosphoric acid
or phosphorous
acid. Phosphoric and phosphorous acids have the formula H3P03 and a molecular
weight of
82.00. Their structures from the International Union of Pure and Applied
Chemistry are
shown below:
OH OH
H -P=O HO-P
OH OH
Phosphoric Acid Phosphorous Acid
CA: 13598-36-2 CA: 10294-56-1
The term "phosphate" means the salts (organic or inorganic) of phosphoric acid
having the formula H3P04, molecular weight of 98.00 and having the following
structure:
O
HO-P-OH
OH
Phosphoric Acid
CA: 7664-38-2
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In the past, various phosphonate compounds have been proposed as useful in
fimgicidal and fertilizer compositions for application to plants. See, e.g.
U.5. Patent Nos.
4,075,324 and 4,119,724 to Thizy, describing phosphorous acid, its inorganic
and organic
salts, as a plant fungicide; U.S. Patent No. 4,139,616 to Dueret, describing
fungicidal
compositions based on phosphorous acid esters and salts thereof; U.S. Patent
No. 4,542,023
to Lacroix et al., describing organophosphorous derivatives as possessing
systemic and
contact fungistatic and fungicidal activity; U.S. Patent Nos. 4,698,334,
4,806,445, and
5,169,646 to Horriere et al., describing fungicidal compositions based on
alkyl phosphonates;
U.S. Patent Nos. 4,935,410 and 5,070,083 to Barlet, describing fixngicidal
aluminum tris-
alkyl-phosphonate compositions; and U.S. Patent No. 5,514,200 to Lovatt,
describing
formulations of phosphorous-containing acid fertilizer for plants. (The
teachings of the
proceeding U.S. Patents are hereby incorporated by reference.) The above
references,
disclosing phosphonate compositions, have been found to be effective for
protecting plants
and, particularly, grape vines, citrus and fiwit trees, and tropical plants
against fungal attack.
1 S Note that phosphonate (P03) alone is typically considered an unacceptable
source of
phosphorus (P) for plants. It is known that P03 must be converted to P04 to be
utilized by a
plant.
Once assimilated, phosphonates (P03) have been shown to enhance the plant's
phytoimmune system. The phosphonate induced stimulation of the phytoimmune
system is
triggered by the induction of ethylene production, followed by a rapid
accumulation of
phytoalexins at the site of infection. Phytoalexins are antibiotics which
result from the
interaction between the host plant and a pathogen. The phytoalexins are
synthesized by and
accumulate in the plant to inhibit the pathogen. The phytoalexins will
accumulate at the site
of an infection to prevent further spread of the disease, thereby reducing
symptomatic
expression of the disease.
In the past, phosphates (P04) were not viewed as a solution to pathological
acerbation
of fungal infections or infections produced by other genera. This is because
phosphates (P04)
are viewed primarily as a fertilizer with only limited, or even detrimental,
phytoimmune
properties. For example, U.S. Patent 5,514,200 teaches that phosphate
fertilizers inhibit
beneficial symbiosis between plant roots and mycorrhizal fungi, and further
promote bacterial
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and fungical growth in the rhizosphere, including the growth of pathogenic
fungi and other
soil-borne organisms. (Col. 2, lines 18-28). Phosphates (P04) have also been
considered to
be a competitive inhibitor for phosphonate assimilation, thus inhibiting the
ability of
phosphonates (P03) to protect against fungus attack. See, Pegg, K.G. and
deBoer, R.F.,
"Proceedings of the Phosphonic (Phosphorous) Acid Work Shop," Australiasian
Plant
Pathology, Vol. 19 (4), pp. 117 and 144, 1990. Yet further, phosphonates (P03)
and
phosphates (P04) were believed to be "biological strangers," with the presence
of
phosphonates (P03) or esters of phosphonates, exerting little or no influence
on enzyme
reactions involving phosphates. Robertson, H.E. and Boyer, P.D., "The
Biological Inactivity
of Glucose 6 - phosphonate (P03), Inorganic Phosphites and Other Phosphites,"
Archives of
Biochemistry and Biophysics, 62 pp. 380 - 395 (1956).
Thus, both forms, inorganic and organic Cu compounds, as well as phosphates
(P04) and
phosphonates (P03) when used individually, suffer from problems. Therefore,
the need
exists for a highly water soluble Cu compound based fungicide and bactericide
that is not
phytotoxic. A need also exists for a water soluble Cu compound based fungicide
and
bactericide that reduces the adverse Cu load on the plant, thus reducing the
non-target
impact to the enviromnent. Further, a need exists for such fungicidal and
bactericidal
compounds that permit use of other metals such as manganese, zinc, iron,
copper and
mixtures thereof, as may be desired for specific fungicidal or bactericidal
properties.
Also, the requirements for a successful phosphonate-based fungicide depend on
the
promotion of the phosphonate-induced pathological acerbation of fungical or
other genus
infections. More particularly, it is desired to have a composition and/or
method that prevents
Phytophthora infestans infection and destruction of plants.
SUMMARY OF THE INVENTION
The present invention relates to a metal chelate fungicide and bactericide
composition that also includes effective amounts of phosphate (P04) and
phosphonate
(P03), and methods of using the composition to control fungicidal and/or
bactericidal
infection in plants. Preferably, the chelate is a composition that is a member
of the
EDDHA (ethylenediamine-di-o-hydroxyphenylacetic acid) family, and the metal is
selected
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from the group consisting of iron, copper, manganese, zinc, tin, and
combinations thereof.
Copper, however, is the most preferred metal. Importantly, the present
invention
addresses the problems discussed before, of solubility, phytotoxicity, and
effectiveness. In
particular, the fungicide and bactericide composition of the invention
provides an improved
antifungal and antibacterial composition for use on plants that contains, as
active
ingredients, fungicidally and/or bactericidally effective amounts of the metal
chelates,
phosphonates, and phosphates in aqueous solution. It has been observed that
the
application of the composition of the invention to a plant substantially
eliminates fungus
and bacteria disease. Not only is the composition effective in eliminating
fungus and
bacteria, but it is substantially non-phytotoxic. Also, the metal chelate in
the composition
of the invention is soluble in aqueous solution. Thus, the composition
provides for
protection of plants against fungal and bacterial infections without the
attendant
phytotoxicity.
Importantly, the composition of the invention is a singular product that
imparts
antifungal and antibacterial protection upon application without being
phytotoxic. The
composition of the invention is, additionally, environmentally safe,
comparatively
inexpensive to use, and has low mammalian toxicity.
Essentially, the present antifungal and bacterial composition is comprised of
an
active material, a fungicidally and/or bactericidally effective amount of a
metal chelate, and
an agriculturally acceptable carrier, such as water. The preferred fungicidal
and
bactericidal compositions is comprised of water and a metal chelate selected
from the group
consisting of Fe-EDDHA (iron ethylenediamine-di-o-hydroxyphenylacetic acid),
Cu-
EDDHA, Mn-EDDHA, Zn-EDDHA, Sn-EDDHA, and mixtures thereof. Other family
members of EDDHA can be substituted therefor, including pEDDHA and EDDHMA.
Desirably, both antifungal and antibacterial effects are achieved with one
composition. .
The composition of the invention also includes phosphate (P04) and phosphonate
(P03) constituents which, when combined, particularly provide for a
synergistic effect that
results in the substantial protection against infection of plants by
Phytophthora, especially
Phytophthora infestans. As such, the phosphate and phosphonate constituents
can be
combined to form a composition, which can be applied to plants, especially
tomatoes and
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potatoes, to prevent infection by Phytophthora infestans and diseases caused
by such
infection. Application can be achieved by using either a dry mix or an aqueous
solution.
The preferred composition for preventing Phytophthora will be comprised of at
least
one potassium phosphonate and at least one potassium phosphate, as it has been
found that
these two constituents, when combined, will cause a synergistic effect which
results in the
substantial prevention of infection by Phytophthora. It is believed, that the
rate by which
infection is prevented is increased by at least 100% when the two constituents
are combined,
as compared to the additive effect of the combined salts. The two constituents
will be
combined in an amount sufficient to prevent infection and manifestation by
various disease
causing organisms, with the particular amounts combined dependent upon the
particular
species of plant to be treated, the specific disease causing organism to be
treated, and the
particular phosphate salt and phosphonate salt that will be combined.
The composition should be applied at least once to the plants to be treated.
While one
application is sufficient, it is typically preferred to make multiple
applications. Essentially,
any plant infected by Phytophthora can be treated, with it most preferred to
apply the
composition to potato and tomato plants. It should also be noted that the
composition not
only inhibits Phytophthora, but is environmentally safe, inexpensive to use,
and has low
mammalian toxicity.
Phosphonate salts useful in the practice of the invention also include those
organic
and inorganic salts taught by U.S. Patent Nos. 4,075,324 and 4,119,724 to
Thizy et al., (see,
e.g., col. 1, In. 51-69 through col. 2, In. 1-4).
DETAILED DESCRIPTION
The present invention relates to a composition that is both a fungicide and a
bactericide and a method for using such composition. The composition is
advantageously
useful in eliminating or at least substantially reducing the effects of
infection by various
fungal and bacterial plant pathogens. The composition of the invention
contains at least
one metal chelate in aqueous solution, with it preferred that the chelate be a
member of the
EDDHA family of compositions, at least one phosphonate salt, and at least one
phosphate
salt. The metal attached to the chelate can be selected from any of a variety
of metals,
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especially those selected from rows 4 or 5 of the periodic table of the
elements, particularly
metals of row 4.
As stated, one component of the present composition is a metal chelate,
preferably
in an amount of water to form an aqueous composition. The metal chelate can be
formed
by a known process, with the reaction summarized as reacting an amount of
metal chloride
hexahydrate with water and an amount of mono-amide di-hydrochloride in a
reaction
vessel. A catalyst, such as sodium hydroxide, is then added which will cause
formation of
the metal oxide EDDHA. Among the metal hexahydrates that can be reacted with
the
mono-amide di-hydrochloride are iron, zinc, tin, manganese, and copper,
preferably zinc,
manganese, and copper, and more preferably copper. The resulting metal
chelates that are
suitable for use include: Fe-EDDHA, Cu-EDDHA, Zn-EDDHA, Mn-EDDHA, Sn-
EDDHA, and combinations thereof. In addition, the corresponding metal chelates
of para-
ethylenediamine-di-o-hydroxyphenylacetic acid (pEDDHA), ethylenediamine-di-o-
hydroxyphenylmethylacetic acid (EDDHMA), and combinations thereof are also
particularly suitable for use.
The term "metal chelate" refers to an organic coordination "complexing"
compound
in which a metal ion is bound to atoms of non-metals, e.g., nitrogen, carbon,
or oxygen, to
form a heterocylic ring having coordinate covalent bonds. The non-metal atoms
may be
attached to the metal ions by from one to six linkages and, thus, are called
uni, bi, tri
dentate, etc., meaning 1-, 2-, or 3-tooth. Suitable metals commonly involved
in chelate
structures include those metals selected from rows 4 or 5 of the periodic
table of the
elements, particularly metals of row 4. Examples of suitable metals include,
but are not
limited to, cobalt, copper, iron, nickel, zinc, tin, and manganese, preferably
copper, iron,
zinc, and manganese, more preferably copper, zinc, and manganese, and most
preferably
copper. Examples of specific metal chelate structures include:
Fe-HEEDTA (hydroxyethylethylenediaminetriacetic acid), Fe-EDTA
(ethylenediaminetetraacetic acid), Fe-DTPA (di-ethylenetriaminepentaacetic
acid), Fe-
EDDHA (ethylenediamine-di-o-hydroxyphenylacetic acid), ethylene-bis-di-
thiocarbamates
of Mn and Zn (EBDC), Cu-EDDHA, Mn-EDDHA, and Zn-EDDHA.
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To form the metal chelate aqueous composition the metal chelate will be mixed
with
an amount of water to form an aqueous solution. Generally, special treatment
of the water
is not required, such as deionizing the water for example. Additionally, the
mixing will
preferably occur under ambient conditions. The metal chelate will be mixed
into the water
in an amount sufficient to cause the finished composition to equal from about
0.01 pounds
to about 2.0 pounds of AI (active ingredient, i.e. the metal) per acre.
Preferably, the
amount of metal chelate is about 0.01 to about 0.8, and more preferably about
0.01 to
about 0.2 pounds of AI per acre. Typically this means adding the metal chelate
to the
water in an amount equal to between about 1% and about 5% by weight (on a
metal basis)
of the total solution. More preferably, the metal chelate will be added in an
amount equal
to between about 2% and about 4% by weight, and most preferably about 3% by
weight of
the total solution.
Once the aqueous composition has been formed by thoroughly blending the
phosphonate salt, phosphate salt, and metal chelate with the water, the
aqueous
composition is then ready for application to plants, in particular
agricultural crops. The
aqueous composition is typically easily applied by spraying or other means of
distributing
the aqueous solution in a sufficient amount to the plants.
The metal chelate must be applied in a sufficient AI amount, without resulting
in
phytotoxicity. Unacceptably high levels of phytotoxicity result in foliar
burn, defoliation
and stem die-back, necrosis, plant stunting, or death. Phytotoxicity can be
rated on an
international scale of 0-10 where 0 is equal to no phytotoxicity and 10 is
complete death of
the plant. It is preferred if the metal chelate is applied in an amount so
that the
phytotoxicity is minimized.
Phytotoxicity rankings of Fe chelates, for example, used in foliar
applications are as
follows: Fe-HEEDTA -- most phytotoxic; Fe-EDTA -- intermediate phytotoxic, Fe-
DTPA
-- less phytotoxic, and Fe-EDDHA -- least phytotoxic. Thus, the Fe-EDDHA is
preferred
because it is the least phytotoxic while still imparting excellent fungicidal
and bactericidal
properties.
Metal chelates disclosed herein will have a water solubility acceptable for
use in the
inventive fungicide and bactericide. For example, the solubility of
sequestrene 138 Fe Iron
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Chelate in pounds per 100 gallons of water, at various temperatures is similar
to the
present metal chelate in aqueous solution. (Solubility weight/100 gals. H20)
is shown in
Table 1 below:
S TEMPERATURE (~C) LBS. OZ.
0 69 11
70 7
75 4
81 11
10 40 84 1
50 88 1
Commercially produced Sequestrene 138 Fe contains 6% Iron as metallic, or 8.5%
iron
as Fez03. The commercial product has a moisture content of not more than 10%.
As
1 S such, this is exemplary of a suitable solubility. Thus, it is desired for
the metal chelate,
in particular the Cu-EDDHA, to have a solubility of about 100% where at least
80 lbs.
of metal chelate is dissolved in 100 gallons of Hz0 at 50° C.
Without being limited to this theory, it is believed that metal chelation
generally
increases the water solubility of the metal ion and the availability in
certain soil
20 conditions of the metal ion where calcareous and high pH situations would
otherwise
prevent metal ions from being available to the plant as a fungicide.
It is believed that certain metal chelates (usually in the form of Mn, Zn, and
Fe)
may be applied foliarly at much reduced rates when compared to inorganic salts
intended for fungicidal use.
2S The preferable method of application is foliar, either by ground or aerial
equipment, but is not limited to that method alone. Injection or soil
applications, for
example, can also be used depending upon the specific crops and pathogens.
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Among the plants that can be treated with the metal chelate in aqueous
solution
are: fruit crops, and agronomic crops, ornamentals, trees, grasses,
vegetables, grains,
and flori-cultural crops, as well as, some aquatic crops, including rice.
The fungicidal and bactericidal properties of the compounds according to the
invention are various, but are particularly interesting in the cases described
in the
following examples.
The following examples set forth preferred concentrations and techniques for
formulation thereof, as well as methods of application and use in test
results,
demonstrating the efficacy of the inventive concentration in protecting plants
against
attack by fungi or bacteria, or both. It is to be understood, however, that
these
Examples are presented by way of illustration only, and nothing therein shall
be taken
as a limitation upon the overall scope of the invention. The specific
components tested
in the Examples were prepared and applied as follows:
To prepare Cu-EDDHA, an appropriate Cu salt need merely be substituted for
the iron salts as discussed before and disclosed in U.S. Patent No. 2,921,847,
which is
incorporated herein by reference.
As used in the Examples, "Ave. % infection" means percent of leaves that
exhibit fungus lesions.
EXAMPLES
Example 1.
Cu-EDDHA and four commercially accepted fungicidal compositions were
applied to Valencia orange on sour orange rootstock. Applications were in 100
gallons
of solution (in the concentrations indicated in the table below) per acre in
mid-summer
to single-tree plots replicated six times in a randomized complete block
("RCB")
design. Seven months later, the percentages of Citrus Greasy Spot infection on
five
branch terminals from each tree were recorded and averaged.
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CITRUS GREASY SPOT TEST
CAUKINS GROVES, INDIANTOWN, FLORIDA
CAVE% INFECTION
TREATMENT RATE/IOO GALLONS2/lO/HH
FCC-455 Spray Oil (Florida 1% 30.0
Citrus
Commission)
Difenconazole 50 gram (gm) 1.56
AI
Difenconazole 100 gm AI 1.0
Cu-EDDHA 3.2% 0.2 lbs. AI 2.5
KOCIDE 101 4 lbs. 23
Untreated -- 35
APPL. Single tree plots x 6 Reps.
* Aug. 5 terminals/tree
The Difenconazole (triazole): specifically, 1-2[2-[4-(4-chlorophenoxy)-2-
chlorophenyl-(4-methyl-1, 3-dioxolan-2-1)-methyl]]-1H-1,2,4-triazole
(available from
Ciba-Geigy, Greenborough, North Carolina) is a triazole fungicide. As can be
seen,
from the table it provided desirable fungus repression. But, triazole is well
known to
be potentially hazardous to human health, in particular it is known to be
damaging to
the human liver.
Also tested, was Cu-EDDHA: (Sodium cupric ethylenediamine-di-o-
hydroxyphenylacetic acid), which is the fungicide/bactericide of the present
invention.
Analysis of the data shows excellent results from applying the Cu-EDDHA.
KOCIDE 101 is a fungicide available from Griffin Corp., Valdosta, Georgia.
The composition FCC-455 spray is also fungicide. The % infection of the plants
treated with the KOCIDE 101 and FCC-455 compositions is considered
unacceptable.
Also, note that KOCIDE 101 is a copper hydroxide composition.
From the table AVE % infection relates to the percentage infection of Citrus
Greasy Spot (Mycosphaerella citri) found on the treated leaves.
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Example 2.
In the present Example, fungicides were again tested on "Valencia" oranges
except the effect of various fungicides on perithecia was tested. Three
different
fungicides, the Cu-EDDHA, TILT (Propiconazole made by Ciba-Geigy), and
difenconozole were applied in 100 gallons per acre (gpa) to single tree plots
of
"Valencia" oranges replicated five times in a RCB design in mid-July.
Twenty mature leaves (from the spring flush) per replicate were harvested
approximately 4 months later and placed under greenhouse conditions and
alternately
wetted and dried to simulate natural defoliation and weathering.
These conditions, in turn, cause the fungus to sporulate by the formation of
perithecia (spore production body of fungus). The spores were counted as a
means of
measuring the fungicidal activity of the treatments. The data is presented
below.
CITRUS GREASY SPOT
SCN NURSERY, DUNDEE, FLORIDA
TREATMENT RATE/100 GALLONS ~ PERITHECIA
Cu-EDDHA 3.2% 0.2 lbs. AI 3.24 b
Cu-EDDHA 3.2% 0.4 lbs. AI 5.93 ab
TILT 3.6 EC 6 oz. Prod. 6.62 ab
Difenconazole 100 gm AI 5.32 ab
Difenconazole 200 gm AI 11.57 ab
CONTROL inoculated 7.97 ab
CONTROL not inoculated 6.42 ab
The conditions of the test were as follows:
Function: ANOVA - 1
Date Case No. 1 to 42
Without selection
One way ANOVA grouped over variable 1
TREATMENT NUMBER
With values from 1 to 7
Variable 3
NUMBER OF PERITHECIA PER 5 MM FIELD AT 2.5 X -- MEAN OF THREE
OBSERVATIONS
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As used herein, a, b, c, and ab indicate statistical significance using
Duncan's
multiple range test. In interpreting the data, a different notation, e.g. b
versus ab,
means there was a statistically significant difference in the results. A
difference in data
of samples with the same letter notation was not statistically significant.
The tests produced important data because if the perithecia is reduced then it
follows that the number of infections are reduced. The Cu-EDDHA showed good
results. The TILT also showed decent results, but is not preferred because it
has
limited uses as promulgated by the FDA (Food and Drug .Administration). Also,
note
that Cu-EDDHA added in a higher AI did not result in enhanced repression of
the
perithecia. This seems to indicate that if too much Cu-EDDHA is added, slight
phytotoxicity will result.
ANALYSIS OF VARIANCE TABLE
DEGREES SUM OF ERROR MEAN
OF SQUARES SQUARE F-VALUE PROB.
FREEDOM
Between 6 226.6508 37.78 1.33 .270
Within 34 965.0170 28.38
Total 40 1191.6678
Example 3.
Cu-EDDHA, KOCIDE 101 (cupric hydroxide), and difenconazole were applied
to single tree plots of "Hamlin" oranges in 100 gpa (in concentration
indicated) in a
RCB design replicated 4 times. Applications were made in either May, June or
May,
and June. Ten fruit/replicates were sampled in July and percent infection of
Melanose
(Diaporthe citri) was determined. See data presented below.
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CITRUS MELANOSE CONTROL
R.E. KEENE FRUIT COMPANY
RATE, % INFECTION
TREATMENT LB AI/100 GALLONSTIn~IING (FRUIT)
Cu-EDDHA 3.2% 0.2 May 9
Cu-EDDHA 3.2% 0.4 May 13
Cu-EDDHA 3.2% 0.8 May 21
Cu-EDDHA 3.2% 0.2 May - June 11
Cu-EDDHA 3.2% 0.4 May - June 15
Cu-EDDHA 3.2% 0.8 May - June 29
Cu-EDDHA 3.2% 0.2 June 14
KOCIDE 101 4.0 May 12
KOCIDE 101 0.4 May - June 10
DIFENCONAZOLE 0.5 June 4
Untreated ~ -- -- 38
4 REPS SINGLE TREE PLOTS.
PENETRATOR (surfactant - non-ionic) @ 4 oz. ALL TREATMENTS
The results indicate that in general not too much Cu-EDDHA should be applied
to the plants. Also, an appropriate application time of year such as May,
should be
chosen.
Example 4.
In the present example, GRAPEFRUIT plants (Citrus paradisi 'Marsh') were
tested with various fungicides to determine the effectiveness in eliminating
greasy spot,
Mycosphaerella citri.
Spray treatments were applied dilute (applied to point of run off) by handgun
in
July to 10-foot high trees at a rate equivalent to 700 gpa. Treatments were
replicated
on 8 single tree plots in a RCB design. Groups of 15 shoots on each of the
east/west
and east side of each tree were tagged and the initial number of leaves was
recorded.
In February, remaining leaves were counted and examined for greasy spot.
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% REMAINING LEAVES
TREATMENT AND RATE/100 GALLONSDEFOLIATION WITH GREASY SPOT
Tribasic copper sulfate (53%1.9 a 20.1 a
Cu) 0.75 1b.
Sunspray 7E oil 1 gal. 3.1 a 27.0 a
Difolatan 80 Sprills 1.25 8.9 b 49.8 b
1b.
Spotless 25W 0.8 1b 1.3 a 22.6 a
Tilt 3.6EC 8 fl. oz. 1.5 a 15.9 a
Cu-EDDHA (3.2% Cu) 1.5 gal. 0.8 a 12.0 a
Untreated 9.7 b 48.5 b
All treatments, except Difolatan (fungicide), reduced greasy spot-induced
defoliation and the percentage number of remaining leaves with greasy spot
symptoms.
There were no significant differences in effectiveness between Tribasic copper
sulfate,
spray oil, Spotless, Tilt, and Cu-EDDHA. There was too little greasy spot rind
blotch
in this test to provide information on the relative efficacy of treatments for
preventing
fruit infection.
Copper sulfate is phytotoxic so that it needs to have its phytotoxicity
reduced.
This is accomplished by combining CaOH with the CuS04. Unfortunately, this
reduces
solubility.
Example 5.
Cu-EDDHA, TILT (propinconazole), difenconazole, and MERTECT ((Merck
Chem., N.J.) thiabendazole) were applied in 100 gpa to 2-year-old laurel oaks
(Quercus
hemispherica) in 2 x 2 gal. pots in a RCB design replicated 4 times. MERTECT
is a
standard well known fungicide that does not include copper. Applications were
made
in July approximately 3 weeks apart and rated in August a month later. See
data
below.
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OAK LEAF BLISTER (Taphrina Caerulescens) CONTROL
TRAILRIDGE NURSERY, KEYSTONE HEIGHTS, FLORIDA
TREATMENT RATE, PRODUCT/ 100 GALLONS*DISEASE INDEX
S Tilt 3.6 emulsifiable8 oz. 1.S
Difenconazole 3.6 2 oz. 2.25
emulsifiable
Cu-EDDHA 3.2% 8 oz. 2.8
MERTECT 8 oz. 1.S
Untreated -- 4.25
*Disease Index: 1 - no disease
2 - light
3 - moderate
4 - heavy
S - dead foliage
2 x 2 gal. trees/exp. unit x 4 Reps in a RCB design ..
1S As can be seen, suitable disease repression occurred with the Cu-EDDHA
composition, even though the concentration is higher than the preferred
amount.
Example 6.
Cu-EDDHA and Kocide (cupric hydroxide) were applied as foliar spray in May
to Hibiscus sinensis cuttings (100/replicate) x 4 replicates in a RCB design.
Treatments
were allowed to dry for one hour and then placed in a commercial propagation
bed
under intermittent mist and rated for bacterial (Erwinia chrysanthemi)
infection one
week later. Data is presented below:
*ERWINIA CONTROL ON HIBISCUS
NELSONS NURSERY, APOPKA, FLORIDA
2S TREATMENT RATE, CU/ 100 /GALLONSAVERAGE % INFECTION
Cu-EDDHA 3.2% 0.2 1b. AI 6
Cu-EDDHA 3.2% 0.4 1b. AI 8
Kocide 101 2 lbs. AI 2S
Untreated -- 100
100 Cuttings/REP X 4 *ERWINIA Chrysanthemi
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The Cu-EDDHA added in an amount equal to 0.2 1b. AI showed excellent
control of Erwina on Hibiscus.
Example 7.
A follow-up experiment to Example 6 was conducted on rooted cuttings which
were dipped as they were removed from the propagation bed and foliarly sprayed
7
days later after being potted. Cu-EDDHA and Kocide 101 were applied at the
rates
specified below in a RCB design utilizing 100 plants/replicate x 4 reps.
Potted cuttings
had not received any previous bactericide treatments prior to potting.
ERWINIA CONTROL ON HIBISCUS
NELSONS NURSERY -- APOPKA, FLORIDA
RATE,
TREATMENT LB. AI/ 100 GALLONS AVERAGE % INFECTION
Cu-EDDHA 3.2% 0.2 19
Cu-EDDHA 3.2% 0.8 32
KOCIDE 101 2.0 - 22
APPLIC. DATES: 7/19 DIP, 7/26/85 SPRAY
100 PLANTS/REP. X 4
Again excellent control was achieved with Cu-EDDHA applied in an amount
equal to 0.2 1b. AI.
Example 8.
The present Example relates to controlling bacterial spots on pepper plants.
The
procedure for the present Example was as follows: Early Cal Wonder variety
pepper
plants were treated at weekly intervals with the following bactericides (g
AI/liter in
parentheses): copper + mancozeb (2 + 1), Cu-EDDHA (0.1), CGA (Ciba Geigy
American)-115944, CGA-151731, CGA-157566, and CGA-164058 (each at 0.25 and
0.5), CGA-143268 (1.0). Treatments were applied weekly in 1000 1/ha for a
total of
eight applications. The crop was artificially inoculated after the first and
third
applications. Disease severity was evaluated after the fourth and eighth
applications.
Phytotoxicity was rated after the eighth application and yields were taken
continually
during the test.
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The results of the testing were determined as such: Disease pressure was
moderate and uniform. After four applications, the best treatments were CGA-
115944,
CGA-151731, and CGA-164058. CGA-157566 was less effective than the three
previously mentioned compounds, but more effective than CGA-143268 which was
equal to copper plus mancozeb and Cu-EDDHA in activity. The ranking of
compounds
changed when treatments were rated 12 days after the last application. Copper
plus
mancozeb control has completely broken down, which was expected because
disease
conditions were severe in the final half of the test and copper should be
applied on a
five-day schedule under these conditions. Cu-EDDHA at only 0.05X the rate of
Kocide 101 (on a metallic copper basis) exhibited some control and was equal
to CGA-
143268, CGA-157566, and CGA-164058. The best bactericide at the second rating
were CGA-115944 and CGA-151731. The phytotoxicity of all treatments was
assessed
after eight applications had been made. The only bactericides which were
phytotoxic
were CGA-115944 and CGA-164058. CGA-164058 was safer than CGA-115944,
which was marginally unacceptable at 0.5 g AI/1. CGA-143268 and CGA-164058
increased yields dramatically. Yields were depressed by CGA-115944, CGA-
151731,
and CGA-157566. Cu-EDDHA had no effect on yield and copper + mancozeb
increased yields moderately.
Example 9.
Croton plants inoculated with Xanthomonas were tested with various fungicides.
Cu-EDDHA at 0.2 and 0.4 lbs. AI/100 gal. and Kocide 101 at 7.4 lbs. AI/Acre
(A)
were applied as foliar applications to croton (Codiaeum variegatum) previously
inoculated with Xanthomonas campestris a day earlier. Treatments were assigned
in a
RCB design and replicated 10 times with single pots. Treatments were applied 3
times
on a weekly schedule and evaluated at 7 and 14 days following the last
application. See
data below.
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Test 1 Codiaeum Inoculated with Xanthomonas
Number of leaves with symptoms
RATE, AI/100 AVERAGE % OF
TREATMENT GALLONS INFECTION
Water noninoculated 0 a
Water inoculated 2.6 c
Cu-EDDHA 3.2% 26 ml (.2 1b.) .6 ab
Cu-EDDHA 3.2% 52 ml (.4 1b.) 1.0 b
Kocide 101 6.8 ml. (7.4 1b.) .9 ab
ANOVA table
I O SOURCE SUM OF SQUARES DF MEAN SQUARE F VALUE
Treatment 37.28 4 9.319 9.177
significant at 1% level
Error 45.7 45 1.016
Total 82.98 49
It was determined that all of the copper treatments provided some control of
Xanthomonas leaf spot of Codiaeum, when compared to the inoculated control.
The
lower rate of Cu-EDDHA and the Kocide 101 gave control equal to the
noninoculated
control treatment.
Example 10.
In the present example, carrots were inoculated with the Alternaria fungus.
The
carrots were then treated with the below listed fungicidal compositions. Also
a control
test was conducted. The percentage of the fungicide in the solution is also
listed below
along with the results. Plot size for testing was a single row of 25 feet by 4
repetitions
in an RCB design. The fungicide was applied eight (8) times with the carrots
then
examined for infection seven ('~ days and twenty-five (25) days after the last
fungicidal
treatment.
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CARROT/ALTERNARIA FUNGICIDE TRIAL
AVERAGE % OF INFECTION
RATE, AI/100
TREATMENT GALLONS 04/05/96 04/23/96
1) K2HP04 1 gal. (0.53 wt. % AI) 6.9 8.2
2) KZHP03 1 gal. (0.55 wt. % AI) 18.7 28.8
3) KZHP04 0.5 gal.(0.26 wt. % 8.9 10.7
+ AI)
KZHP03 +
0.5 gal. (0.27 wt. %
AI)
4) Cu-EDDHA 0.2 1b AI 8.8 11.6
Fe-EDDHA 0.2 1b AI 12.7 ~ 12.9
5)
6) CONTROL - 23.0 34.8
*EDDHA e-di-o-hydroxyphenylacetic
(Ethylenediamin acid)
PLOT SIZE: Single Row X 25 ft. X 4 reps in a RCB design.
Application dates: 2/2, 9,15,22,3/8,14,22, and 28. Rated 4/5 and 4/23/96
NOTE: Second rating was 25' days after last fungicide application. Plots were
inoculated with Alternaria dauci.
The tests were conducted in Sanford, FL.
As can be seen, Cu-EDDHA effectively limited percentage of fungicidal
infection.
It can be concluded that the Cu-EDDHA as well as the Fe-EDDHA are effective
fungicides.
The above Examples demonstrate that the EDDHA metal chelate compositions are
useful in protecting plants against attack by fungus with the application of
the EDDHA
metal chelate solution.
It will be further appreciated that foliar application of the EDDHA metal
chelate
compositions will be effective as a common agricultural practice to control
bacterial
infections in plants.
It will be appreciated by those skilled in the art that beneficial effects
demonstrated
in the Examples by the use of Cu-EDDHA will also be obtained when the Mn, Sn,
Fe,
and Zn EDDHA form metal chelates are employed.
The present invention also relates to compositions and methods for use in
preventing diseases, such as late blight, caused by the genus Phytophthora. In
particular, the present invention relates to compositions and methods for use
in
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WO 02/056680 PCT/USO1/45376
preventing plant diseases caused by Phytophthora infestans. The composition of
the
invention comprises at least one phosphate (P04) constituent and at least one
phosphonate (P03) constituent in addition to at least one metal chelate, with
it most
preferred that a composition comprising at least one potassium phosphonate and
at least
one potassium phosphate be used. A mixture of mono- and dipotassium
phosphonate
salts can be readily used as the potassium salt, and a mixture of mono- di-
and
tripotassium phosphate salts can be readily used as the phosphate salt. Once
the
composition is formed, it can be applied to plants to prevent infection by
Phytophthora
infestans and manifestations related to the infection. The composition can be
applied as
either a dry mix or an aqueous solution to plants prior to infection by the
Phytophthora
infestans organism.
The composition for preventing Phytophthora infestans contains a combination
of
phosphonate and phosphate constituents. Any of a variety of phosphates are
suitable
for use, including KZHP04, K3P04, KHZP04, (NH3)Z HP04, (NH3) HZP04, and
combinations thereof. The phosphonates, like the phosphates, can be selected
from any
of a variety of compositions, including KZHP03, KHzP03 (NH3)2 HP03, (NH3)
HZP03,
and combinations thereof. Any phosphate and phosphonate constituent
combination can
be used as long as infection by and manifestation of Phytophthora infestations
is
inhibited. Additionally, it is necessary for the constituents to have suitable
solubility in
a carrier and to be of a constitution to allow easy distribution in an area
where plants to
be treated are grown. More preferably, the phosphonate and phosphate
constituents,
when combined, will have a synergistic effect in inhibiting Phytophthora
infestans.
The most preferred phosphate (P04) and phosphonate (P03) constituents for use
in
preventing Phytophthora infestans infection are combinations of KzHP03 and
KzHP04.
As such, the phosphate (P04) and phosphonate (P03) constituents are combined
to form
the composition used to prevent Phytophthora infestans infection.
While the discussed constituents are preferred for use in treating plants and
preventing infection by the Phytophthora organism, variations of the phosphate
and
phosphonate constituents can be used. As such, it is preferred if the compound
comprises a fungicidally effective amount of at least a first salt having the
following
formula:
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WO 02/056680 PCT/USO1/45376
RZ _
R1-O-P-O Me n+
O
and a second salt having the following formula:
O
R1-O-P-OH
O
R3
where R1 is selected from the group consisting of H, K, an alkyl radical
containing
from 1 to 4 carbon atoms, halogen-substituted alkyl or nitro-substituted alkyl
radical,
an alkenyl, halogen-substituted alkenyl, alkynl, halogen-substituted alkynl,
alkoxy-
substituted alkyl radical, ammonium substituted by alkyl and hydroxy alkyl
radicals;
RZ and R3 are selected from a group consisting of H and K;
Me is selected from a group consisting of K, alkaline earth metal cations,
aluminum atom, and the ammonium cation; and
n is a whole number from 1 to 3, equal to the valence of Me.
Optionally, the second salt can be of the formula:
O -
Rl-O-P-O Me°+
O
Rs
with the above listed formula constituents still applicable.
The constituents should be preferably mixed with a suitable carrier to
facilitate
distribution to an area where the plants to be treated are grown. The carrier
should be
agriculturally acceptable, with water (H20) most preferred.
As an example of how to form the composition, it is preferred to first form a
potassium phosphonate aqueous solution, with the phosphonate formation as
follows:
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H3P03 is produced by the hydrolysis of phosphorus trichloride according to the
reaction: PC13 + 3H20 ~ H3P03 + 3HCl. The HCl is removed by stripping under
reduced pressure, and the phosphonic acid (H3P03) is sold as a 70% acid
solution.
The phosphonic acid is then neutralized in aqueous solution by potassium
hydroxide according to the reactions: H3P03 + KOH ~KHZP03 + H20
KHZP03 + KOH '---K2HP03 + HZO
to about pH 6.5, and to produce a 0-22-20 liquid weighing 11.15 lbs./ gal.
This
solution is commercially available and is sold under the trademark "Phos-
Might" by
Foliar Nutrients, Inc., Cairo, GA 31728.
The phosphate (P04) is produced by reacting mono potassium phosphate (0-51.5-
34) with 45 % potassium hydroxide in aqueous solution to produce dipotassium
phosphate, by the following reaction: KHZPO4 + KOH ~ K2HP04 + H20 with a
product density of 1.394 g/mL at 20° C and a solution pH of 7.6
producing a 0-18-20
analysis. This solution is commercially available and is sold under trademark
"K-Phos"
by Foliar Nutrients, Inc., Cairo, GA 31724.
After the potassium phosphonate and potassium phosphate constituents, or other
phosphonate and phosphate constituents, are formed, they can be combined to
produce
the potassium phosphonate and potassium phosphate composition, e.g. a mixture
of the
potassium salts of P03 and P04. The phosphonate and phosphate composition can
then
be combined with the metal chelate to form the composition of the invention.
This
composition is used to then treat plants for the prevention of infection by
the
Phytophthora genus, especially Phytophthora infestans.
Varying amounts of each compound, for example, KZHP03, KHZP03, KZHP04, or
KHZP04 in an aqueous solution, are combined at rates ranging from 0.1
millimolar to
1000 millimolar, preferably 1 millimolar to 500 millimolar, more preferably 5
millimolar to 300 millimolar, and most preferably 20 millimolar to 200
millimolar,
depending on crop host and the pathogen complex and level of infection. A 5%
vol./vol. aqueous solution of KZHP04 is equivalent to 2.6% by weight and is
approximately 151 millimolar, and a 5% vol./vol. aqueous solution of KZHP03 is
equivalent to 2.7% by weight and is approximately 173 millimolar. A 20
millimolar
aqueous solution of KzHP04 is equivalent to 0.35 % by weight, and a 20
millimolar
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WO 02/056680 PCT/USO1/45376
aqueous solution of KZHP03 is equivalent to 0.32% by weight. Alternatively,
the
amount of the first salt is equal to one part by weight and the amount of the
second salt
is equal to between 0.001 and 1,000 parts by weight, i.e. the weight ratio of
first salt to
second salt is 1:0.001 to 1:1,000. It is preferred if the aqueous composition
is
comprised of 21.7% KzHP04 and 21.5% K2HP03 or 11.8% P04 and 10.7% P03, all of
which are soluble.
Once formed, the composition will be applied to various plants to prevent
fungus
infection, particularly infection by the Phytophthora genus, and more
particularly
Phytophthora infestans infection. The preferable method of application is
foliar, either
by ground or aerial equipment, but is not limited to that method alone.
Injection or soil
applications, for example, could also be efficacious depending on specific
crops and
pathogens. While it is preferred to apply the composition in an aqueous
solution, other
forms of application may be used, including dusts, flowables, water
dispersable
granules, granules and inert emulsions, as well as oils. At least one
application should
be made; however, multiple applications of the composition can be made.
The inventive composition has utility on fruit crops, agronomic crops,
ornamentals,
trees, grasses, vegetables, grains, and floricultural crops, as well as some
aquatic
crops, including water cress. The crops most likely infected by Phytophthora
infestans
are potatoes (Solanum tuberosum) and tomatoes (Lycopersicon esculentum). As
such,
the present composition is especially useful in treating potato and tomato
plants to
prevent Phytophthora infection.
The following examples set forth the preferred concentrations and techniques
for
formulation thereof, as well as methods of application, use and test results
demonstrating the efficacy of the inventive concentration in protecting plants
against
attack by Phytophthora infestans. It is to be understood, however, that these
Examples
are presented by way of illustration only, and nothing therein shall be taken
as a
limitation upon the overall scope of the invention. The specific components
tested in
the Examples were prepared and applied as follows.
In each of Examples 11 and 12, treatments were applied as a one gallon
solution by
a back pack sprayer, maintained at about 60 psi, in sufficient quantities of
water to
achieve thorough coverage. The spray rate used was equivalent to approximately
25
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gallons per acre. All treatments were applied to the appropriate number of
experimental units assigned in a randomized complete block (CRB) design
replicated
four times.
As used in the following examples, "Percent Late Blight" means the percent of
plants that exhibit blight. "Lesions Per Plant" relate to the number of
lesions on a
particular plant caused by the infectious inoculum. The "No. Infected
Leaflets" relates
to the number of infected leaves per plant.
Example 11.
Potatoes (Solanum tuberosum, variation Atlantic) were infected with a
pathogen,
Phytophthora infestans, to determine whether suitable treatments could be
developed to
eliminate the pathogen from the infected plants and, more importantly, prevent
infection of the plants by the pathogen. The Phytophthora pathogen causes late
blight
in infected plants. The plants were treated with the below listed
compositions, twice,
with the applications being seven (7) days apart. The composition of the
inoculant
added to the plants is listed below in the table. One week (7 days) after the
last
inoculation was made to the plants, the potato plants were then infected with
the
pathogen, Phytophthora infestans. The infectious inoculum was equal to 12,000
sporangia per millimeter (ml), with 20 ml administered per plant. The Genotype
of the
pathogen was US-8 and the Matingtype was A2. Seven days after inoculation with
the
pathogen, the results were tabulated to determine the percentage of blight in
the plants
and the number of lesions per plant. Additionally, the number of infected
leaflets per
plant were tabulated. The results are as follows:
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SUMMARY LATE BLIGHT OBSERVATIONS
GREENHOUSE EXPERIMENT
NO.
LESIONS INFECTED
% LATE PER LEAFLETS
TREATMENT RATE/ACRE BLIGHT PLANT PER PLANT
KZHP03 1 % v/v 0.39 0.5 0.5
+ +
KzHP04 1 % v/v
Cu-EDDHA 0.2 Ib. AI 12.30 35.3 26.9
KZHP03 1 % v/v 1.85 2.4 1.8
KZHP04 1 % v/v 18.45 41.4 31.1
CONTROL 28.12 84.4 50.1
Tests were made on single 6" pots x 4 reps in CRB design.
As can be seen, an inoculum of just phosphonate (P03) showed good results in
controlling the blight. However, better results were achieved using the
phosphate
(P04) and phosphonate (P03) composition. The (P04) and (P03) combination
demonstrated exceptional blight depression, indicating that potato blight can
be better
controlled using a composition comprised of (P03) and (P04). This indicates
that a
synergistic effect is achieved with a (P03) and (P04) combination.
Example 12.
Tomatoes (Lycopersicon esculentum, FL 40) were infected with a pathogen,
Phytophthora infestans, to determine whether suitable treatments could be
developed to
prevent infection of the plants by the pathogen. The Phytophthora pathogen
causes late
blight in infected plants. The plants were treated with the below listed
compositions,
twice, with the application dates being seven (7) days apart. The composition
of the
inoculant added to the plants is listed below in the table. One week (7 days)
after last
inoculation was made to the plants, the tomato plants were then infected with
the
pathogen, Phytophthora infestans. The infectious inoculum was equal to 12,000
sporangia per millimeter (ml), with 20 ml administered per plant. The Genotype
of the
pathogen was US-17 and the Matingtype was A1. Seven days after inoculation
with the
pathogen, the results were tabulated to determine the percentage of blight in
the plants
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and the number of lesions per plant. Additionally, the number of infected
leaflets per
plant were tabulated. The results are as follows:
GREENHOUSE TOMATO LATE BLIGHT TRIAL
NO.
INFECTED
LESIONS LEAFLETS
TREATMENT RATE/ACRE PER PLANT PER PLANT
KZHP03 2% v/v 6.0 2.5
KZHP04
SIMAZINE 4L 0.1 1b. AI 52.3 36.8
KZHP03 1% v/v 56.7 21.5
KZHP04 1% v/v 74.8 36.5
CONTROL 66.8 33.8
Excellent results were achieved using the phosphate (P04) and phosphonate
(P03) composition. The (P04) and (P03) combination demonstrated exceptional
blight
depression, indicating that the blight can be better controlled using a
composition
comprised of (P03) and (P04). This indicates that a synergistic effect is
achieved with
a (P03) and (P04) combination.
The above Examples demonstrate that the inventive compositions are useful in
protecting plants against attack by the Phytophthora infestans infection with
the
application of one solution.
The disclosures in all references cited herein are incorporated by reference.
Alternatively, the composition of the invention can be used to prevent
infection
by Phycomycetes, Ascomycetes, and other fungal pathogens, as well as bacteria.
In the following Examples, the composition of the samples tested are as
follows:
Sample 1: 15.1% KZHP03 + 15.1% KZHP04 + 69.8% inert ingredients (H20)
Sample 2: Cu EDDHA (3.2% Cu) - 0.2 1b AI/100 gal.
Sample 3: 80% v/v Sample 1 + 1 1b. 6% Fe-EDDHA
Sample 4: 80% v/v Sample 1 + 20% v/v 6% Mn-EDTA
Sample 5: 80% v/v Sample 1 + 20% v/v 10% Zn-EDTA
Sample 6: 80% v/v Sample 1 + 10% v/v 6% Mn-EDTA + 10% v/v 10% Zn-EDTA
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Sample 7: 80% v/v Sample 1 + 0.2 1b. AI/100 gal. (Cu-EDDHA)
Example 13.
Single 5 gal. containers of live oak trees (Quercus virginia), inoculated with
Phyllactinia guttata, were treated using a SOLO backpack sprayer at 60 psi at
25 gpa
using the following compositions. Treatments were replicated four times and
assigned
in a randomized complete block design.
LIVE OAK POWDERY MILDEW TRIAL
DISEASE SEVERITY
RATE/100 GALLONSPRE- POST-
O REATMENT (V/V) PHYTO-
APPLICATION
4/20 APPLICATION
6/15 TOXICITY
1) Sample 2 gal. 3.0 2.0 0
1
2) Sample 0.2 1b. AI 2.75 2.5 0
2
3) Sample 2 gal. 2.5 2.0 0
3
4) Sample 2 gal. 3.0 1.5 0
4
5) Sample 2 gal. 3.0 1.0 0
7
6) CONTROL - 3.0 4.0 0
Powdery Mildew - Phyllactinia guttata
Appl. Dates: 4/27, 5/11, 6/1, and 6/15/00
Rated 6/15/00, Clay County, FL.
Disease Severity 1-5: 1=1-10%, 2=11-25%, 3=26-50%, 4=51-75% and 5=76-100%
PHYTOTOXICITY RATINGS: 0-10 0=no phytotoxicity, 10=100% kill
Example 14.
Single 5 gal. containers of live dogwoods (Corpus florida), inoculated with
Oidium spp. , were treated using a SOLO backpack sprayer at 60 psi at 25 gpa
using the
following compositions. Treatments were replicated four times and assigned in
a
randomized complete block design.
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DOGWOOD POWDERY MILDEW TRIAL
DISEASE SEVERITY
RATE/100 GALLONSPRE-EXISTING
REATMENT (V/V) POST-APLICATION
PHYTO-
4/27 6/15
TOXICITY
1) Sample 2 gal. 2.5 1.5 0
1
2) Sample 2 gal. 3.0 1.0 0
4
3) Sample 2 gal. 2.5 1.5 0
5
4) Sample 2 gal. 2.0 1.75 0
6
5) Sample 2 gal. 2.5 1.0 0
7
6) CONTROL - 2.75 3.0 0
Powdery Mildew - Oidium spp.
Appl. Dates: 4/27, 5/11, 5/25, and 6/8/00
Rated 6/15/00
Disease Severity 1-5: 1=1-10%, 2=11-25%, 3=26-50%, 4=51-75% and 5=76-100%
PHYTOTOXICITY RATINGS: 0-10 0=no phytotoxicity, 10=100% kill
In Example 13 above, formulation Sample 7 demonstrates that the pre-
application
Disease Severity factor as measured on April 20, 2000, of 3.0 was reduced to
1.0
demonstrating the combination phosphate, phosphonates and Cu EDDHA (a metal
chelate) is effective in treating the live oak powdery mildew. Similarly,
Example 14
demonstrates that formulations Sample 4 (P03 + P04 + Mn EDTA) and Sample 7
(P03 +
P04 + Cu EDDHA) are effective in treating dogwood powdery mildew as evidenced
in
disease severity from 3.0 to 1.0 and 2.5 to 1.0, respectively.
Thus, there has been shown and described a method of use for fungicidal and
bactericidal compositions, which provide improved efficacy in controlling
fungi and
bacterial infections in plants. More particularly, the compositions and method
related
to metal chelates, and preferably a copper chelate in the form of Cu-EDDHA
(disodium
cupric ethylenediamine-di-o-hydroxyphenylacetic acid), in an aqueous solution,
also
including an effective amount of phosphate (P04) and phosphanate (P03), which
fulfills
all the objects and advantages sought therefore. It is apparent to those
skilled in the
art, however, that many changes, variations, modifications, and other uses and
applications for the subject fungicidal and bactericidal compositions are
possible and,
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also, such changes, variations, modifications, and other uses and applications
which do
not depart from the spirit and scope of the invention are deemed to be covered
by the
invention which is limited only by the claims which follow.
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