U.S. patent number RE37,890 [Application Number 09/244,141] was granted by the patent office on 2002-10-22 for controlled delivery compositions and processes for treating organisms in a column of water or on land.
This patent grant is currently assigned to Lee County Mosquito Control District. Invention is credited to Richard Levy.
United States Patent |
RE37,890 |
Levy |
October 22, 2002 |
**Please see images for:
( Certificate of Correction ) ** |
Controlled delivery compositions and processes for treating
organisms in a column of water or on land
Abstract
Controlled release compositions of matter are disclosed
comprising complexes for treating a population of one or more
aquatic organisms in a column of water. The complexes comprise at
least one system wherein the system comprises at least one
bioactive agent as a component selected for treating a population
of aquatic organisms, at least one carrier component, and at least
one coating component for regulating the controlled release rate
and release profile of the bioactive agent in water or at least one
bioactive agent and one joint-function component that can serve as
both a carrier and coating to regulate the controlled release rate
and release profile of the bioactive agent in water, with or
without optional binder components and/or additional formulation
materials. The components are selected to sink or float so that the
complexes will permeate and/or remain in any planar or volumetric
segment of a water column for a period of time that is sufficient
to effectively treat a population of aquatic organisms. Methods for
treating a column of water are also disclosed which comprises
delivering the compositions to a column of water or to a dry
preflood area (pretreatment) that will develop in a column of water
or a flood area. The composition and process can also be used to
treat terrestrial organisms.
Inventors: |
Levy; Richard (Fort Myers,
FL) |
Assignee: |
Lee County Mosquito Control
District (FL)
|
Family
ID: |
27410676 |
Appl.
No.: |
09/244,141 |
Filed: |
February 4, 1999 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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409301 |
Mar 24, 1995 |
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406344 |
Mar 17, 1995 |
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Reissue of: |
434313 |
May 2, 1995 |
05698210 |
Dec 16, 1997 |
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Current U.S.
Class: |
424/406; 424/405;
424/407; 424/409; 424/417; 424/418; 424/419; 424/420; 424/421;
424/485; 424/487; 424/488; 424/489; 424/93.1; 424/93.461 |
Current CPC
Class: |
A01N
49/00 (20130101); A01N 25/26 (20130101); A01N
57/14 (20130101); A01N 25/34 (20130101); A01N
25/10 (20130101); A01N 63/30 (20200101); A01N
63/22 (20200101); A01N 43/90 (20130101); A01N
63/23 (20200101); A01N 57/14 (20130101); A01N
25/34 (20130101); A01N 25/10 (20130101); A01N
49/00 (20130101); A01N 25/34 (20130101); A01N
25/10 (20130101); A01N 43/90 (20130101); A01N
25/34 (20130101); A01N 25/10 (20130101); A01N
43/90 (20130101); A01N 2300/00 (20130101); A01N
49/00 (20130101); A01N 2300/00 (20130101); A01N
57/14 (20130101); A01N 2300/00 (20130101); A01N
63/22 (20200101); A01N 25/34 (20130101); A01N
25/10 (20130101); A01N 63/22 (20200101); A01N
25/26 (20130101); A01N 25/34 (20130101); A01N
63/23 (20200101); A01N 2300/00 (20130101); A01N
63/23 (20200101); A01N 25/26 (20130101); A01N
25/34 (20130101); A01N 63/30 (20200101); A01N
25/34 (20130101); A01N 25/10 (20130101); A01N
63/30 (20200101); A01N 25/26 (20130101); A01N
25/34 (20130101); A01N 63/23 (20200101); A01N
25/34 (20130101); A01N 25/10 (20130101); Y10S
424/09 (20130101); Y10S 514/918 (20130101); Y10S
424/08 (20130101); Y10T 428/1352 (20150115); Y10T
428/1307 (20150115); Y10S 514/919 (20130101); Y10S
424/11 (20130101); Y10S 206/811 (20130101); Y10T
428/139 (20150115); Y10T 428/13 (20150115); Y10T
428/1348 (20150115); Y10S 424/10 (20130101); Y10S
514/92 (20130101) |
Current International
Class: |
A01N
25/10 (20060101); A01N 25/34 (20060101); A01N
25/26 (20060101); A01N 43/90 (20060101); A01N
49/00 (20060101); A01N 63/00 (20060101); A01N
57/00 (20060101); A01N 57/14 (20060101); A01N
025/10 () |
Field of
Search: |
;424/405-409,417-421,485-490,93.1,93.46,93.461 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0 453 397 |
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Oct 1991 |
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EP |
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0 624 366 |
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Nov 1994 |
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EP |
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0631 781 |
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Jan 1995 |
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EP |
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0 647 448 |
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Apr 1995 |
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EP |
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0 823 255 |
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Feb 1998 |
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EP |
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WO 90/04386 |
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May 1990 |
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WO |
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WO 92/20229 |
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Nov 1992 |
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WO |
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WO 93/01804 |
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Feb 1993 |
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WO |
|
Primary Examiner: Levy; Neil S.
Attorney, Agent or Firm: Finnegan, Henderson, Farabow,
Garrett & Dunner, L.L.P.
Parent Case Text
.Iadd.
CROSS-REFERENCE TO RELATED APPLICATION
This application is a reissue of U.S. Pat. No. 5,698,210 issued
Dec. 16, 1997 from U.S. Ser. No. 434,313 filed May 2, 1995
incorporated herein by reference..Iaddend.
This application is a continuation in part application of U.S.
patent application Ser. No. 08/409,301, filed Mar. 24, 1995, now
abandoned, which is a continuation in part application of U.S.
patent application Ser. No. 08/406,344 filed Mar. 17, 1995, now
abandoned, both of which are incorporated herein by reference.
Claims
What I claim is:
1. A composition of matter consisting essentially of a complex for
treating a population of one or more aquatic organisms, said
complex consisting essentially of at least one controlled delivery
system, said controlled delivery system consisting essentially of
.Iadd.an admixture of .Iaddend.from about 50% to about 99% by
weight of at least one carrier component .Iadd.selected from
silicas, cellulose fibers, metal oxides, clays, infusorial earth,
finely ground slag or lava, paper, hydrophobic wood pin chips,
waste wood, sawdust, sand, vermiculite, ground cork, corn cob
grits, bagasse, seed hulls, particulate carbon materials, starches
or modified starches, carrageenan, algin, xanthates, or agar, or
combinations thereof.Iaddend., from about 0.0001% to about 50% by
weight of at least one bioactive agent as a component selected for
treating a population of one or more aquatic organisms, from about
1.0% to about 50% by weight of at least one coating component for
regulating the controlled release rate and release profile of said
bioactive agent, wherein said coating is water soluble or
biodegradable or erodible, said components being selected so that
said complex will remain in an application site for a period of
time sufficient to effectively treat a population of one or more of
said organisms, said coating component consisting essentially of
.[.water soluble organic polymers, wherein said water soluble
organic polymers are polyvinyl alcohol, polyethylene oxide
hydroxypropyl methyl cellulose or methyl cellulose,.]. fatty
alcohols .Iadd.and esters thereof.Iaddend., fatty acids.[.,.]. and
esters thereof, .[.or.]. phthalyl esters, .Iadd.or waxes, said
coating component optionally combined with a water soluble organic
polymer wherein said water soluble organic polymer is polyvinyl
alcohol, polyvinyl alcohol copolymers, polyethylene oxide,
hydroxypropyl methyl cellulose, or methyl cellulose, or
combinations thereof, .Iaddend.and wherein said composition is free
of superabsorbent polymers.
2. A composition of matter consisting essentially of a complex for
treating a population of one or more aquatic organisms in a column
of water, said complex consisting essentially of at least one
controlled delivery system, said controlled delivery system
consisting essentially of .Iadd.an admixture .Iaddend.from about
50% to about 99% by weight of at least one carrier component
.Iadd.selected from silicas, cellulose fibers, metal oxides, clays,
infusorial earth, finely ground slag or lava, paper, hydrophobic
wood pin chips, waste wood, sawdust, sand vermiculite, ground cork,
corn cob grits, bagasse, seed hulls, particulate carbon materials,
starches or modified starches, carrageenen, algin, xanthates, or
agar, or combinations thereof.Iaddend., from at about 0.0001% to
about 50% by weight of at least one bioactive agent as a component
selected for treating a population of one or more aquatic
organisms, and from about 1.0% to about 50% by weight of at least
one coating component for regulating the controlled release rate
and release profile of said bioactive agent in water, wherein said
coating is water soluble or biodegradable or erodible, said
components being selected so that said complex will remain in an
application site for a period of time sufficient to effectively
treat a population of one or more of said organisms, said coating
component consisting essentially of .[.water soluble organic
polymers, wherein said water soluble organic polymers are polyvinyl
alcohol, polyethylene oxide, hydroxy propyl methyl cellulose or
methyl cellulose,.]. fatty alcohols .Iadd.and esters
thereof.Iaddend., fatty acids and esters thereof, .[.or.]. phthalyl
esters, .Iadd.or waxes, said coating component optionally combined
with a water soluble organic polymer selected from polyvinyl
alcohol, polyvinyl alcohol copolymers, polyethylene oxide,
hydroxypropyl methyl cellulose, or methyl cellulose, or
combinations thereof, .Iaddend.said components, also being selected
to sink or float so that said complex will permeate and remain in
any planar or volumetric segment between the top and bottom of a
water column for a period of time sufficient to effectively treat a
population of one or more aquatic organisms, and wherein said
composition is free of superabsorbent polymers.
3. The composition of claim 1 or 2 wherein one of said components
is selected to sink, one of said components is selected to float,
and the remaining component selected to sink or float.
4. The composition of claim 1 or 2 wherein said .[.carriers are
silicas, cellulose fibers, metal oxides, clays, infusorial earth,
finely ground slag or lava,.]. .Iadd.coating compound is cetyl
alcohol or stearyl alcohol, optionally combined with
.Iaddend.polyvinyl alcohol, polyvinyl alcohol copolymers,
polyethylene oxide, hydroxy propyl methyl cellulose, .[.paper,
hydrophobic wood pin chips, cetyl alcohol, stearyl alcohol,
vermiculite, ground cork, corn cob grits, bagasse, seed hulls,
paper, particulate carbon materials, starches or modified starches,
carrageenen, algin, xanthates, agar, or powdered polymeric
materials, and.]. .Iadd.methyl cellulose or .Iaddend.combinations
thereof.
5. The composition of claim 1 or 2 wherein said carrier is a
hydrophobic or hydrophilic silica, a silicate, diatomaceous earth
or sand, and combinations thereof.
6. The composition of claim 5 wherein said carrier is silica having
a surface area of from about 50 to about 450 m.sup.2 /g, an average
agglomerate size of from about 3.5 to about 100 .mu.m, an average
primary particle size of from about 12 to about 30 nm, a tapped
density of from about 50 to about 240 g/l, a pH from about 3.6 to
about 9 and a dibutyl phthalate (DBP) adsorption of from about 160
to about 335 g/100 g.
7. The composition of claim 5 wherein said carrier is a silicate
having a surface of from about 30 to about 40 m.sup.2 /g, an
average agglomerate size of from about 4 to about 6 .mu.m, a tapped
density of from about 285 to about 315 g/l, a pH of from about 9.5
to about 10.5 and a DBP adsorption of from about 150 to about 170
g/100 g.
8. The composition of claim 1 or claim 2 wherein said coating has a
specific gravity equal to or greater than 1 or less than 1.
9. The composition of claim 8 wherein said coating having a
specific gravity greater than 1 is triethyl citrate, acetyltriethyl
citrate, tri-n-butyl citrate, acetyltri-n-butyl citrate,
acetyltri-n-hexyl citrate, tri-n-hexyltrimellitate, dicyclohexyl
phthalate, diethyl phthalate, butyl phthalyl butyl glycolate,
dimethyl isophthalate, .[.or water-soluble films of polyvinyl
alcohol, polyethylene oxide, methyl cellulose, hydroxypropyl methyl
cellulose, or paper,.]. and combinations thereof.
10. The composition of claim 8 wherein said coating having a
specific gravity less than 1 is n-butyryl-tri-n-hexyl citrate,
monostearyl citrate, stearyl alcohol, cetyl alcohol, myristyl
alcohol, octadecanoic acid, glyceryl stearate, or waxes, and
combinations thereof.
11. The composition of claim 1 or 2 wherein said bioactive agents
are .[.pesticides,.]. insecticides, toxicants, monomolecular
surface films, petroleum oils, insect growth regulators, plant
growth regulators, animal growth regulators, .[.growth
regulators,.]. microbial control agents, pharmaceuticals,
medicaments, antibiotics, pathogens, biological control agents,
parasites, bactericides, viricides, fungicides, algaecides,
herbicides, nematicides, amoebicides, miticides, acaricides,
predicides, schistisomicides, molluscicides, larvicides, pupicides,
ovicides, adulticides, nymphicides, attractants, repellents, growth
stimulants, feeding stimulants, nutrients, hormones,
chemosterilants, or pheromones, and combinations thereof.
12. The composition of claim 1 or 2 wherein said bioactive agent is
selected to treat mosquitoes.
13. The composition of claim 12 wherein said bioactive agent is
Bacillus thuringiensis var. israelensis, Bacillus sphaericus,
Lagenidium giganteum, methoprene, diflubenzuron, pyriproxyfen,
temephos, chlorpyrifos, primiphos-methyl, lambda cyhalothrin,
pyrethrins, 2 mol ethoxylate of isostearyl alcohol, lecithins, or
petroleum oils, and combinations thereof.
14. The composition of claim 1 or 2 wherein said bioactive agent is
selected to treat aquatic plants.
15. The composition of claim 14 wherein said bioactive agent is
acrolein, aromatic solvents, water soluble copper compounds,
dalapon, dichlorbenil, 2,4-D, diquat, endothall, glyphosate,
simazine, or fluridone, and combinations thereof.
16. The composition of claim 1 or 2 further including a binder.
17. The composition of claim 16 wherein said binder is sulfonated
polystyrene homopolymers, sulfonated styrene maleic anhydride
polymers, sulfonated vinyl toluene maleic anhydride polymers, vinyl
pyrrolidone polymers or copolymers, poly(isobutylene-co-disodium
maleate) copolymers, acrylamide polymers or copolymers,
acrylonitrile-starch graft polymers or copolymers, carboxymethyl
cellulose polymers or copolymers, acrylate polymers or copolymers,
poly(vinyl alcohol) polymers or copolymers, poly(ethylene
oxide)polymers or copolymers, acrylic acid or acrylic ester
homopolymers or copolymers, natural gums, synthetic gums,
poly(ethylene glycol), clays, gypsum, plaster of paris, wax, paper,
cellulose, latex, methyl vinyl ether maleic acid ester copolymers,
starches or modified starches, and combinations thereof.
18. The composition of claim 1 or 2 further including a
joint-function carrier/coating agent.
19. The composition of claim 1 or 2 wherein said bioactive agent is
Bacillus thuringiensis israelensis, methoprene, 2 mol ethoxylate of
isostearyl alcohol, or the dipotassium salt of endothall, said
coating is cetyl alcohol, triethyl citrate, acetyl triethyl
citrate, tributyl citrate, acetyltributyl citrate,
acetyltri-n-hexyl citrate, n-butyltri-n-hexyl citrate, dicyclohexyl
=phthalate, butyl phthalyl butyl glycolate, or tri-n-hexyl
trimellitate, said carrier is hydrophobic silica, hydrophilic
silica, hydrophobic wood pin chips, or sand, said composition
includes an optional binder comprising soluble starches or modified
starches sulfonated polystyrene, a sulfonated vinylic polymer, an
optional acrylic copolymer suspending agent, an optional
joint-function carrier/coating comprising water soluble polyvinyl
alcohol, and combinations thereof.
20. The composition of claim 1 or 2 further including at least one
additional component to further regulate the controlled release
rate and release profile of the bioactive agent in water wherein
such components are diluents, adjuvants, dyes, alcohols, acetone,
ketones, oils, surfactants, water, emulsifiers, film-forming
agents, compatibility agents, wetting agents, salt, natural or
synthetic polymers, hydrocolloids, buoyancy modifiers, ultraviolet
absorbers, photo-protecting agents, suspending agents, elastomers,
penetrants, deflocculating agents, dispersing agents, stabilizing
agents, antifoaming agents, sticking agents, solvents, co-solvents,
catalysts, or synergists, and combinations thereof.
21. The composition of claim .Iadd.1 or .Iaddend.2 in the form of a
sprayable liquid.
22. The composition of claim .Iadd.1 or .Iaddend.2 in the form of a
powder.
23. The composition of claim 1 or 2 in the form of an agglomerate.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed to compositions and processes for
controlled delivery of bioactive agents to a population of aquatic
organisms located in any planar or volumetric segment of a column
of water by ground or aerial application techniques. Organisms of
special interest are disease-carrying or biting or non-biting
nuisance insects, and parasitic animals or plants, especially
weeds. Compositins for controlled delivery of bioactive agents to
terrestrial organisms are also described.
2. Description of Related Art
Various methods have been devised for delivering biologically
active materials to control pests and vegetation. For example,
Yaffe et al., U.S. Pat. No. 3,274,052 describes a process and a
composition in which molten droplets of a normally solid toxicant
are sprayed on the surface of a granular carrier whereupon they
adhere to and solidify on the surface of the carrier as an adherent
coating. When employed for treating aquatic environments, the
specific gravity of the granules, and the rate of release of the
toxicant is adjusted during the manufacture to provide surface,
intermediate or bottom contact, or penetration into mud to control
the specific organisms involved. Neither methods nor compositions
are described for adjusting the specific gravity.
Hedges et al., U.S. Pat. No. 3,917,814, describes a non-poisonous
insecticidal composition consisting of diatomaceous earth having a
sorptive silica gel adhered to the surface.
Jacobson et al., U.S. Pat. No. 5,180,585, describes an
antimicrobial composition consisting of inorganic core particles
coated with a metal or metal compound having antimicrobial
properties.
Thies et al., U.S. Pat. No. 4,464,317, describes a process for
encapsulating a pesticide with an inorganic silicate coating. The
encapsulated materials according to the inventors are capable of
fragmenting upon storage in water to provide controlled release of
a pesticide such as a mosquito control agent. Non-encapsulated
materials were shown to have about half the active life of the
encapsulated materials.
Levy, U.S. Pat. Nos. 4,818,534; 4,983,389; 4,983,390; and
4,985,251, describe various insecticidal, herbicidal, terrestrial,
and flowable insecticidal delivery compositions based on bioactive
materials and superabsorbent polymers.
One of the problems encountered in delivering bioactive materials
to aquatic environments is that the aquatic organism to be treated
is not immediately susceptible to being contacted with the
bioactive material because of its location in a column of water
either at the surface, the bottom, or some intermediate region in
between. Because of the specific gravity of the bioactive material,
in many instances it cannot be targeted to precisely treat the
organisms of interest in the water column. By way of example,
bioactive materials that have a specific gravity greater than water
will generally be ineffective for treating aquatic organisms at the
surface of a column, and vice-versa. Aquatic organisms that persist
at some intermediate level are also difficult to treat for the same
reasons.
The foregoing illustrates that various delivery systems have been
devised for bioactive materials, and the need to have a controlled
delivery system suitable for delivering these materials to aquatic
organisms. Although there is some suggestion that by adjusting the
specific gravity of a toxicant composition of matter, it would be
suitable for delivering the toxicant to an aquatic environment
either at the surface, the bottom or at some intermediate level,
the means for adjusting the specific gravity have not been
disclosed.
Accordingly, the present invention is directed to compositions and
processes for treating a population of one or more aquatic
organisms in a column of water in which the foregoing and other
disadvantages are overcome.
The present invention is also directed to compositions and
processes for pretreating a dry (preaquatic) habitat area before it
has been flooded by rain or tides, and which is a breeding site for
the target aquatic organism(s), i.e. a preflood area. Pretreating a
flooded aquatic habitat area before the target aquatic organism(s)
breed is also with the scope of the invention, as well as flooded
habitats where the organisms exist.
The foregoing illustrates that various delivery systems have been
devised for bioactive materials, and the need to have a controlled
delivery system suitable for delivering these materials to one or
more terrestrial organisms, i.e. non-aquatic organisms. Although
there are some systems that are available to provide control of
these organisms, it would be advantageous to provide additional
compositions for addressing the problems caused by such organisms
whether they are plant, insect, or other animal pests.
Accordingly, the present invention is directed to compositions and
processes for treating one or more terrestrial organisms in which
the foregoing and other disadvantages are overcome.
Specifically, the advantages sought to be obtained according to the
present invention are to provide compositions of matter or
processes for treating a population of one or more aquatic
organisms in a column of water, or one or more terrestrial
organisms. Throughout the specification it is intended that the
terms "treat," "treating," or "treatment" are intended to mean
enhancing development of an organism, prolonging life of an
organism, stopping or reversing the development of a condition in
an organism, stopping the development of an organism, or
eradicating an organism.
SUMMARY OF INVENTION
These and other advantages are realized by the present invention
which comprises compositions of matter and processes which
substantially obviates one or more of the limitations and
disadvantages of the related art.
Additional features and advantages of the invention will be set
forth in the written description which follows, and in part will be
apparent from this description, or may be learned by practice of
the invention. The objectives and other advantages of the invention
will be realized and attained by the compositions of matter and
processes particularly pointed out in the written description and
claims hereof.
To achieve these and other advantages, and in accordance with the
purpose of the invention, as embodied and broadly described, the
invention comprises compositions of matter for treating an aquatic
column of water comprising a bioactive agent as a component for
treating a population of one or more aquatic organisms, a carrier
component, and a coating component for regulating the controlled
release rate (i.e., fast, slow, pulsed or delayed), and release
profile (i.e. zero-order, first-order, and square-root-of-time
kinetics) of the bioactive agent in water. The compositions of
matter of the invention can optionally be combined with a binder
component to aid in agglomerating the compositions, or a variety of
formulation ingredients to enhance the performance of the
compositions.
Compositions of matter are also described for treating a population
of one or more aquatic organisms in a column of water comprising a
bioactive agent as a component for treating a population of one or
more aquatic organisms, and a joint-function carrier component that
not only carries the bioactive material but also is a coating
component for regulating the controlled release rate, and release
profile of the bioactive agent in water. The compositions of matter
of the invention can optionally be combined with a binder component
to aid in agglomerating the compositions, or a variety of
formulation ingredients to enhance the performance of the
compositions.
Further in this regard, a composition of matter is provided
comprising a complex for treating a population of one or more
aquatic organisms in a column of water, the complex comprising at
least one controlled delivery system wherein the controlled
delivery system comprises at least one bioactive agent as a
component for treating a population of one or more aquatic
organisms, at least one carrier component, at least one coating
component for regulating the controlled release rate, and release
profile of the bioactive agent in water, with or without one or
more binder component(s) for agglomerating said composition into
larger units such as granules, pellets, and briquets, or additional
formulation ingredients.
In another complex, the controlled delivery system comprises at
least one bioactive agent as a component for treating a population
of aquatic organisms, at least one joint-function carrier component
that is also a coating component for regulating the controlled
release rate, and release profile of the bioactive agent in water,
with or without one or more binder components for agglomerating
said composition into larger units such as granules, pellets, and
briquets, or additional formulation ingredients.
In yet another complex, the controlled delivery system comprises at
least one bioactive agent as a component for treating a population
of one or more aquatic organisms, at least one joint-function
carrier component that is also a coating component for regulating
the controlled release rate, and release profile of the bioactive
agent in water, at least one additional component such as an
additional coating component to further regulate or modify the
controlled release rate, and release profile of the bioactive agent
in water, with or without one or more binder components for
agglomerating said composition into larger units such as granules,
pellets, and briquets, or additional formulation ingredients.
The components are selected to sink or float so that each complex
or composition will permeate, and remain in any planar or
volumetric segment of a water column for a period of time
sufficient to effectively treat a population of one or more aquatic
organisms.
A method is also provided in which the foregoing compositions are
delivered to the column of water in order to time-release the
bioactive agent(s) in the water so as to make it available to treat
the aquatic organisms.
The invention also comprises compositions of matter for treating
one or more terrestrial organisms comprising a bioactive agent as a
component for treating a population of one or more terrestrial
organisms, a carrier component, and a coating component for
regulating the controlled release rate, and release profile of the
bioactive agent. These compositions of matter of the invention can
optionally be combined with a binder component to aid in
agglomerating the compositions or a variety of formulation
ingredients to enhance the performance of the compositions.
Compositions of matter are also described for treating a population
of one or more terrestrial organisms comprising a bioactive agent
as a component for treating a terrestrial organism, and a
joint-function carrier component that not only carries the
bioactive material but also is a coating component for regulating
the controlled release rate, and release profile of the bioactive
agent. The compositions of matter of the invention can optionally
be combined with a binder component to aid in agglomerating the
compositions, or a variety of formulation ingredients to enhance
the performance of the compositions.
Further in this regard, a composition of matter is provided
comprising a complex for treating a population of one or more
terrestrial organisms, the complex comprising at least one
controlled delivery system wherein the controlled delivery system
comprises at least one bioactive agent as a component for treating
a terrestrial organism, at least one carrier component, at least
one coating component for regulating the controlled release rate,
and release profile of the bioactive agent, with or without one or
more binder component(s) for agglomerating said composition into
larger units such as granules, pellets, and briquets, or additional
formulation ingredients.
In another complex, the controlled delivery system comprises at
least one bioactive agent as a component for treating a population
of one or more terrestrial organisms, at least one joint-function
carrier component that is also a coating component for regulating
the controlled release rate, and release profile of the bioactive
agent, with or without one or more binder components for
agglomerating said composition into larger units such as granules,
pellets, and briquets, or additional formulation ingredients.
In yet another complex, the controlled delivery system comprises at
least one bioactive agent as a component for treating a population
of one or more terrestrial organisms, at least one joint-function
carrier component that is also a coating component fore regulating
the controlled release rate, and release profile of the bioactive
agent, at least one additional component such as an additional
coating component to further regulate or modify the controlled
release rate, and release profile of the bioactive agent, with or
without one or more binder components for agglomerating said
composition into larger units such as granules, pellets, and
briquets, or additional formulation ingredients.
A method is also provided in which the foregoing compositions are
delivered to a terrestrial environment in order to time-release the
bioactive agent(s) so as to make it available to treat the
terrestrial organisms. The terrestrial environment is one that is a
habitat or potential habitat for the terrestrial organisms.
It is understood that both the foregoing general description and
the following detailed description are exemplary, and explanatory,
and further, the following description is intended to provide a
more detailed explanation of the invention as claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a degradable container, such as a
water soluble polyvinyl alcohol pouch containing the composition of
the present invention; and
FIG. 2 is a perspective view of a dispensing container having
apertures for dispensing the composition of the present invention
to an aquatic or terrestrial habitat.
DETAILED DESCRIPTION
The effectiveness of bioactive materials, especially on aquatic
organisms, is generally dependent on delivery of the material to
the specific organisms that are targeted for treatment, i.e.,
effectiveness is dependent on the bioavailability of the material
which can be problematic in aqueous environments. For example, some
bioactive materials when delivered to an aqueous environment will
not remain in the region of interest, where the aquatic organisms
are located, for a length of time sufficient to provide complete
treatment of the organism. This is generally remedied by several
successive treatments which is costly in terms of the labor and
machinery expenses incurred in multiple applications.
An example would be the use of a bioactive material having a
specific gravity greater than one, used for the treatment of
aquatic organisms that persisted at the surface of a body of
water.
Similar problems would also occur where the bioactive material has
a specific gravity less than one, and the aquatic organisms have a
habitat beneath the surface of, or at the bottom of a body of
water. In this case, the bioactive material could be injected by
means of a tube or other device beneath the surface of the water,
but since it has a specific gravity less than one, it would not
persist in the region where it is delivered, and would also require
multiple applications in order to be effective.
In order to overcome these difficulties, compositions and processes
have been provided for treating a column of water where
compositions can be specifically formulated to persist either at
the top or the bottom of the column or at any planar or volumetric
segment in between the top and the bottom.
One composition of matter of the present invention is based on at
least one bioactive agent for treating a population of one or more
aquatic organisms, at least one carrier component, and at least one
coating component for regulating the controlled release rate, and
release profile of the bioactive agent in water, with or without
one or more binder components for agglomerating said composition
into larger units such as granules, pellets, and briquets, or
additional formulation ingredients.
A second composition of matter is based on at least one bioactive
agent for treating a population of one or more aquatic organisms,
at least one joint-function carrier component that is also a
coating component for regulating the controlled release rate, and
release profile of the bioactive agent in water, with or without
one or more binder components for agglomerating said composition
into larger units such as granules, pellets, and briquets, or
additional formulation ingredients.
A third composition of matter is based on at least one bioactive
agent for treating a population of one or more aquatic organisms,
at least one joint-function carrier component that is also a
coating component for regulating the controlled release rate, and
release profile in water, and at least one additional component
such as an additional coating component to further regulate or
modify the controlled release rate, and release profile of the
bioactive agent in water, with or without one or more binder
components for agglomerating said composition into larger units
such as granules, pellets, and briquets, or additional formulation
ingredients.
The various components are selected to sink or float so that each
complex or composition will permeate, and remain in any planar or
volumetric segment of a water column for a period of time
sufficient to effectively treat a population of one or more aquatic
organisms.
The aforementioned compositions of matter of the present invention
can be placed in one or more differentially water soluble, flexible
or rigid, degradable or biodegradable packets, pouches, capsules,
canisters, extrusions, coatings, and the like, of polyvinyl
alcohol, polyethylene oxide, and hydroxypropyl methyl cellulose
films of various thicknesses (e.g., 1-3 mil) to further modify the
coating regulated controlled release rate, and release profile of
the bioactive agent(s) formulated in the powdered or agglomerated
compositions.
Furthermore, the controlled release rate, and release profile of
one or more bioactive agents from all compositions of matter of the
present invention can be optionally modified by placing said
compositions (i.e., powdered or agglomerated) into various shaped
(e.g., spherical, cylindrical, etc.) disposable or reusable,
biodegradable, degradable or nondegradable, dispensers (e.g.,
plastic or metal) such as water soluble polyvinyl alcohol pouch 10
having a continuous outer wall 12 that envelops the composition of
the invention therein (not illustrated) or metal container 14
having outer wall 16 and bottom wall 18 and 20, with one or more
orifices (e.g., holes, slots, etc.) 22 and 24 through which the
bioactive agent formulation therein (not illustrated) will be
delivered.
Dispensing devices can be of various densities for use in aqueous
environments, and can be anchored in various surface, and/or
subsurface locations of an aquatic habitat or can be freely
dispensed to float, and/or sink at will. These optional dispensing
devices can also be utilized in pretreatment or dry aquatic
habitats that are scheduled to become aquatic e.g. by the advent of
rain, and/or tides.
The carrier comprises a material that will float or sink, and is
based on either inorganic or organic compounds that are hydrophobic
or hydrophilic. Materials that are especially of interest in this
regard are silicas (including sand and diatomaceous earth),
cellulose fibers such as PRE-CO-FLOC.RTM. which is derived from
purified virgin wood pulp, which is fully bleached in a sulfite
pulp process having an average fiber length of from about 50 to
about 90 microns, and a thickness of from about 7 to 30 microns,
metal oxides, clays, infusorial earth, slag, or lava, all of which
are finely ground or have a small particle size, but can be
agglomerated into larger components with the addition of a binder
component. Hydrophilic materials that have been surface treated to
be hydrophobic, e.g., by a silicone coating are also suitable.
Other carriers include films of polyvinyl alcohol, polyethylene
oxide, and hydroxypropyl methyl cellulose. MONO-SOL.RTM. LXP-1832
which is a FDA approved hydroxypropyl methyl cellulose (MHPC) and
is edible. MONO-SOL.RTM. PXPN-1257 MHPC, and the MONO-SOL.RTM.
6000, 7000 and 8000 series which are polyvinyl alcohol polymer or
copolymer films, thermolytically processed hydrophobic "pin chips"
(waste wood, or saw dust) (Sea Sweep.RTM.), cetyl alcohol, stearyl
alcohol, vermiculite, ground cork, corn cob grits, bagasse from
sugar cane or grapes and the like, seed hulls such as rice hulls,
or any cereal crop hulls such as oat hulls, wheat hulls barley
hulls and the like, paper, and especially dust free paper granules
such as BIODAC.RTM., manufactured from recycled, cellulosic based
paper waste and containing from about 47 to about 53 wt. % paper
fiber, from about 28 to about 34 wt. % clay, and especially paper
grade clays or mixtures thereof, including Kaolin, about 14 to
about 20 wt. % calcium carbonate or art known equivalents thereof
and mixtures thereof, and from about 0.01 to about 0.9 wt. % of an
inorganic pigment such as titanium dioxide, or the art known
equivalents thereof, and mixtures thereof. Other materials that may
be employed as carriers include particulate, i.e. granular or
powdered carbon materials including powdered or granular charcoal,
petroleum coke, coke from coal, CVD carbon, carbon black, lamp
black, activated carbon, and graphite, powdered polymeric
materials, such as powdered olefinic polymer materials, e.g.,
homopolymers, and/or copolymers of polyethylene or polypropylene,
fluorinated polymers such as polytetrafluoroethylene, or
polyvinylidene fluoride, or chlorinated polymers such as
polyvinylchloride homopolymers and copolymers, acrylate polymers
such as acrylic acid and alkyl acrylic acids or esters or amides
including the homopolymers and copolymers thereof, and the like.
Polysaccharides can also be employed as carriers including starches
and modified starches, especially as both are described herein,
carrageenen, algin, which is intended to include alginates as well,
xanthates, and agar. The carriers can be combined to alter or
enhance the performance characteristics of a composition, two,
three or four carriers being especially suitable in this
regard.
The especially preferred materials in this regard comprise silicas
and silicates.
Precipitated silicas employed in this regard are produced from
solutions of water glass into which sulfuric acid is introduced
under fixed conditions. They are formed in the aqueous phase, and
depending on the conditions of precipitation, it is possible to
produce products with smaller or somewhat larger primary particles,
which then basically determine particle size and specific surface
area. The precipitates obtained are then washed and dried by
methods known in the art.
Silicates are also manufactured by a precipitation method, however,
the acids which are necessary for precipitation are replaced
partially or completely by solutions of metallic salts such as
aluminum sulfate, and the like. The precipitation parameters can
also be adjusted to suit the various raw materials.
The silicas obtained in this way can be dried by a spray drying
technique to obtain particles that are substantially spherical,
have a size anywhere from about 50 to about 150 .mu.m, and have
excellent flow properties.
Spray dried precipitated silicas may also be ground so that the
densities will vary anywhere from about 80 g/l to about 270 g/l,
and the particle size anywhere from about 4 .mu.m to 800 .mu.m.
Precipitated silicas and silicates can also be dried by standard
drying processes, for example in turbo-driers or rotating driers.
Silicas and silicates dried in this conventional way must always be
subsequently ground. The average particle size and the tapped
density also depend on the degree of grinding. The tapped density
in this regard can be from about 80 g/l to about 240 g/l, and the
particle size from about 4 .mu.m to about 15 .mu.m.
Silicas can also be produced by means of a high temperature flame
hydrolysis during which silicon tetrachloride is hydrolyzed in an
oxyhydrogen flame, which is sometimes referred to as pyrogenic
silica. The tapped density of these silicas is somewhere around 50
g/l. Both the precipitated silicas and the pyrogenic silicas can be
after-treated in a secondary stage in order to change the naturally
hydrophilic surface to a hydrophobic surface e.g. by a suitable
chlorosilane to react with a silanol group on the surface of the
silica.
The term "DBP absorption" refers to dibutyl phthalate absorption as
defined in ASTM D2414 which the industry employs to measure surface
area of finally divided materials. See, e.g., Degussa, Technical
Bulletin, Pigments Synthetic Silicas for Plant Protection and Pest
Control, No. 1, 5th Ed., issued July 1990.
The silicas and silicates are further described in Technical
Bulletin Pigments, Synthetic Silicas For Plant Protection and Pest
Control. No. 1 Degussa, Pig. 27-6-2-79OME, 5th Ed., Date of Issue:
Jul. 19, 1990, CAB-O-SIL.RTM. FUMED SILICAS. TD-117 7M/11/92,
Copyright 1990 Cabott Corporation, and Bergna, The Colloid
Chemistry of Silica, ACS, 1994 all of which are incorporated herein
by reference.
Silicas that are especially suitable, include both the hydrophilic
and the hydrophobic silicas which have been treated with a
chlorosilane, and generally have a surface area of from about 50 to
450 m.sup.2 /g, an average agglomerate size of from about 3.5 to
about 100 .mu.m, or an average primary particle size of from about
12 to 30 nm, a tapped density of from about 50 to 240 g/l, a pH of
from about 3.6 to about 9, and a DBP adsorption of about 160 to 335
g/100 g.
The silicates that may be employed in this regard comprise those
that have a surface area from about 30 to about 40 m.sup.2 /g, an
average agglomerate size of from about 4 to about 6 .mu.m, a tapped
density of from about 285 to 315 g/l, a pH of from about 9.5 to
about 10.5, and a DBP adsorption of from about 150 to about 170
g/100 g.
The other inorganic carriers and some of the polymeric organic
carriers noted in this regard will also have substantially the same
surface area and particle size, although the density will vary
depending upon the material employed. Larger surface areas and
particle sizes can also be utilized. Extruded films that are
water-soluble can also be effective carriers in certain
formulations. Other carriers that may be employed are described by
Stilman, Immobilization On Polymers, 1983 which is incorporated
herein by reference.
The various bioactive agents that are employed in the compositions
of the present invention to treat populations of adult or immature
(e.g., egg, larvae, pupae, nymphs) organisms comprise technical or
formulated (technical plus inerts) pesticides, insecticides,
toxicants, monomolecular surface films, petroleum oils, insect
growth regulators, plant growth regulators, animal growth
regulators, microbial control agents, pharmaceuticals, medicaments,
antibiotics, pathogens, bioactive control agents, parasites,
pharmaceuticals or medicaments, bactericides, and viricides,
fungicides, algaecides, herbicides, nematicides, amoebicides,
acaricides, miticides, predicides, schistisomicides, molluscicides,
larvicides, pupicides, ovicides, adulticides, nymphicides,
attractants, repellents, growth stimulants, feeding stimulants,
nutrients, hormones, chemosterilants, or pheromones, and
combinations thereof, such as the two, three of four component
combinations. Two or more bioactive agents can be combined in the
same composition to achieve multifunctional performance from a
single application.
Insecticidal bioactive materials include Bacillus thuringiensis,
and especially subspecies kurstaki and israelensis, Bacillus
sphaericus, Bacillus popilliae, Seriatia marcescens, and Lagenidium
giganteum, which are sometimes referred to as bioactive agents
employed for the control of insects. Fungal larvicides may also be
employed such as Lagenidium giganteum mycelium or Lagenidium
giganteum oospores or mixtures thereof. Pyrethrin and pyrethroid
larvicides can also be used. Fungal materials can also be effective
against mosquito larvae. Insect growth regulators can be used such
as (S)-methoprene, diflubenzuron, or pyriproxyfen. Aliphatic
petroleum hydrocarbons may also be used as mosquito larvicides or
non-petroleum hydrocarbon oils that form a monomolecular film on
the water to be treated. Compositions and processes for control of
various species of mosquitoes, and other pest dipterans in aquatic
habitats are of particular interest. Bioactive agents of specific
interest for use in these compositions include Bacillus
thuringiensis var. israelensis, Bacillus sphaericus, Lagenidium
giganteum, methoprene, diflubenzuron, pyriproxyfen, temephos, 2 mol
ethoxylate of isostearyl alcohol, lecithins, and petroleum oils,
and combinations thereof, such as the two, three or four component
combinations. Other insecticides may also be employed including
products such as malathion, resmethrin, dichlorvos, bendiocarb,
fenitrothion or chlorpyrifos. Insecticides such as pyrethrin and
pyrethroid can be effective as larvicides for mosquitoes.
Various herbicides that may be employed, especially effective
aquatic herbicides include Amitrole.RTM., ammonium sulfamate,
Bromacil.RTM., copper salts, dalapon, Dichlorbenil.RTM.,
Diquat.RTM., Diuron.RTM., Endothall.RTM., Fenac.RTM.,
Picloram.RTM., Prometon.RTM., Silvex.RTM., Simazine.RTM.,
trichloroacetic acid, 2,4-D, 2,4,5-T, Velpar.RTM., TSMA, dicamba,
endothall, silvex, prometon, chlorate, sodium metaborate, monuron,
and various combinations thereof, such as the two, three or four
component combinations. Other insecticides, herbicides or
fungicides that may be employed are set forth by Page &
Thomson, The Quick Guide, Thomson publications 1987, Thomson,
Agricultural Chemicals, Book I, Insecticides; Book II, Herbicides;
Book III, Fumigants, Growth Regulators, Repellants, 1985-87
revisions, all of which are incorporated herein by reference.
Control of floating and submersed aquatic weeds is also of special
interest. Bioactive agents included in the compositions and
processes for these applications isolven acrolein, aromatic
solvents (xylene), copper sulfate and other water soluble copper
salts or compounds, dalapon, dichlorbenil, 2,4-D, diquat,
endothall, glyphosate, simazine, and fluridone, and combinations
thereof, such as the two, three or four component combinations.
The aquatic organisms that are of special interest and which can be
treated by the compositions of the present invention, and in accord
with the methods of the present invention include disease carrying
or biting or non-biting insects (e.g., mosquitoes, sand flies,
black flies, midges), or other animals (e.g., fish, barnacles,
snails) or aquatic and wetland plants, and especially parasitic
animals (e.g., nematodes, mollusks, protozoans, and bacteria) or
floating or submersed nuisance weeds e.g., algae, duckweed,
hydrilla, water hyacinth, chara, watermilfoil, cattail bass weed,
burreed, coontail, and the various pondweeds including bushy,
curly-leaf, flat stem, floating-leaf, horned, and sago; water star
grass, arrowhead, bladderwort, bulrush, hornwort, creeping water
primrose, pickerelweed, spatterdock, cow lily, yellow water lily,
waterweed, water chestnut, water smart weed, white water lily,
naiad, watershield, elodea, hydroilia, alligatorweed, cattails,
giant cutgrass, guineagrass, knotgrass, maidencane, paragrass,
phragmites, spatterdock, and torpedograss.
It should be noted that any bioactive agent, and combinations
thereof, such as the two, three or four component combinations,
designed for promoting (e.g., nutrients) or terminating (e.g.,
pesticides, or herbicides) the life of aquatic or terrestrial
organisms can be utilized in the compositions of matter, depending
on the desired end result. Specific controlled release compositions
will be designed to deliver the desired bioactive agent(s) in the
targeted portion(s) of the water column of an aquatic habitat.
These bioactive materials, and organisms are further described by
Levy in U.S. Pat. No. 4,818,534, columns 12-14; U.S. Pat. No.
4,983,389, columns 11-13; U.S. Pat. No. 4,985,251, columns 4, 10,
and 12-14; all the foregoing being incorporated herein by
reference.
The coatings that may be employed according to the present
invention are selected so as to act as materials that will regulate
the controlled release rate and release profile of bioactive agents
over a period of time in an aqueous medium, and accordingly have to
be water soluble or partially water soluble and biodegradable, or
insoluble in water, and biodegradable or erodible, and/or
film-forming on contact with water. Coatings may also protect
bioactive agents from photodegradation or biodegradation. The
coatings have a specific gravity equal to or greater than one or
less than one, and are liquids or solids, and generally consists of
either fatty alcohols or acids, or fatty alcohol esters of citric,
glycolic, trimelletic or phthalic acid, or any mono, di- or
tricarboxylic acid having from one to about 18 carbon atoms,
whether saturated or unsaturated, aliphatic or cyclic, and which
are well known in the art. The fatty alcohols in this regard
comprise those alcohols having from about 5 to about 18 carbon
atoms, and include the saturated as well as unsaturated aliphatic
fatty alcohols. The aliphatic acids or alcohols include the
straight chain and branched chain isomers.
The coatings having a specific gravity less than one may comprise
n-butyryl-tri-n-hexyl citrate, monostearyl citrate, stearyl
alcohol, cetyl alcohol, myristyl alcohol, octadecanoic acid,
glyceryl stearate, or waxes whereas the coatings having a specific
gravity greater than one comprise, triethyl citrate, acetyltriethyl
citrate, tri-n-butyl citrate, acetyltri-n-butyl citrate,
acetyltri-n-hexyl citrate, tri-n-hexyltrimellitate, dicyclohexyl
phthalate, diethyl phthalate, butyl phthalyl butyl glycolate,
dimethyl isophthalate, or water-soluble films of polyvinyl alcohol,
polyethylene oxide, methyl cellulose, paper, and hydroxypropyl
methyl cellulose, and combinations thereof, such as the two, three
or four component combinations. It should be noted that
water-soluble films can act in a coating/carrier capacity in
certain compositions of matter. Two or more coatings can be
combined to modify or enhance the controlled release rate or
release profile of one or more bioactive agents in a
composition.
The coatings, bioactive agents and carriers may also be combined
with water soluble or insoluble, hydrophilic or hydrophobic,
biodegradable or erodible, cross-linked or non-crossed-linked,
binder materials such as sulfonated polystyrene homopolymers,
sulfonated styrene maleic anhydride polymers, sulfonated vinyl
toluene maleic anhydride polymers, vinyl pyrrolidone polymers or
copolymers, poly (isobutylene-co-disodium maleate) copolymers,
acrylamide polymers or copolymers, acrylonitrile-starch graft
polymers or copolymers, carboxymethyl cellulose polymers or
copolymers, acrylate polymers or copolymers, poly(vinyl alcohol)
polymers or copolymers, poly(ethylene oxide) polymers or
copolymers, acrylic acid or acrylic ester homopolymers or
copolymers, modified food starch (CAPSUL.RTM. and N-LOCK.RTM.),
natural or synthetic gums, poly(ethylene glycol), clays, gypsum,
plaster of paris, wax, paper, and especially paer as described
herein including without .[.limitaion.]. .Iadd.limitation.Iaddend.,
BIODAC.RTM., cellulose, latex, methyl vinyl ether maleic acid ester
copolymers, and various starches and modified starches as described
by Davidson Book Of Water-Soluble Gums And Resins, 1980, chapter
22, BP. 22-1 to 22-79 which is incorporated herein by reference,
and combinations thereof such as the two, three or four component
combinations to agglomerate the controlled release compositions
into larger units such as granules, pellets, briquets, or
extrusions.
The foregoing polymers or copolymers which comprise superabsorbent
polymers are especially useful in forming agglomerates of the
compositions of the present invention. The various processes are
known for forming these agglomerates some of which are described in
Ferro-Tech General Catalog, Form 317, 8-1-83, revised December 1985
which is incorporated herein by reference, and is published by the
Ferro-Tech.RTM. Corporation, 467 Eureka Road, Wyandotte, Mich.
48192, which is incorporated herein by reference.
The controlled release compositions may also be combined with other
formulating materials or ingredients or components wherein such
components are diluents, adjuvants, dyes, alcohols, acetone,
ketones, oils, surfactants, water, emulsifiers, film-forming
agents, compatibility agents, wetting agents, salt, natural or
synthetic polymers, hydrocolloids, buoyancy modifiers, ultraviolet
absorbers, photo-protecting agents, suspending agents, elastomers,
penerrants, deflocculating agents, dispersing agents, stabilizing
agents, antifoaming agents, sticking agents, solvents, co-solvents,
catalysts, or synergists, and the like, and combinations thereof,
such as the two, three or four component combinations.
Components of the present invention can be homogeneously or
heterogeneously combined into the desired controlled delivery
compositions or complexes for treating a population of aquatic
organisms in an aquatic or preaquatic environment by admixing the
individual solid, and/or liquid formulation components in a
concentration, and order to effectively impregnate or encapsulate
the carrier(s) with the desired concentration of coating agent(s)
and bioactive agent(s).
Admixing with one or more optional binders, and/or formulation
materials can be utilized to agglomerate the composition(s) into
larger units, and/or to achieve optimum controlled release
performance. Formulation components can also be fabricated into
solid controlled delivery compositions by coupling aqueous admixing
procedures with solvent based admixing procedures.
To further modify the controlled delivery rate and release profile
of compositions of matter of the present invention, powdered or
agglomerated compositions can be placed into flexible or rigid
polyvinyl alcohols, polyethylene oxide, and/or hydroxypropyl methyl
cellulose film containers (e.g., pouches, packets, capsules,
extrusions) of varying water solubilities. In addition,
compositions can be optionally placed into various shaped (e.g.,
spherical, cylindrical, etc.) dispensers (e.g., plastic, glass,
metal, etc.) having a specific gravity greater than or less than
one, with one or more orifices (e.g., holes, slots, etc.) in the
wall(s) of the dispensing device to modify the controlled release
rate and release profile of the bioactive agent from the
compositions of matter through the orifice(s) into a water column.
Pretreatment application of these dispensing devices is also within
the scope of the present invention.
An example of a commercially available products that may be
employed in this regard comprise DISSOLVO.TM.-POUCH which is a
polyvinyl alcohol film pouch. The various dimensionally stable
solvable pouches are further describe by Miller in Pesticides
Formulations and Application System; 8th Vol. ASTM STP 980, D. A.
Hovde et al., EDS. American Society for Testing and Materials,
Phil. 1988, which is incorporated herein by reference.
The compositions of the present invention can be formulated to
time-release one or more bioactive agents from the carrier to treat
a population of organisms in specific areas of a water column of an
aquatic environment according to zero-order, first-order, or
square-root-of-time kinetics. In general, depending on the type,
concentration, and number of coatings utilized on a composition,
and the formulation procedures utilized in fabricating the
compositions, controlled delivery of one or more bioactive agents
from the carrier can be fast, slow, delayed or pulsed. Controlled
release formulations can be prepared wherein the materials for the
preparation of such controlled release compositions are described
by Wilkins, Controlled Delivery of Crop-Protection Agents, 1990,
Kydonieus, Controlled Release Technologies: Methods, Theory And
Applications, Volumes 1 and 2, 1980; Barker Controlled Release Of
Biologically Active Agents, 1987, Marrion, The Chemistry And
Physics Of Coatings, 1994; Muller Carriers For Controlled Drug
Delivery And Targeting, CRC press; Duncan and Seymour, Controlled
Release Technology 1989; and Karsa and Stephenson, Encapsulation
And Controlled Release 1993, all of which are incorporated herein
by reference.
Controlled release solid compositions utilized in the present
invention for treating a population of one or more aquatic
organisms consist of about 0.001% to about 50% by weight (w/w) of
at least one coating agent, about 0.0001% to about 50% (w/w) of at
least one bioactive agent, and about 50% to about 99% (w/w) of at
least one carrier, with or without about 0.0001% to about 75% (w/w)
of one or more binders, and/or one or more formulating materials or
about 0.1% to about 99.9% (w/w) of at least one joint-function
carrier/coating agent, about 0.001% to about 90% (w/w) of at least
one bioactive agent; with or without about 0.0001% to about 75%
(w/w) of one or more binders, and/or one or more formulating
materials.
Controlled release solid compositions utilized in the present
invention for specifically treating a population of one or more
species of mosquitoes in their aquatic stages, typically consist of
about 1.0% to about 25% (w/w) of at least one coating agent, about
0.01% to about 30% (w/w) of at least one bioactive agent, and about
70 to about 95% (w/w) of at least one carrier; with or without
about 0.01% to about 60% (w/w) of one or more binders, and/or
formulating materials or about 50% to about 99% (w/w) of at least
one joint-function carrier/coating, about 0.1% to about 30% (w/w)
of at least one bioactive agent; with or without about 0.01% to
about 60% (w/w) of one or more binders, and/or formulating
materials. Solid compositions of the present invention can
optionally be suspended in water or oil for application as a liquid
spray.
In the embodiment of the present invention comprising complexes for
treating a population of one or more aquatic organisms in a column
of water, the complexes comprise at least one controlled delivery
system, and especially from about one to about three controlled
delivery systems. Each controlled delivery system in turn comprises
at least one carrier, at least one bioactive agent as a component
for treating a population of one or more aquatic organisms, and at
least one coating component or at least one joint-function
carrier/coating agent for regulating the controlled release rate
and release profile of the bioactive agent in water with or without
one or more binder components as an agglomeration aid or one or
more additional formulation materials, which is intended to mean
anywhere from one to about three of each of these components.
By properly selecting one or more of the various bioactive
components, and/or other components, a composition of matter can be
provided that will be effective to treat a population of one or
more aquatic organisms or a plurality of aquatic organisms at
either the surface, subsurface, the bottom or, the entire column of
water.
Each one of these components is selected to sink or float so that
the complex will permeate and remain in any planar or volumetric
segment of a water column for a period of time sufficient to treat
a population of one or more aquatic organisms.
It should be noted in this regard that even though silica has a
specific gravity greater than one, a finely divided silica that has
been surface treated with silicone, as noted herein, will float
because of the hydrophobic properties imparted to it by the
silicone coating. Accordingly, the hydrophobicity of the components
in the composition of matter has to be taken into account when
formulating the composition of the present invention by adjusting
the type, and/or quantity of the hydrophobic component(s)
employed.
Similarly, the density or the flotation properties of the other
components of the compositions of matter of the invention have to
be taken into account, as well as the quantity of such components
when formulating the compositions of the invention so that it will
be delivered to the appropriate planar or volumetric segment of the
column of water that is to be treated according to the processes of
the invention. When this formulation method is employed, a
controlled delivery composition of matter can be prepared having a
buoyancy selected to treat any part of a water column, or an entire
water column.
Thus, a controlled delivery composition of matter can be prepared
based on a carrier that sinks, and a bioactive material and coating
that floats, each being employed in amounts that can be readily
determined, so that the bioactive material will be taken to the
bottom of a water column by the carrier, and upon exposure to water
in the column, the coating will be released, and carry the
bioactive material to the surface to treat any surface organisms or
any organisms encountered in moving toward the surface. An example
of a controlled delivery system like this comprises sand coated
with the optimum concentration of cetyl alcohol in combination with
a bioactive material that floats.
Similarly, a carrier can be selected that floats in combination
with a coating that floats, and a bioactive material that sinks,
where the types and quantities of each are experimentally
determined so that the composition floats. Upon exposure to water,
the coating will release the bioactive material which will move
towards the bottom of the column, and treat any aquatic organisms
that are at the bottom or encountered in moving toward the bottom
of the column. An example of a controlled delivery composition of
matter that will function in this way comprises silica that floats,
i.e., hydrophobic finely divided silica coated with a silicone
material, in combination with cetyl alcohol, and any known
bioactive material that sinks.
Another controlled delivery composition of matter can be prepared
based on a carrier and bioactive agent that sinks, and a coating
that floats each being employed in amounts that can readily be
determined so that the bioactive material will be taken to the
bottom of a water column by the carrier, and upon exposure to the
water the coating will be released, and initially carry the
bioactive agent to the surface to treat any surface organisms
encountered in moving toward the surface, and then after being
maintained at the surface for some period of time, the bioactive
agent will slowly move toward the bottom where it will be available
to treat organisms on the downward movement through the water
column, and at the bottom of the water column. An example of a
controlled delivery system like this comprises sand coated with an
optimum concentration of cetyl alcohol in combination with a
bioactive agent that sinks.
Furthermore, compositions of matter of the invention comprising a
joint-function carrier/coating agent, and bioactive agent, such as
a sinking, and/or floating joint-function carrier/coating agent, or
a joint-function carrier/coating agent, an additional coating
agent, and a bioactive agent can be developed to distribute a
bioactive agent to desired areas or volumes of a water column over
time, or to one or more terrestrial organisms over time. Especially
suitable joint-function carrier/coating agents comprise polyvinyl
alcohol, polyethylene oxide, hydroxypropyl methyl cellulose, cetyl
alcohol or stearyl alcohol and various combinations thereof such as
the two, three or four component combinations.
All compositions can be optionally combined with a binder to
agglomerate the composition into larger units such as granules,
pellets, and briquets, or an additional formulation ingredient. In
addition, all compositions can also be optionally dispensed in a
water column enclosed within water soluble film containers, and/or
dispensed from devices having one or more orifices open.
From these descriptions, it is obvious that one or more floating,
and/or sinking carriers, coatings, and bioactive agents with or
without binders or additional formulation ingredients can be
combined in various permutations, and combinations into controlled
release compositions that are designated to target desired areas or
volume segments of a water column of an entire water column to
treat a population of one or more aquatic organisms.
It should be noted in this regard that the water column is defined
as a volume of water underneath the surface of water of a specified
area that requires treatment, the body of water including ponds,
lakes, bays, wetlands, marshes, swamps, tidal basins, lagoons,
sounds, creeks, streams, rivers, oceans, ditches, swales, sewage
treatment controlled delivery systems, potholes, tree holes, rock
holes, bromeliads, tires, which is to say moving or stagnant water
containing one or more target organisms. Thus, the treated column
of water can be either moving or stationary, and have any water
quality that can be utilized as a habitat for the target
organism(s).
By treating a column of water, as that term is employed herein, it
is intended not only to provide the compositions of matter of the
present invention to a column of water that is infested with
aquatic organisms that exist in the column, but also a column of
water that has the potential of being infested with aquatic
organisms. Compositions of matter of the present invention are also
provided for pretreatment application to a dry habitat that has not
yet flooded by rain, tides, and the like, to produce a defined
water column where aquatic organisms are known to breed, i.e. a
preflood area. Compositions of matter for pretreatment of an
existing water column that is not yet infested with aquatic
organisms or that are infested with organisms are also within the
scope of the invention.
The compositions of the present invention can be applied by ground
or aerial techniques as dry powders, agglomerates such as granules,
pellets, and briquets, and encapsulated within water soluble or
degradable pouches or capsules of polyvinyl alcohol, polyethylene
oxide, hydroxypropyl methyl cellulose, paper, or gelatin, and/or
within devices having one or more orifices in contact with the
water column. The compositions of the present invention can also be
applied as water, and/or oil based formulations.
In the following examples powdered and agglomerated controlled
delivery compositions of matter are utilized as examples to
illustrate the present invention, and were designed to target
surface, subsurface, or both surface, and subsurface areas of an
aquatic habitat. Larvae of Anopheles spp. mosquitoes were used as
models to demonstrate the efficacy of surface active compositions,
while larvae of Aedes spp. and Culex spp. mosquitoes were used to
demonstrate subsurface efficacy.
Insecticidal bioactive agents admixed with a variety of carriers
and coatings or joint-function carrier/coatings, with or without
binders or formulating materials, were commercial formulations of
the bacteria Bacillus thuringiensis var. israelensis (B.t.i.)
(Acrobe.RTM. Technical Powder, Acrobe.RTM. Biolarvicide or
Vectobac.RTM. Technical Powder), the insect growth regulator
methoprene (Dianex.RTM. Emulisifiable Concentrate), a mixture of
Acrobe.RTM. TP, and Dianex.RTM. EC, the organophosphate temephos
(Abate.RTM. 4-E) or an experimental monomolecular surface film
(POE(2) 2 mol ethoxylate of isostearyl Alcohol). Additional
insecticidal bioactive agents admixed with a variety of coatings
and carriers, with or without binders or formulation materials,
that were not utilized in mosquito bioassays, were commercial
formulations of the insect growth regulators diflubenzuron
(Dimilin.RTM. Wettable Powder) or pyriproxyfen (Nylar.RTM.
Technical or Emulsifiable Concentrate), the bacteria Bacillus
sphaericus (ABG-6184), the fungus Lagenidium giganteum, and the
petroleum oil (GB-1111). Examples of liquid or solid coatings
utilized in the compositions of matter to regulate the controlled
release rate and release profile of the bioactive agent(s) from the
carrier were esters of citrate (Citroflex.RTM.2, A-2, 4, A-4, A-6
or B-6), phthalate, glycolate, trimellitate (Morflex.RTM. 150, 190,
or 560), cetyl alcohol, and/or polyvinyl alcohol films
(MonoSol.RTM. 7000 or 8000 series). Coatings ranged from water
soluble to insoluble, and had specific gravities less than or
greater than one. Solid carriers utilized in the compositions of
matter as surface or subsurface-active bioactive agent delivery
matrices were hydrophobic (Sipernate.RTM.D17, and Aerosil.RTM.R972)
or hydrophilic (Wesslon.TM., Wesslon.TM.50, Sipernat.RTM.22S, and
FK 500 LS) Degussa silicas, sand (Texblast.RTM.), cetyl alcohol
(Sigmas.RTM.)(specific gravity less than one), and/or polyvinyl
alcohol films (MonoSol.RTM.7000 or 8000 series) (specific gravity
greater than one). Polymeric binders utilized in the examples to
agglomerate the powdered compositions into larger units were
soluble starch (Difco.RTM.), sulfonated polystyrene
(Versa.RTM.TL-502), sulfonated vinylic copolymers (Narlex.RTM.
D-82), acrylic copolymer (Carboset.RTM.514H), and acrylic polymer
(Carbopole.RTM.ETD 2001 Resin). Additional formulation materials
such as water, soluble or insoluble alcohols (2-propanol, 2-ethyl
hexanol, 2mol ethoxylate of isostearyl alcohol) or ketones
(acetone, methyl ethyl ketone) were also utilized as admixture
components in selected compositions.
A series of bioassays were designed to demonstrate the short or
long-term mosquito-controlling effectiveness of a variety of
powdered and agglomerated compositions that were formulated to
time-release one or more mosquitocidal bioactive agents in specific
areas of a water column or the entire water column. Composition
transfer bioassays were utilized to evaluate the controlled release
duration of selected powdered or agglomerated formulations. The
efficacy of pretreatment compositions was also evaluated. Powdered
or agglomerated compositions were evaluated at ca. 27.degree. C. in
0.019 m.sup.2 1/2 gal plastic containers containing 1000 ml of
fresh water (purified by reverse osmosis filtration) or brackish
(10% Instant Ocean.RTM./distilled water) water and ten 1st to 4th
instar larvae of the Anopheles, Aedes, or Culex species. Bioassays
were also conducted with mixed species populations. Tests with each
powdered or agglomerated controlled delivery composition were
replicated three times.
The following examples are illustrative of the controlled delivery
fabrication protocols, types of powdered and agglomerated
controlled release compositions, and processes for treating a
population of aquatic organisms in a column of water.
EXAMPLE 1
The admixing protocol for the components utilized in the powdered
composition (Code J) in this bioassay series against mosquito
larvae was as follows: 10 g cetyl alcohol (heated to 60.degree. C.)
and 5 g triethyl citrate (Citroflex.RTM.2) were each added
separately to 300 g acetone in 1/2 gal plastic beakers and mixed
with a laboratory hand mixer (GE.RTM. Model 420A) for ca. 5
minutes. 5 g of B.t.i. (Acrobe.RTM.TP) was then slowly added to
each coating formulation while mixing for an additional 5 minutes.
85 g and 90 g hydrophobic silica (Sipernat.RTM.D17) were slowly
added to the cetyl alcohol and triethyl citrate formulations of
bacteria, respectively, while mixing for an additional 21/2-3 hr to
drive off the acetone and assure that the B.t.i. and each coating
were uniformly impregnated on the silica carrier. Powdered
compositions were placed in a low humidity room (27-38% RH:
76.degree.-79.degree. F.) for an additional 4 hr to assure
volatilization of the acetone. Each powdered formulation was stored
in zip-lock (trade mark) bags or glass bottles. Sub samples of each
of the two formulations were admixed at a 1:1 ratio for an
additional 5 minutes to achieve the powdered composition utilized
for testing.
Results of short-term bioassays against Anopheles, Aedes, and Culex
species in fresh or brackish water with a powdered controlled
delivery composition comprising a 1:1 blend of an acetone-base (300
g) admixture formulation (w/w) of 5 g of B.t.i. (specific gravity
greater than one/insoluble in water) labeled Acrobee.RTM.TP (3864
ITU/mg), 10 g cetyl alcohol (specific gravity less than
one/insoluble in water), and 85 g hydrophobic silica
(Sipernat.RTM.D17) and another acetone-base (300 g) admixture
formulation (w/w) of 5 g Acrobee.RTM.TP, 5 g triethyl citrate
(Citroflex.RTM.2; specific gravity greater than one/water soluble),
and 90 g Sipernat.RTM.D17 indicated that the multiply
coated/encapsulated B.t.i. could be released from the hydrophobic
silica carrier at varying intervals/rates and provide effective
control of both surface and subsurface feeding mosquito larvae at
extrapolated application rates of ca. 2.5 lb/surface acre of water
(Table 1). The efficacy of the composition against the Anopheles
species indicated that Acrobe.RTM.TP can be maintained at the
surface feeding area of an aquatic habitat for a sufficient period
of time to effectively allow the Anopheles larvae to ingest lethal
concentrations of toxic crystals of B.t.i. Efficacy against Aedes
and Culex species suggested that the dense B.t.i. was slowly
released from the surface-active carrier/coating formulation below
the surface of the water through the water column where the toxic
crystals were accessible to the subsurface and bottom feeding
species. In general, the powdered controlled delivery composition
was effective in releasing sufficient concentrations of B.t.i. over
a 1 to 5 day posttreatment period to produce 100% control of
surface or subsurface feeding mosquito larvae in fresh or brackish
water. Controlled release of B.t.i. from the silica carrier to
surface and/or subsurface areas of a water column was a function of
the type and concentration of coating agents. The initial point of
B.t.i. release and distribution at the water interface was a
function of the hydrophobic nature of the carrier.
TABLE 1 (Example 1). Coating-Regulated Delivery of Acrobe .RTM. TP
form a Hydrophobic Silica Carrier* % Control of Larvae at Indicated
Posttreatment Mosquito Larval Water Time Period (Days)** Species
Insar Quality 1 2 3 4 5 Surface Feeders (Anopheles spp.) An.
albimanus 2nd Fresh 100.0 -- -- -- -- An. albimanus 3rd Fresh 83.3
90.0 100.0 -- -- An. albimanus 4th Fresh 23.3 60.0 80.0 100.0 --
An. albimanus 2nd Brackish 90.0 100.0 -- -- -- An. Albimanus 3rd
Brackish 83.3 96.7 100.0 -- -- An. albimanus 4th Brackish 53.3 76.7
96.7 100.0 -- An. quadrimaculatus 2nd Fresh 100.0 -- -- -- -- An.
quadrimaculatus 3rd Fresh 70.0 100.0 -- -- -- An. quadrimaculatus
4th Fresh 50.0 50.0 53.3 96.7 100.0 Subsurface Feeders (Aedes and
Culex spp.) Ae. aegypti 1st Fresh 100.0 -- -- -- -- Ae. aegypti 3rd
Fresh 53.3 90.0 100.0 -- -- Ae. taeniorhynchus 3rd Brackish 90.0
93.3 96.7 100.0 -- Cx. quinquefasciatus 3rd Fresh 26.7 43.3 83.3
100.0 -- *5% Acrobe .RTM. TP (w/w) utilized in the controlled
release composition. Cetyl alcohol and triethyl citrate utilized as
B.t.i. release-rate regulators (formulation ratio of 1 part cetyl
alcohol/B.t.i. to 1 part triethyl citrate/B.t.i.). **B.t.i.
compositions applies as a powder at ca. 2.5 l/acre.
EXAMPLE 2
Another series of bioassays with other types of powdered controlled
release compositions were conducted against larvae of Anopheles,
Aedes, and mixed populations of Anopheles and Culex species in
fresh and brackish water. In formulating these compositions of
matter. B.t.i. Acrobe.RTM.TP) was admixed with other types of
hydrophobic (Aerosile.RTM.R972) and/or hydrophilic (FK 500 LS)
silica hydrophobic wood "pin chips" or saw dust (Sea Sweep.RTM.),
or sand (Texblast.RTM.) carriers and cetyl alcohol and/or triethyl
citrate (Citroflex.RTM. 2) coating agents into powdered controlled
delivery compositions that had an affinity for targeting selected
areas of an aquatic habitat (Table 2).
Results of a series of short-term bioassays with these powdered
controlled release compositions are presented in Table 3. The data
indicated that the type(s) of powdered carrier(s) (e.g.,
hydrophobic and/or hydrophilic) and the type(s) and concentration
of coating/encapsulation agent(s) e.g., specific gravity greater
than and/or less than one/water soluble and/or insoluble) utilized
in a powdered composition would dictate the orientation of delivery
in a water column and the rate of release of larvicidal bacteria.
All powdered compositions provided 100% control of larvae in fresh
or brackish water. In general, results indicated that specific
carriers and coatings could be combined with B.t.i. in a manner to
selectively target subsurface/bottom feeding mosquito larvae or
mixed populations of surface and subsurface/bottom feeding mosquito
larvae. The type of carrier was observed to initially orient the
bioactive agent (i.e., B.t.i.) in a surface or subsurface plane of
the water column while the type of coating agents would dictate
controlled release persistence, rate, direction, and/or a change in
the initially observed surface or subsurface release plane of
B.t.i.
TABLE 2 (Example 2). Formulation Components in Powdered Controlled
Delivery Compositions* Compo- sition No. Concentration of
Admixtures in Powdered Compositions 1 5 g B.t.i. (Acrobe .RTM.TP) +
5 g cetyl alcohol + 5 g triethyl citrate (Citroflex .RTM.2) + 42.5
g hydrophobic silica (Aersoil .RTM.R972) + 42.5 g hydrophilic
silica (FK 500 LS) 2 5 g B.t.i. (Acrobe .RTM.TP) + 10 g cetyl
alcohol + 85 g hydrophilic silica (FK 500 LS) 3 10 g B.t.i. (Acrobe
.RTM.TP) + 10 g triethyl citrate (Citroflex .RTM. 2) + 180 g
hydrophobic "pin chips" (Sea Sweep .RTM.) 4 5 g B.t.i. (Acrobe
.RTM.TP) + 20 g cetyl alcohol + 75 g sand (Texblast .RTM.) *Cetyl
alcohol (heated to 60.degree. C.) and/or triethyl citrate was added
to 300 g acetone and mixed for 5 minutes with a GE .RTM. Model 420A
hand mixer in a 1/2 gal plastic beaker. B.t.i. was slowly added to
solvent-base formulation of coating(s) while mixing for an
additional 5 minutes. Hydrophobic and/or hydrophilic silica or sand
was admixed with the other components while mixing was continues #
for ca. 3 hr to drive off the acetone and assure a homogeneous dry
mixture of all the components. Hydrophobic "pin chips" were ground
with a Micro-Mill .RTM. into a fine powder. Triethyl citrate was
added to a stainless steel bowl containing 800 g acetone and mixed
for ca. 5 minutes with a KitchenAid .RTM. KSM 90 (speed #6) hand
mixer. B.t.i. was added slowly and mixing was continued for ca. 5
minutes. Ground "pin chips" were slowly added to the mixture while
blending # was continued on speed #2 for ca. 4 hr until the
powdered formulation was dry. All powdered compositions were placed
in a low-humidity room (ca. 27-38% RH) for ca. 3 hr to assure
volatilization of the solvent. Powdered compositions were stored in
zip-lock bags or glass bottles.
TABLE 3 (Example 2). Coating-Regulated Delivery of Acrobe .RTM. TP
From Several Types of Hydrophobic and Hydrophilic Carriers.* %
Control of Larvae at Indicated Posttreatment Mosquito Larval Water
Composition Time Period (Days)** Species Instar(s) Quality No. 1 2
3 4 5 6 7 Subsurface Feeders (Aedes and Culex spp.) Ae. aegypti 2nd
Fresh 1 76.7 90.0 96.7 100.0 -- -- -- Ae. aegypti 3rd Fresh 2 93.3
96.7 100.0 -- -- -- -- Ae. taeniorhynchus 3rd Brackish 1 90.0 100.0
-- -- -- -- -- Ae. taeniorhynchus 3rd Brackish 2 63.3 90.0 100.0 --
-- -- -- Ae. taeniorhynchus 3rd Brackish 3 40.0 83.3 96.7 96.7
100.0 -- -- Cx. quinquefasciatus 3rd Fresh 1 63.3 83.3 96.7 100.0
-- -- -- Cx. quinquefasciatus 3rd Fresh 3 93.3 100.0 -- -- -- -- --
Cx. quinquefasciatus 4th Fresh 1 100.0 -- -- -- -- -- -- Cx.
quinquefasciatus 4th Fresh 2 100.0 -- -- -- -- -- --
Subsurface/Surface Feeders (Culex and Anopheles spp.)*** Cx.
quinquefasciatus/ 3rd/2nd Fresh 2 83.3 93.3 93.3 96.7 100.0 -- --
An. albimanus Cx. quinquefasciatus/ 3rd/2nd Fresh 4 50.0 63.3 66.7
90.0 90.0 93.3 100.0 An. albimanus *5% Acrobe .RTM. TP utilized in
all controlled release compositions. Cetyl alcohol and/or triethyl
citrate utilized as B.t.i. release-rate regulators. **B.t.i.
compositions applied as a powder at ca. 2.5 lb/acre. ***Mixed Culex
and Anopheles larvae (1:1).
EXAMPLE 3
Powdered admixtures of B.t.i. (Acrobe.RTM.TP), a hydrophobic silica
(Sipernat.RTM.D17) carrier, acetyl alcohol coating, and a soluble
starch, sulfonated polystyrene (Versa.RTM.TL-502) or sulfonated
vinylic (Narlex.RTM.D-82) polymeric binder were also agglomerated
by hand into a series of controlled delivery briquets (Table 4).
Small cubettes (ca. 3.5.times.3.5.times.4.5 mm) were sectioned from
each type of B.t.i. briquet and utilized in a series short-term
bioassays against 2nd instar larvae of Anopheles and Culex species
in fresh and brackish water. One cubette per bioassay test chamber
(i.e., plastic 1/2 gal beakers) was equivalent to an extrapolated
application rate of ca. 5 lb/surface acre of water.
Evaluation of 3 types of Acrobe.RTM.TP cubettes against Anopheles
and Culex larvae indicated that the rate of control was a function
of the coating-regulated release of B.t.i. from the encapsulated
silica and the rate of binder-regulated dissociation of the
powdered components from the agglomerated matrices in fresh or
brackish water (Table 5). Observations indicated that the initial
orientation of the Narlex.RTM., soluble starch, and Versa.RTM.
cubettes on introduction to water was sinks, sinks, and floats,
respectively. Dissociation of Narlex.RTM. and Versa.RTM. cubettes
into smaller powder-like components occurred in ca. 5 minutes after
introduction into the fresh or brackish water, while soluble starch
cubettes dissociated into several small subagglomerated units in
about 24 hr after introduction to fresh or brackish water. The
smaller subagglomerated units were observed to dissociate into
still smaller powder-like components over a several day period. The
hydrophobic silica carrier coated with the insoluble, low specific
gravity cetyl alcohol and B.t.i. was observed to float upon being
released from the initial surface or subsurface orientation of the
cubette in the aquatic habitat. The series of agglomerated B.t.i.
compositions produced 100% control of larvae within 1 to 9 days
posttreatment.
TABLE 4 (Example 3). Formulation Components in Agglomerated
Controlled Delivery Compositions* Composi- tion Code Concentration
of Admixtures in Agglomerated Compositions A 5 g [5 g B.t.i (Acrobe
.RTM. TP) + 10 g cetyl alcohol + 85 g hydrophobic silica (Sipernat
.RTM. D17)] + 5 g sulfonated poly- styrene polymer (Versa .RTM.
TL-502) B 5 g [5 g B.t.i. (Acrobe .RTM. TP) + 10 g cetyl alcohol +
85 g hydrophobic silica (Sipernat .RTM. D17)] + 5 g sulfonated
vinylic copolymer (Narlex .RTM. D-82) C 5 g [5 g B.t.i. (Acrobe
.RTM. TP) + 10 g cetyl alcohol + 85 g hydrophobic silica (Sipernat
.RTM. D17)] + 5 g soluble starch *Cetyl alcohol (heated to
60.degree. C.) was added to 300 g acetone and mixed for ca. 5
minutes with a GE .RTM.Model 420A hand mixer in a 1/2 gal plastic
beaker. B.t.i. was slowly added into the solvent-base formulation
of coating while mixing for an additional 5 minutes. Hydrophobic
silica was mixed with the other components while mixing was
continued for ca. 3 hr to drive off the acetone and assure a
homogeneous dry # mixture of all components. The powdered
composition was placed in a low humidity room (ca. 27-38% RH) for
ca. 4 hr to assure volatilization of solvent. A ratio of one part
of this powdered 3-part bioactive agent/coating/carrier formulation
was mixed with one part binder (sulfonated polystyrene polymer,
sulfonated vinylic copolymer or soluble starch) for ca. 5 minutes.
The 1:1 composition was then hand compacted into # 25 .times. 20
.times. 5 mm vinyl specimen molds (Cryomold .RTM.) and placed in a
high humidity curing room (ca. 80% RH and 80.degree. F.) for ca. 96
hr. Molds containing each composition were then transferred to a
drying room (ca. 27-38% RH, 76-79.degree. F.) for an additional 96
hr. The dry solidified briquet compositions in each mold were
stored in a plastic zip-lock bags. Subsections of each briquet
(i.e., ca. # 3.5 .times. 3.5 .times. 4.5 mm cubettes) were utilized
in the bioassays. One cubette (ca. 0.01 g) was utilized against
mosquito larvae in each bioassay test chamber (3
replications/agglomerated composition).
TABLE 5 (Example 3). Coating-Regulated Delivery of Acrobe .RTM. TP
from Agglomerated Compositions* % Control of 2nd Instar Larvae at
Indicated Posttreatment Mosquito Water Composition Time Period
(Days)** Species Quality Code 1 2 3 4 5 6 7 8 9 Surface Feeders
(Anopheles spp.) An. albimanus Fresh A 93.3 100.0 -- -- -- -- -- --
-- An. albimanus Fresh B 100.0 -- -- -- -- -- -- -- -- An.
albimanus Brackish A 90.0 100.0 -- -- -- -- -- -- -- An. albimanus
Brackish B 90.0 100.0 -- -- -- -- -- -- -- An. albimanus Brackish C
16.7 33.3 33.3 43.3 86.7 96.7 100.0 -- -- An. quadrimaculatus Fresh
A 93.3 100.0 -- -- -- -- -- -- -- An. quadrimaculatus Fresh B 96.7
100.0 -- -- -- -- -- -- -- Subsurface Feeders (Culex spp.) Cx.
quinquefasciatus Fresh A 100.0 -- -- -- -- -- -- -- -- Cx.
quinquefasciatus Fresh B 93.3 100.0 -- -- -- -- -- -- -- Cx.
quinquefasciatus Fresh C 23.3 43.3 63.3 70.0 83.3 86.7 90.0 96.7
100.0 *5% Acrobe .RTM. TP (w/w) utilized in each agglomerated
controlled release B.t.i. composition. Compositions contained
B.t.i., a cetyl alcohol coating, a hydrophobic silica carrier, and
a sulfonated polystyrene polymer, sulfonated vinylic copolymer, or
soluble starch binder (formulation ratio of 1 part bioactive
agent/coating/carrier to 1 part binder). **B.t.i. compositions
applied as an agglomerated cubette at ca. 5 lb/acre.
EXAMPLE 4
A controlled delivery system for solvent-base (i.e., acetone)
precipitation was developed to agglomerate an aqueous admixture
suspension of a joint-function carrier/coating water soluble
polyvinyl alcohol film (MonoSol.RTM. 8000 series) and B.t.i.
(Acrobe.RTM. Biolarvicide). The procedure utilized a series of
acetone washes to rapidly congeal the aqueous homogeneous mixture
of polyvinyl alcohol film and B.t.i. into a unified mass by
removing the water entrapped within the solid. Polyvinyl alcohol
films (specific gravity greater than one) are soluble in water and
insoluble in acetone while B.t.i. is suspendible in water but
insoluble in acetone or water.
Compositions were prepared utilizing the following protocol: 12 g
polyvinyl alcohol film (MonoSol.RTM. 8000 series) was dissolved in
46.8 g distilled water in a plastic beaker. 1.2 g Acrobe.RTM.
Biolarvicide was mixed with the water-base joint-function
carrier/coating with a GE.RTM. 420A hand mixer for ca. 2 minutes.
The formulation was poured into 2 ounce glass medicine bottles and
vigorously hand shaken for ca. 1 minute. 7 to 10 g polyvinyl
alcohol film/B.t.i./water formulation was added to a plastic
centrifuge tube (ca. 60 ml capacity) containing ca. 35-40 g
acetone. The centrifuge tube was capped and vigorously hand shaken
to solidify the polyvinyl alcohol film and B.t.i. into a unified
mass within the aqueous-acetone medium. The solid mass was removed
and placed into 50 ml glass beakers containing ca. 40 g acetone for
a series of five one minute washes to remove entrapped water from
within the solid matrix. The solid mass was removed from the
acetone and thoroughly air-dried in a low humidity room (ca. 27-38%
RH) for ca. 72 hr. The solid compositions were stored in zip-lock
(trade mark) bags until bioassay. The remaining stock formulation
of water, polyvinyl alcohol film, and B.t.i. was stored in a
refrigerator (ca. 40.degree. F.) for future use.
A series of short-term bioassays were conducted against larvae of
Anopheles, Aedes, and Culex species in fresh and brackish water
with 2.times.2.times.2 mm cubettes that were sectioned from each
agglomerated mass of polyvinyl alcohol film and B.t.i. (Table 6).
An application rate of one cubette (ca. 0.01 g) per bioassay test
chamber (i.e., 1/2 gal plastic beaker) was extrapolated to be ca. 5
lb/surface acre of water (3 replications/test). Results indicated
that 100% control of surface or subsurface feeding larvae could be
achieved in fresh or brackish water within 1 to 5 days
posttreatment. Based on the specific gravity of the components,
cubettes were expected to sink upon introduction to fresh and
brackish water. However, observations indicated that the
agglomerated polyvinyl alcohol film compositions initially floated
and began to solubilize over a 24 hr period, thereby rapidly
releasing significant quantities of B.t.i. from the surface to
subsurface areas while also retaining B.t.i. in the polyvinyl
alcohol film that had spread over the surface of the water. It
appears that air bubbles entrapped within the polyvinyl alcohol
film matrix during the vigorous admixing procedure in combination
with the suspending agents/surfactants present in the Acrobe.RTM.
Biolarvicide formulation were responsible for the initial surface
orientation of the cubettes, and the film-forming properties of the
water soluble cubettes. The data on the rates of mortality of
surface (i.e., Anopheles spp.) and subsurface (i.e., Aedes and
Culex spp.) feeding larvae support the aforementioned observations
concerning film-forming solubilization of cubettes and release of
B.t.i. in the experimental aquatic habitats.
TABLE 6 (Example 4). Coating-Regulated Delivery of Acrobe .RTM.
Biolarvicide from an Agglomerated Joint-Function Composition* %
Control of Larvae at Indicated Posttreatment Mosquito Larval Water
Time Period (Days)** Species Instar Quality 1 2 3 4 5 Surface
Feeders (Anopheles spp.) An. albimanus 2nd Fresh 70.0 76.7 100.0 --
-- An. albimanus 2nd Brackish 46.7 50.0 100.0 -- -- An. albimanus
3rd Fresh 40.0 46.7 90.0 100.0 -- An. albimanus 3rd Brackish 43.3
46.7 100.0 -- -- An. quadrimaculatus 2nd Fresh 93.3 93.3 100.0 --
-- An. quadrimaculatus 3rd Fresh 30.0 30.0 66.7 90.0 100.0
Subsurface Feeders (Aedes and Culex spp.) Ae. taeniorhynchus 2nd
Brackish 100.0 -- -- -- -- Ae. taeniorhynchus 3rd Brackish 100.0 --
-- -- -- Cx. quinquefasciatus 2nd Fresh 100.0 -- -- -- -- Cx.
quinquefasciatus 3rd Fresh 100.0 -- -- -- -- *9% Acrobe .RTM.
Biolarvicide (w/w) in each controlled release B.t.i. composition.
Compositions contained a water and solvent-free joint-function
carrier/coating polyvinyl alcohol film (91%) and bioactive agent
9%. **B.t.i. compositions applied as agglomerated cubettes at ca.
5.0 lb/acre.
EXAMPLE 5
A series of short-term controlled release bioassays were also
conducted against larvae of Anopheles, Aedes, and Culex species in
fresh and brackish water to determine the mosquito-controlling
efficacy of powdered compositions comprising admixtures of B.t.i.
(Vectobac.RTM. TP), the insect growth regulator methoprene
(Dianex.RTM.EC), a joint-action formulation of Dianex.RTM.EC and
B.t.i. (Acrobe.RTM.TP) or an organophosphate (Abate.RTM.4-E) and
acetyl alcohol coating and hydrophobic silica (Sipernat.RTM. D17)
carrier. Abate.RTM.4-E was also admixed with a water soluble
polyvinyl alcohol film (MonoSol.RTM. 8000series) joint-function
carrier/coating to form a solid agglomerated composition that was
sectioned into cubettes (ca. 3.5.times.3.5.times.4.5 mm). Admixing
procedures for formulating these powdered or agglomerated
controlled delivery compositions are presented in Table 7.
Results of bioassays with the powdered and cubette compositions
indicated that controlled delivery of formulations of an
organophosphate (specific gravity greater than one), insect growth
regular (specific gravity less than one) and a bacteria (specific
gravity greater than one) insect growth regulator (specific gravity
less than one) from a hydrophobic silica or joint-function
polyvinyl alcohol film carrier was regulated by the
physico-chemical characteristics of the cetyl alcohol or polyvinyl
alcohol film coatings admixed into the formulation (Table 8). The
data indicated that the surface-active powdered or agglomerated
(cubette) floating compositions were effective in delivering at
varying rates one or more bioactive agents at and/or below the
surface of the water where Anopheles, Aedes, and Culex species
could be targeted by the specific type(s) of bioactive agent(s)
released from the carrier into different vertical and horizontal
areas of the water column. One hundred percent control of all
immature mosquitoes was observed within 1 to 21 days posttreatment
when the compositions were applied as a direct treatment or
pretreatment in fresh or brackish water at an extrapolated rate of
2.5 lb/surface acre of water for powdered compositions and 5.0
lb/surface acre of water for agglomerated compositions.
TABLE 7 (Example 5). Formulation Components in Powdered and
Agglomerated Controlled Delivery Compositions Compo- sition
Concentration of Admixtures in Code Powdered and Agglomerated
Compositions Powdered Compositions* D 0.5 g methoprene (Dianex
.RTM. EC) + 10 g cetyl alcohol + 89.5 g hydrophobic silica
(Sipernat .RTM. D17) E 5 g [0.5 g methoprene (Dianex .RTM. EC) + 10
g cetyl alcohol + 89.5 g hydrophobic silica (Sipernat .RTM. D17)] +
5 g [5 g B.t.i. (Acrobe .RTM. TP) + 10 g cetyl alcohol + 85 g
hydrophobic silica (Sipernat .RTM. D17)] F 5 g B.t.i. (Vectobac
.RTM. TP) + 10 g cetyl alcohol + 85 g hydrophobic silica (Sipernat
.RTM. D17) G 0.5 g temephos (Abate .RTM. 4-E) + 10 g cetyl alcohol
+ 89.5 g hydrophobic silica (Sipernat .RTM. D17) Agglomerated
Compositions** H 0.3 g temephos (Abate .RTM. 4-E) + 12 g polyvinyl
alcohol film (MonoSol .RTM. 8000 series) + 47.7 g distilled water +
acetone bath series *Cetyl alcohol (heated to 60.degree. C.) was
added to 300 g acetone and mixed for ca. 5 minutes with GE .RTM.
Model 420A hand mixer in a 1/2 gal plastic beaker. B.t.i.
methoprene or methoprene and B.t.i. or temephos was slowly added to
the solvent-base formulations of coating while mixing for an
additional 5 minutes. Hydrophobic silica was added to each
solvent-base bioactive agent/coating formulation while mixing was
continued for # ca. 3 hr to drive off the acetone and assure that
the silica was uniformly encapsulated with the homogeneous mixture
of each bioactive agent and coating. Two bioactive agents were
combined into a single formulation by admixing each bioactive
agent/coating/carrier formulations at a 1:1 mixing ratio. Each
powdered composition was placed in a low humidity room (ca. 27-38%
RH) for ca. 4 hr to assure volatilization of the solvent. The dry #
powdered compositions were stored in zip-lock bags or glass bottles
until being utilized in mosquito bioassays. **Polyvinyl alcohol
film was dissolved in distilled water in a plastic beaker. Temephos
was mixed with the aqueous formulation of joint-function
coating/carrier with a GE .RTM. Model 420A hand mixer for ca. 2
minutes. The insecticide formulation was poured into 2 ounce glass
medicine bottles and vigorous shaken by hand for ca. 1 minute. 7-10
g water-base polyvinyl alcohol film/temephos formulation was added
into a plastic # centrifuge tube (ca. 60 ml capacity) containing
ca. 35-40 g acetone. The centrifuge tube was capped and vigorous
hand shaken to solidify the polyvinyl alcohol film and B.t.i.
admixture into a unified mass within the aqueous-acetone medium.
The solid mass was removed and placed into 50 ml glass beakers
containing ca. 40 g acetone for a series of five one minute washes
to remove entrapped water from within the solid matrix. The solid
mass was # removed from the acetone and thoroughly air-dried in a
low humidity room (ca. 27-38% RH) for ca. 72 hr. The solid
compositions were stored in zip-lock bags or glass bottles until
being used for mosquito bioassays. Remaining stock formulation of
water, polyvinyl alcohol, and temphos was stored in a refrigerator
(ca. 40.degree. F.) for future use.
TABLE 8 (Example 5). Coating-Regulated Delivery of Dianex .RTM. EC,
Dianex .RTM. EC/Acrobe .RTM. TP, Vectrobac .RTM. TP or Abate .RTM.
4-E from Powdered or Agglomerated Compositions* No. Days to Achieve
100% Mosquito Larval Water Control of Larvae, Pupae, Species Instar
Quality and/or Emerging Adults Powdered Composition - Dianex .RTM.
EC (0.5% AI Formulation) - Code D An. albimanus 1st Fresh 21** An.
albimanus 1st Brackish 20** Ae. aegypti 3rd Fresh 16 Ae.
taeniorhynchus 3rd Brackish 14 Powdered Composition - Dianex .RTM.
EC/Acrobe .RTM. TP (0.5%/5% AI 1:1 Formulation) - Code E Ae.
taeniorhynchus 3rd Brackish 4 Cx. quinquefasciatus 3rd Fresh 18
Powdered Composition - Vectobac .RTM. TP (5% AI Formulation) - Code
F Cx. quinquefasciatus 2nd Fresh 10 Powdered Composition - Abate
.RTM. 4-E (0.5% AI Formulation) - Code G An. albimanus 1st Fresh 1
An. albimanus 1st Fresh 2** An. albimanus 1st Brackish 1 An.
albimanus 1st Brackish 2** Ae. taeniorhynchus 3rd Brackish 1 Cx.
quinquefasciatus 3rd Fresh 1 Agglomerated Composition - Abate .RTM.
4-E (0.5% AI Aqueous/2.4% AI Dry Formulation) - Code H An.
albimanus 4th Fresh 1 An albimanus 4th Brackish 1 An.
quadrimaculatus 4th Fresh 1 Ae. taeniorhynchus 3rd Brackish 1 Cx.
quinquefasciatus 2nd Fresh 1 *Powdered controlled release
compositions consisted of a cetyl alcohol coating, bioactive
agent(s), and hydrophobic silica carrier. Agglomerated (cubette)
controlled release compositions consisted of a water and
solvent-free joint-function polyvinyl alcohol film coating/carrier
(97.6%) and bioactive agent (2.4%). Powdered and agglomerated
compositions applied to the water at rates of 2.5 and 5.0 lb/acre,
respectively. **Presoaked (pretreatment) in water for 9 days before
transfer to bioassay containers.
EXAMPLE 6
A series of long-term controlled release transfer-bioassays were
conducted against multiple broods of larvae of Anopheles, Aedes,
and Culex species in fresh or brackish water with a variety of
powdered or agglomerated compositions composed of one or more
bioactive agents having differential degrees of specific gravity
greater than or less than one, one or more coatings having specific
gravities with differential degrees of greater than or less than
one as well as differential degrees of water solubility or
insolubility, and a carrier having hydrophobic or hydrophilic
characteristics, with or without a binder component. Carrier
components consisted of either a hydrophobic silica (Sipernat.RTM.
D17) or hydrophilic silica (FK 500 LS or Wesslon.TM. 50). Bioactive
agents utilized in the admixture compositions were B.t.i.
(Acrobe.RTM. TP), a combination of B.t.i. and methoprene
(Dianex.RTM. EC) or temephos (Abate.RTM. 4-E). Coatings utilized as
bioactive agent release rate and release profile regulators were
cetyl alcohol (specific gravity less than one/insoluble in water),
triethyl citrate (Citroflex.RTM. 2; specific gravity greater than
one/water soluble), acetyltriethyl citrate (Citroflex.RTM. A-2;
specific gravity greater than one/water soluble), tributyl citrate
(Citroflex.RTM. 4; specific gravity greater than one/insoluble in
water), acetyltributyl citrate (Citroflex.RTM. A-4; specific
gravity greater than one/insoluble in water), acetyltri-n-hexyl
citrate (Citroflex.RTM. A-6: specific gravity greater than
one/insoluble in water), n-butyltri-n-hexyl citrate (Citroflex B-6;
specific gravity less than one/insoluble in water), dicyclohexyl
phthalate (Morflex.RTM. 150; specific gravity greater than
one/insoluble in water), butyl phthalyl butyl glycolate
(Morflex.RTM.190; specific gravity greater than one/insoluble in
water), and tri-n-hexyl trimellitate (Morflex.RTM. 560; specific
gravity greater than one/insoluble in water). Binders admixed with
selected formulations to assist in agglomerating the fine
components into larger units (e.g., briquets) were either a
sulfonated polystyrene polymer (Versa.RTM. TL-502), a sulfonated
vinylic copolymer (Narlex.RTM. D-82) or a water soluble starch.
Components utilized in the admixing procedures to formulate the
controlled release compositions are presented in Table 9.
Results of a series of long-term transfer bioassays in fresh and
brackish water against several broods of larvae of Anopheles,
Aedes, and Culex species with a variety of powdered and
agglomerated (i.e., cubette) compositions of B.t.i. (Acrobe.RTM.
TP) or methoprene (Dianex.RTM. EC) and B.t.i. have indicated that
these controlled release compositions can be effective in slowly
distributing lethal concentrations of a bacteria and/or insect
growth regulator for a prolonged period to surface and/or
subsurface areas of a water column that were readily accessible to
the feeding and/or orientation of various species of larvae (Table
10). The data indicated that the direction(s), duration, and
rate(s) of controlled release of the bioactive agent(s) in an
aquatic habitat were functions of the surface or subsurface
orientation of the carrier(s), and the type and concentration of
coating(s) and bioactive agent(s) utilized in the powdered or
agglomerated compositions. The results indicated that 100% control
of multiple broods of larvae of Anopheles, Aedes or Culex species
could be obtained in fresh or brackish water for at least 3-8 weeks
when powdered or agglomerated compositions were applied to the
water at rates of ca. 2.5 and 5.0 lb/acre, respectively. Powdered
and agglomerated compositions were still producing 100% control of
larval populations when tests were terminated.
TABLE 9 (Example 6). Formulation Components in Powdered and
Agglomerated Controlled Delivery Compositions Composition
Concentration of Admixtures in Powdered Code/No. and Agglomerated
Compositions Powdered Compositions* J (Example 1) 5 g [5 g B.t.i.
(Acrobe .RTM. TP) + 10 g cetyl alcohol + 85 g hydrophobic silica
(Sipernat .RTM. D17)] + 5 g [5 g B.t.i. (Acrobe .RTM. TP) + 5 g
triethyl citrate (Citroflex .RTM. 2) + 90 g hydrophobic silica
(Sipernat .RTM. D17)] 2 (Example 2) 5 g B.t.i. (Acrobe .RTM. TP) +
10 g cetyl alcohol + 85 g hydrophilic silica (FK 500 LS) K 5 g
B.t.i. (acrobe .RTM. TP) + 5 g triethyl citrate (Citroflex .RTM. 2)
+ 90 g hydrophilic silica (Wesslon .TM. 50) L 5 g B.t.i. (Acrobe
.RTM. TP) + 5 g acetyltriethyl citrate (Citroflex .RTM. A-2) + 90 g
hydrophilic silica (Wesslon .TM. 50) M 5 g B.t.i. (Acrobe .RTM. TP)
+ 5 g tributyl citrate (Citroflex .RTM. 4) + 90 g hydrophilic
silica (Wesslon .TM. 50) N 5 g B.t.i. (Acrobe .RTM. TP) + g
triethyl citrate (Citroflex .RTM. 2) + 90 g hydrophobic silica
(Sipernat .RTM. D17) O 5 g B.t.i. (Acrobe .RTM. TP) + 5 g
acelytriethyl citrate (Citroflex .RTM. A-2) + 90 g hydrophobic
silica (Sipernat .RTM. D17) P 5 g B.t.i. (Acrobe .RTM. TP) + 5 g
tributyl citrate (Citroflex .RTM. 4) + 90 g hydrophobic silica
(Sipernat .RTM. D17). Q 5 g B.t.i. (Acrobe .RTM. TP) + 5 g
acetyltributyl citrate (Citroflex .RTM. A-4) + 90 g hydrophobic
silica (Sipernat .RTM. D17) R 5 g B.t.i. (Acrobe .RTM. TP) + 5 g
(acetyltri-n-hexyl citrate (Citroflex .RTM. A-6) + 90 g hydrophobic
silica (Sipernat .RTM. D17) S 5 g B.t.i. (Acrobe .RTM. TP) + 5 g
n-butyltri-n-hexyl citrate (Citroflex .RTM. B-6) + 90 g hydrophobic
silica (Sipernat .RTM. D17) T 5 g B.t.i. (Acrobe .RTM. TP) + 2.5 g
triethyl citrate (Citroflex .RTM. 2) + 2.5 g tributyl citrate
(Citroflex .RTM. 4) + 90 g hydrophobic silica (Sipernat .RTM. D17)
U 5 g B.t.i. (Acrobe .RTM. TP) + 5 g dicyclohexyl phthalate
(Morflex .RTM. 150) + 90 g hydrophobic silica (Sipernat .RTM. D17)
V 5 g B.t.i. (Acrobe .RTM. TP) + 5 g butyl phthalyl butyl glycolate
(Morflex .RTM. 190) + 90 g hydrophobic silica (Sipernat .RTM. D17)
W 5 g B.t.i. (Acrobe .RTM. TP) + 5 g tri-n-hexyl trimellitate
(Morflex .RTM. 560) + 90 g hydrophobic silica (Sipernat .RTM. D17)
E (Example 5) 5 g [5 g B.t.i. (Acrobe .RTM. TP) + 10 g cetyl
alcohol + 85 g hydrophobic silica (Sipernat .RTM. D17)] + 5 g [0.5
g methoprene (Dianex .RTM. EC) + 10 g cetyl alcohol + 89.5 g
hydrophobic silica (Sipernat .RTM. D17)] Agglomerated
Compositions** A (Example 3) 5 g [5 g B.t.i. (Acrobe .RTM. TP) + 10
g cetyl alcohol + 85 g hydrophobic silica (Sipernat .RTM. D17)] + 5
g sulfonated polystyrene polymer (Versa .RTM. TL-502) B (Example 3)
5 g [5 g B.t.i. (Acrobe .RTM. TP) + 10 g cetyl alcohol + 85 g
hydrophobic silica (Sipernat .RTM. D17)] + 5 g sulfonated vinylic
copolymer (Narlex .RTM. D-82) C (Example 3) 5 g [5 g B.t.i. (Acrobe
.RTM. TP) + 10 g cetyl alcohol + 85 g hydrophobic silica (Sipernat
.RTM. D17)] + 5 g soluble starch *Cetyl alcohol (heated to
60.degree. C.), triethyl citrate, a combination of triethyl citrate
and cetyl alcohol, acetyltriethyl citrate, tributyl citrate,
acetyltributyl citrate, acetyltri-n-hexyl citrate,
n-butyltri-n-hexyl citrate, dicyclohexyl phthalate, butyl phthalyl
butyl glycolage, tri-n-hexyl trimellitate, or a 1:1 combination of
triethyl citrate and tributyl citrate was added to 300 g acetone
and mixed for ca. 5 minutes (speed #6: wire whip) # with a Kitchen
Aid .RTM. KSM 90 hand mixer in a 41/2 qt stainless steel bowl or
with a GE .RTM. hand mixer Model 420A. B.t.i. or a B.t.i. and
methoprene mixture was slowly added to the solvent-base
formulations of coatings while mixing (stir, speed #6, wire whip)
was continued for ca. 5 minutes. Hydrophobic or hydrophilic silica
was added to each solvent-base bioactive agent/coating formulation
while mixing (stir, speed #6, wire whip, flat # beater blade) was
continued for ca. 3 hr to drive office the acetone and assure that
the silica was uniformly encapsulated with the homogeneous mixture
of each bioactive agent and coating. Two bioactive agents were
combined into a single formulation by admixing each bioactive
agent/coating/carrier formulation at a 1:1 mixing ratio. Each
powdered composition was placed in a low humidity room (ca. 27-38%
RH) for ca. 3 to 4 hr to assure volatilization of the # solvent.
The dry powdered compositions were stored in zip-lock bags or glass
bottles until being utilized in mosquito bioassays. **Cetyl alcohol
(heated to 60.degree. C.) was added to 300 g acetone and mixed for
ca. 5 minutes with a GE .RTM. Model 420A hand mixer in a 1/2 gal
plastic beaker. B.t.i. was slowly added into the solvent-base
formulation of coating while mixing for an additional 5 minutes.
Hydrophobic silica was mixed with the other components while mixing
was continued for ca. 3 hr to drive off the acetone and assure a
homogeneous dry mixture of all components. # The powdered
composition was placed in a low humidity room (ca. 27-38% RH) for
ca. 4 hr to assure volatilization of solvent. A ratio of one part
of this powdered 3-part bioactive agent/coating/carrier formulation
was mixed with one part binder (sulfonated polystyrene polymer,
sulfonated vinylic copolymer or soluble starch) for ca. 5 minutes.
The 1:1 composition was then hand compacted into 25 .times. 20
.times. 5 mm vinyl specimen molds (Cryomold .RTM.) # and placed in
a high humidity curing room (ca. 80% RH and 80.degree. F.) for ca.
96 hr. Molds containing each composition were then transferred to a
drying room (ca. 27-38% RH, 76-79.degree. F.) for an additional 96
hr. The dry solidified briquet compositions in each mold were
stored in plastic zip-lock bags. Subsections of each briquet (i.e.,
ca. 3.5 .times. 3.5 .times. 4.5 mm cubettes) were utilized in the
bioassays. One cubette (ca. 0.01 g) was utilized # against mosquito
larvae in each bioassay test chamber (3 replications/agglomerated
composition).
TABLE 10 (Example 6). Coating-Regulated Controlled Delivery of
Acrobe .RTM. TP or Acrobe .RTM. TP/Dianex .RTM. EC from Powdered or
Agglomerated Compositions* No. Days to Achieve 100% Larval Larval
Instar/ Control at Composition Transfer Mosquito Composition
Transfer Water Composition Period (No. Days Between Transfers) Test
Duration Species Period (T)** Quality Code/No. T.sub.0
(T.sub.0.fwdarw. T.sub.1) T.sub.1 (T.sub.1.fwdarw. T.sub.2) T.sub.2
(Days)*** Powdered Composition - ACROBE .RTM. TP (5% AI
Formulation) Ae. aegypti 3rd/T.sub.0, T.sub.1 Fresh J 3 (31) 6 --
-- 40 Ae. taeniorhynchus 3rd/T.sub.0, 1st/T.sub.1 Brackish 2**** 1
(14) 4 -- -- 31 Ae. taeniorhynchus 2nd/T.sub.0, T.sub.1 Brackish
K***** 7 (15) 9 -- -- 61 Ae. taeniorhynchus 2nd/T.sub.0, T.sub.1
Brackish L***** 2 (20) 4 -- -- 56 Ae. taeniorhynchus 2nd/T.sub.0,
T.sub.1 Brackish M***** 2 (20) 9 -- -- 61 An. albimanus
2nd/T.sub.0, T.sub.1 Fresh N 3 (17) 5 -- -- 25 An. albimanus
2nd/T.sub.0, T.sub.1 Fresh O 1 (19) 1 -- -- 21 An. albimanus
2nd/T.sub.0, T.sub.1 Fresh P 1 (19) 4 -- -- 24 An. albimanus
2nd/T.sub.0, T.sub.1 Fresh Q 1 (19) 2 -- -- 22 An. albimanus
2nd/T.sub.0, T.sub.1 Fresh R 1 (19) 1 -- -- 21 An. albimanus
2nd/T.sub.0, T.sub.1 Fresh S 2 (18) 1 -- -- 21 An. albimanus
2nd/T.sub.0, T.sub.1 Fresh T 1 (19) 1 -- -- 21 An. albimanus
2nd/T.sub.0, T.sub.1 Fresh U 1 (19) 1 -- -- 21 An. albimanus
2nd/T.sub.0, T.sub.1 Fresh V 1 (19) 3 -- -- 23 An. albimanus
2nd/T.sub.0, T.sub.1 Fresh W 1 (19) 1 -- -- 21 An. albimanus
2nd/T.sub.0, T.sub.1 Brackish N 3 (17) 8 -- -- 28 An. albimanus
2nd/T.sub.0, T.sub.1 Brackish O 1 (19) 10 -- -- 30 An. albimanus
2nd/T.sub.0, T.sub.1 Brackish P 1 (19) 15 -- -- 35 An. albimanus
2nd/T.sub.0, T.sub.1 Brackish Q 1 (19) 6 -- -- 26 An. albimanus
2nd/T.sub.0, T.sub.1 Brackish R 1 (19) 2 -- -- 22 An. albimanus
2nd/T.sub.0, T.sub.1 Brackish S 1 (19) 7 -- -- 27 An. albimanus
2nd/T.sub.0, T.sub.1 Brackish T 1 (19) 1 -- -- 21 An. albimanus
2nd/T.sub.0, T.sub.1 Brackish U 10 (10) 8 -- -- 28 An. albimanus
2nd/T.sub.0, T.sub.1 Brackish V 1 (19) 5 -- -- 25 An. albimanus
2nd/T.sub.0, T.sub.1 Brackish W 1 (19) 2 -- -- 22 Powdered
Compositions - ACROBE .RTM. TP (5% AI Formulation) Cx.
quinquefasciatus 2nd/T.sub.0, T.sub.1 Fresh K 2 (17) 7 (26) 13 65
Cx. quinquefasciatus 2nd/T.sub.0, T.sub.1 Fresh L 1 (18) 14 (19) 14
66 Cx. quinquefasciatus 2nd/T.sub.0, T.sub.1 Fresh M 2 (17) 5 (28)
17 69 Powdered Compositions - ACROBE .RTM. TP/DIANEX .RTM. EC
(5%/0.5% AI 1:1 Formulation) Ae. taeniorhynchus 3rd/T.sub.1,
T.sub.2 Brackish E 4 (17) 13 -- -- 34 Agglomerated Compositions -
ACROBE .RTM. TP (5% AI Formulation) An. albimanus 2nd/T.sub.0,
T.sub.1 ; 1st/T.sub.2 Fresh A 2 (12) 3 (21) 9 47 An. albimanus
2nd/T.sub.0, T.sub.1 ; 1st/T.sub.2 Fresh B 1 (13) 3 (21) 8 46 An.
albimanus 2nd/T.sub.0, T.sub.1 ; 1st/T.sub.2 Fresh C 9 (05) 4 (20)
7 45 An. albimanus 2nd/T.sub.0, T.sub.1 ; 1st/T.sub.2 Brackish A 2
(12) 8 (16) 1 53 An. albimanus 2nd/T.sub.0, T.sub.1 ; 1st/T.sub.2
Brackish B 2 (12) 3 (21) 16 54 An. albimanus 2nd/T.sub.0, T.sub.1 ;
1st/T.sub.2 Brackish C 7 (07) 1 (23) 18 56 *Powdered and
agglomerated controlled release compositions of Acrobe .RTM. TP or
Acrobe .RTM. TP/Dianex .RTM. EC applied at rates of ca. 2.5 and 5.0
lb/acre, respectively. **T.sub.0 = Initial composition
introduction; T.sub.1,2 = No. post-introduction composition
transfers. ***Compositions remained in water for test duration as a
pretreatment without larvae or during larvae challenges in T.sub.0,
T.sub.1, and T.sub.2 and between transfer periods T.sub.0 -T.sub.2
with dead larvae/pupae. Compositions briefly removed with a 100
mesh sieve to transfer formulations from T.sub.0, to T.sub.1 and
T.sub.2 test chambers. Test terminated even though compositions
were still effective in producing 100% control of immatures.
****Powdered compositions initially introduced into water for 12
days with larvae (pretreatment) before being transferred into
T.sub.0 test chamber with larvae. *****Powdered compositions
initially introduced into water for 30 days with larvae
(pretreatment) before being transferred into T.sub.0 test chamber
with larvae.
EXAMPLE 7
A series of short-term bioassays were conducted in fresh or
brackish water against larvae of Anopheles, Aedes, and/or Culex
species with controlled release compositions comprising admixtures
of the insect growth regulator methoprene (Dianex.RTM.EC), the
bacteria B.t.i. (Acrobe.RTM. TP) or an experimental monomolecular
surface film (POE(2) Isostearyl Alcohol), one or more hydrophobic
(FK 500 LS, Sipernat.RTM. 22S, Wesslon.TM.) and/or hydrophobic
(Sipernate.RTM. D17) silica or hydrophobic "pin chips"
(SeaSweep.RTM.) carriers, and one or more cetyl alcohol (specific
gravity less than one, insoluble in water), triethyl citrate
(Citroflex.RTM.2; specific gravity greater than one, soluble in
water), tributyl citrate (Citroflex.RTM.4; specific gravity greater
than one, insoluble in water), and/or n-butyryl tri-n-hexyl citrate
(Citroflex.RTM. B-6; specific gravity less than one, insoluble in
water) coatings, and/or one or more joint-function polyvinyl
alcohol films (specific gravity greater than one, soluble in water)
that can act as a coating and carrier. All coatings showed
differential surface spreading potentials when applied to the
water. Specific formulation components for each of the compositions
utilized in these bioassays are presented in Table 11.
Results of larval bioassays against single or mixed species
populations indicated that the initial orientation of delivery of
an insect growth regulator, bacteria or monomolecular surface film
from a controlled delivery composition was dictated by the surface
and/or subsurface characteristics of the bioactive
agent/coating-encapsulated carrier(s) in an aquatic habitat (Table
12). Changes over time in the initial orientation or direction and
rate of delivery in a water column were determined by the specific
gravity, solubility, and film-forming characteristics of the
coating agent(s) and bioactive agent(s) encapsulated on the
carrier(s).
The data indicated that 100% larval control of mixed populations of
Anopheles and Culex species occurred in all powdered B.t.i.
formulations (2.5 lb/acre application) in 24 hr posttreatment;
however, the rates of control within the 24 hr period were observed
to be formulation (i.e., coating) dependent. Complete control
(i.e., 100%) of larvae of Aedes with two powdered compositions of
POE(2) Isostearyl Alcohol (5 lb/acre application) was observed in
11 and 13 days posttreatment while 100% control of larvae of Culex
mosquitoes exposed to two "pin chip" compositions of methoprene
(2.5 lb/acre application) was observed in 28 and 30 days
posttreatment. Mixed populations of Anopheles larvae were killed in
both water qualities within 24 hr posttreatment with all polyvinyl
alcohol film compositions. These agglomerated admixture
formulations (i.e., cubettes) initially floated and differentially
solubilized within 24 hr. It appears that air entrapped within the
polyvinyl alcohol matrices caused the formulations to float.
Cubette agglomeration and hardness were affected by the type of
solvent utilized in the fabrication process. Polyvinyl alcohol
film(s) and B.t.i. compositions (Codes 12, 13, 14) were secondarily
admixed with 0.15-0.5 g soluble starch, Carboset.RTM. 514H,
Carbopol.RTM. ETD 2001, Narlex.RTM.D-82, Versa.RTM. TL-502,
Citroflex .RTM. A-2, Morflex.RTM. 150, FK500 LS, Sipernat.RTM. D17,
ethoxylated alcohols and/or salts (e.g., NaCl Instant Ocean.RTM.).
Additions of one or more binder, coating agents, carriers, and/or
additional ingredients to the formulations indicated in Codes 12,
13, 14 were observed to significantly affect component dissociation
from the cubettes as well as the surface/subsurface orientation of
the cubettes/cubette components in the water column. The type of
salt(s) utilized in the aqueous formulation and the type of
solvent(s) utilized in the aqueous agglomeration and drying
protocols were observed to have a significant affect on the
agglomeration performance and rigidity of the matrices containing
the additional admixture ingredients.
TABLE 11 (Example 7). Formulation Components in Powdered, Chipped
or Agglomerated Controlled Delivery Compositions Com- posi- tion
Concentration of No. Admixtures in Powdered and Chipped
Compositions Powdered Compositions* 5 10 g B.t.i. (Acrobe .RTM. TP)
+ 20 g cetyl alcohol + 85 g hydro- phobic silica (Sipernat .RTM.
D17)] + 85 g hydrophilic silica (Wesslon .TM.) 6 10 g B.t.i.
(Acrobe .RTM. TP) + 10 g cetyl alcohol + 10 g triethyl citrate
(Citroflex .RTM. 2) + 85 g hydrophobic silica (Sipernat .RTM. D17)
and 85 g hydrophilic silica (Wesslon .TM.) 7 10 g B.t.i. (Acrobe
.RTM. TP) + 10 g cetyl alcohol + 10 g n-buty- rltri-n-hexyl citrate
(Citroflex .RTM. B-6) + 85 g hydrophobic silica (Sipernat .RTM.
D17) + 85 g hydrophilic silica (Wesslon .TM.) 8 24.75 g
Monomolecular Surface Film (POE(2) Isostearyl Alcohol) + 0.25 g
triethyl citrate (Citroflex .RTM. 2) + 75 g hydrophilic silica
(Sipernat .RTM. 22S) 9 24.75 g Monomolecular Surface Film (POE(2)
Isostearyl Alcohol) + 0.25 g tributyl citrate (Citroflex .RTM. 4) +
75 g hydrophilic silica (Sipernat .RTM. 22S) Chipped Compositions**
10 5 g methoprene (Dianex .RTM. EC) + 5 g triethyl citrate
(Citroflex .RTM. 2) + 90 g "pin chips" (SeaSweep .RTM.) 11 5 g
methoprene (Dianex .RTM. EC) + 5 g n-butyrltri-n-hexyl citrate
(Citroflex .RTM. B-6) + 90 g "pin chips" (Seasweep .RTM.)
Agglomerated Compositions*** 12 3 g B.t.i. (Acrobe .RTM.
Biolarvicide) + 12 g polyvinyl alcohol film (MonoSol .RTM. 8000
series) + 45 g distilled water + acetone, methyl ethyl ketone or
2-propanol bath series 13 3 g B.t.i. (Acrobe .RTM. Biolarvicide) +
12 g polyvinyl alcohol film (MonoSol .RTM. 7000 series) + 45 g
distilled water + acetone, methyl ethyl ketone or 2-propanol bath
series 14 3 g B.t.i. (Acrobe .RTM. Biolarvicide) + 6 polyvinyl
alcohol film (MonoSol .RTM. 8000 series) + 6 g polyvinyl alcohol
film (MonoSol .RTM. 7000 series) + 45 g distilled water + acetone,
methyl ethyl ketone or 2-propanol bath series *Cetyl alcohol
(heated to 60.degree. C.), triethyl citrate, tributyl citrate,
and/or n-butyrltri-n-hexyl citrate was added to 600 g acetone and
mixed for ca. 5 minutes (speed #6, wire whip) with a Kitchen Aid
.RTM. KSM 90 hand mixer in a 41/2 qt stainless steel bowl. B.t.i.
or the experimental monomolecular surface film was slowly added to
the solvent-base formulations of coatings while mixing (stir, speed
#6, wire whip) as continued for ca. 5 # minutes. Hydrophobic and/or
hydrophilic silica was added to each solvent-base bioactive
agent/coating formulation while mixing (stir, speed #6, wire ship,
flat beater blade) was continued for ca. 3 hr to drive off the
acetone and assure that each silica was uniformly encapsulated with
the homogeneous mixture of each bioactive agent and coating(s).
Each powdered composition was placed in a low humidity room (ca.
27-38% RH) for ca. 3 to 4 hr to assure # volatilization of the
solvent. The dry powdered compositions were stored in zip-lock bags
or glass bottles until being utilized in mosquito bioassays.
**Triethyl citrate or n-butyrltri-n-hexyl citrate methoprene were
added to 300 g acetone in 1000 ml Nalgene bottles and placed on a
paint shaker (Miller Strokemaster .TM.) for ca. 1 hr to assure that
the insect growth regulator formulation was well mixed. "Pin chips"
(ca. 2 .times. 8 mm) were added to the bottles containing the
acetone/methoprene/citrate formulations and hand shaken for ca.
10-30 seconds to assure that the "pin # chips" were saturated with
the formulations. "Pin chips" continued to soak in the formulations
for ca. 18 hr before being removed on sieves and placed in drying
room (ca. 27-38% RH) for ca. 24 hr to assure volatilization of the
acetone. The dry "pin chip" formulations were placed into zip-lock
bags until being used for mosquito bioassays. ***One or more
polyvinyl alcohol films were dissolved in distilled water in a
plastic beaker. B.t.i. was mixed with the aqueous formulations of
joint-function coating/carrier with a Kitchen Aid .RTM. KSM 90 hand
mixer for ca. 1 to 2 minutes. The insectide formulations were
poured into 2 ounce glass medicine bottles and vigorously shaken by
hand for ca. 1 minute. 7-10 g water-base polyvinyl alcohol
films/B.t.i. formulations were added to plastic # centrifuge tubes
(ca. 60 ml capacity) containing ca. 35-40 g acetone, methyl ethyl
ketone or 2 propanol. The centerfuge tube was capped and vigorously
hand shaken to solidify to polyvinyl alcohol film(s) and B.t.i.
admixtures into a unified mass within the aqueous-acetone,
aqueous-methyl ethyl ketone or aqueous-2-propanol medium. The solid
mass from each tube was removed and placed into 50 ml glass beakers
containing ca. 40 g acetone, methyl ethyl ketone # or 2-propanol
for a series of five one minute washes to remove entrapped water
from the solid matrix. The solid mass was removed from each
acetone, methyl ethyl ketone or 2-propanol bath and thoroughly
air-dried in a low humidity room (ca. 27-38% RH) for ca. 72 hr. The
solid compositions were stored in zip-lock bags or glass bottles
until being used for mosquito bioassays. Remaining stock
formulations of water, polyvinyl alcohol film(s), and B.t.i. were #
stored in a refrigerator (ca. 40.degree. F.) for future use.
TABLE 12 (Example 7). Coating-Regulated Delivery of Acrobe .RTM.
TP, Dianex .RTM. EC or POE/2) Isostearyl Alcohol from Powdered,
Chipped or Agglomerated Compositions Mosquito Larval Water
Composition No. Days to Achieve 100% Control of Species Instar
Quality No. Larvae, Pupae and/or Emerging Adults Powdered
Composition - Acrobe .RTM. TP (5% AI Formulation)* An. albimanus/
2nd/2nd Fresh 5 1 Cx. quinquefasciatus An. albimanus/ 2nd/2nd Fresh
6 1 Cx. quinquefasciatus An. albimanus/ 2nd/2nd Fresh 7 1 Cx.
quinquefasciatus An. albimanus/ 2nd/2nd Brackish 5 1 Cx.
quinquefasciatus An. albimanus/ 2nd/2nd Brackish 6 1 Cx.
quinquefasciatus An. albimanus/ 2nd/2nd Brackish 7 1 Cx.
quinquefasciatus Powdered Compositions - POE(2) Isostearyl Alcohol
(25% AI Formulation)** Ae. taeniorhynchus 3rd Brackish 8 11 Ae.
taeniorhynchus 3rd Brackish 9 13 Chipped Compositions - Dianex
.RTM. EC (5% AI Formulation)*** Cx. quinquefasciatus 2nd Fresh 10
26 Cx. quinquefasciatus 2nd Fresh 11 23 Agglomerated Compositions -
Acrobe .RTM. TP (20% AI Formulation)**** An. albimanus 2nd Fresh 12
1 An. albimanus 2nd Fresh 13 1 An. albimanus 2nd Fresh 14 1 An.
albimanus 2nd Brackish 12 1 An. albimanus 2nd Brackish 13 1 An.
albimanus 2nd Brackish 14 1 *Powdered controlled delivery
compositions of B.t.i. one or more cetyl alcohol and/or citrate
coatings, and one or more hydrophobic and/or hydrophilic silica
carriers were applied at a rate of ca. 2.5 lb/acre (i.e., 0.005
g/bioassay test chamber). **Powdered controlled delivery
compositions of a monomolecular surface film, a citrate coating,
and a hydrophilic silica carrier were applied at a rate of ca. 5
lb/acre (i.e., 0.01 g/bioassay test chamber). ***Chipped controlled
delivery compositions of methoprene, a citrate coating, and a
hydrophobic "pin chip" carrier were applied at a rate of ca. 2.5
lb/acre (i.e., 5 "pin chips"; 0.005 g/bioassay test chamber).
****Agglomerated controlled delivery compositions (i.e., cubettes)
of B.t.i. (20%) and a water and solvent-free joint-function
polyvinyl alcohol film coating/carrier (80%) were applied at a rate
of ca. 5 lb/acre (i.e., one, 0.01 g cubette/bioassays test
chamber). Aqueous insecticide formulations fabricated into solid
mass by a series of solvent precipitation and evaporation
procedures.
EXAMPLE 8
In another evaluation, 0.01, 0.05, and 0.1 g Pemulen.RTM. TR-1 or
Premulen.RTM. TR-2 acrylic copolymer suspending agents were added
to 47.5 g distilled water in 50 ml glass medicine bottles and
vigorously shaken by hand for ca. 2-3 minutes to form a homogeneous
mixture. 2.5 g of the powdered controlled release compositions of
B.t.i. (Acrobe.RTM. TP), one or more hydrophobic and/or hydrophilic
silica carriers and one or more Citroflex.RTM., Morflex.RTM. and/or
cetyl alcohol coatings (Examples 1-7) were added to each of the
aqueous acrylic copolymer formulations and placed on a mechanical
shaker and vigorously mixed for ca. 5 minutes to assure that the
silica-base compositions were uniformly suspended throughout the
water column. Results of the suspendability tests indicated that
these powdered compositions could be readily dispensed in water
with conventional spray equipment. Suspension of compositions in
petroleum or nonpetroleum oils for spray application is also
proposed.
EXAMPLE 9
In another test, an aqueous formulation of the aquatic herbicide
Aquathol.RTM.K (dipotassium salt of endothall) was admixed with a
joint-function (carrier/coating) polyvinyl alcohol film
(MonoSol.RTM. 8000 series, M-7030, M-8533 or M-8030) and
agglomerated into a solidified controlled delivery mass in a series
of solvent precipitation and evaporation procedures. The admixing
protocol utilized was similar to procedures described in Examples
4, 5, and 7. As indicated in the earlier examples, polyvinyl
alcohol film (specific gravity greater than one) is soluble in
water (temperature dependent) but insoluble in most organic and
inorganic solvents, hydrocarbons or oils. These properties are also
similar for polyethylene oxide and hydroxypropyl methyl cellulose
water-soluble films. MonoSol.RTM. 8000 series was obtained from the
manufacturer as solid sheets/pouches and dissolved in water (20%
polyvinyl alcohol film) while MonoSol.RTM. M-7030, M-8533 and
M-8030 were obtained as water-base solutions (16.1-16.4% polyvinyl
alcohol film).
The following formulations were utilized in fabricating the
joint-function polyvinyl alcohol compositions of Aquathol.RTM.K:
Composition AK1--4 g dipotassium salt of endothall
(Aquathol.RTM.K)+12.5 g polyvinyl alcohol film (MonoSol.RTM. 8000
series)+46 distilled water+acetone bath series; Composition AK2--2q
dipotassium salt of endothall (Aquathol.RTM.K)+7.4 g polyvinyl
alcohol film (MonoSol.RTM. M-7030)+40.6 g distilled water+acetone
bath series; Composition AK3--2 g dipotassium salt of endothall
(Aquathol.RTM.K)+7.3 g polyvinyl alcohol film (MonoSol.RTM.
M-8533)+40.7 distilled water+acetone bath series; and Composition
AK4--2 g dipotassium salt of endothall (Aquathol.RTM.K)+7.3 g
polyvinyl alcohol film (MonoSol.RTM. M-8030)+40.7 g. distilled
water+acetone bath series.
The dried agglomerated briquet compositions of AK1, AK2, AK3, and
AK4 consisted of 24.4, 21.5, 21.7, and 21.8% (w/w) dipotassium salt
of endothall, respectively. Commercial Aquathol.RTM.K granules
contain only 10.1% dipotassium salt of endothall.
Results of the admixing procedures indicated that high levels of
Aquathol.RTM.K can be agglomerated into solid polyvinyl
alcohol-base compositions for fast-release application into an
aquatic habitat for control of nuisance vegetation. All
compositions solubilized in fresh water within 2 hr of introduction
and showed differential degrees of floating or sinking depending on
the type and/or concentration of polyvinyl alcohol utilized in the
formulation.
Loading levels were significantly higher than the standard
commercially available granular Aquathol.RTM.K product (i.e., 10.1%
dipotassium salt of endothall), and therefore, a lesser amount (on
a weight basis) per acre of MonoSol.RTM./Aquathol.RTM.K would be
required to treat an acre of aquatic weeds when compared to the
amount or weight of conventional Aquathol.RTM.K granular product
needed per acre to be equivalent to the concentration of
dipotassium salt of endothall in the composition. The results
indicated that significantly higher loading levels can be obtained
with the polyvinyl alcohol-base protocol. Addition of one or more
coatings, surfactants, binders, and the like is expected to change
the controlled release profiles of the compositions. Any herbicide
can be fabricated into a solid controlled delivery composition
utilizing the joint-function polyvinyl alcohol-base admixing
protocol.
The foregoing coating component, bioactive agents and carrier
components can be selected to control or eliminate various
terrestrial organisms, and especially nuisance plant and animal
organisms such as weeds, rodents and insects, including but not
limited to cockroaches, ants, fire ants, termites, and other
varieties of biting insects, disease carrying insects, crop eating
insects, and wood eating insects. The coatings that are selected in
this regard are the degradable ones, e.g. biodegradable coatings
selected from those listed above, and those that also will protect
the bioactive agent from degradation, especially ultraviolet light
degradation. The coatings are also selected to release the
bioactive agent over a period of time so as to increase the
effectiveness of the bioactive agent.
The compositions of the invention can also be utilized in the
treatment of parasitic or insect caused diseases in animals,
especially the G.I. tract of animals such as ruminants, by
selecting those components of the composition that are approved for
animal use. When properly administered they can be employed to
provide time release compositions for the treatment of various
diseases and disorders. Non-bioactive compounds or compositions can
be used in lieu of the bioactive agents for the treatment of
certain disorders such as the treatment of hoven in ruminants by
means of surfactant silicone compounds. Some non-limiting examples
of other compounds that may be used in the treatment of animals is
disclosed by Drummond et al., Control of Arthropod Pests of
Livestock: A Review of Technology, 1988, CRC Press, Inc. which is
incorporated herein by reference.
In the course of preparing the various compositions of the
invention it was further discovered that in many instances the
materials employed as coatings, carriers, and binders were
interchangeable. Joint-function carrier coating materials have been
described, but in the broader aspects of the invention, the
coating, carrier, and binder compounds or compositions are to be
categorized primarily by the way they are employed in the
compositions i.e. by the way the function because of the
interchangeability of the various compounds and compositions that
are useable in this regard.
The principles, preferred embodiments, and modes of operation of
the present invention have been described in the foregoing
specification. The invention which is intended to be protected
here, however, is not to be construed as limited to the particular
forms disclosed, since these are to be regarded as illustrative
rather than restrictive. Variations and changes may be made by
those skilled in the art without departing from the spirit of the
invention.
* * * * *