Patent Publication Number: US-10785977-B2

Title: Methods and compositions for environmentally friendly pest control

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
     This application is a Continuation of U.S. application Ser. No. 15/442,199, filed Feb. 24, 2017, which claims priority to U.S. Provisional Application No. 62/395,164, filed Sep. 15, 2016, the contents of which are hereby incorporated by reference in its entirety. 
    
    
     BACKGROUND 
     1. Field 
     The present disclosure relates to spray formulations, especially pesticidal formulations of the sort which may be diluted with water to form a sprayable preparation, for example, a pressure pack (“aerosol”) preparation or a spray, particularly an ultra-low volume (ULV) spray for domestic, horticultural, agricultural, environmental, or industrial use. In particular, the present disclosure relates to pesticidal formulations devoid of Volatile Organic Compounds. 
     2. Description of Related Art 
     Water-based sprays are advantageous because they cost less than oil-based sprays and are often less toxic to mammals. However, particularly when the ambient temperature is high, the water in the spray droplets evaporates and the droplets become smaller and drift more readily from the area being sprayed. The size of the droplets is frequently specially chosen to suit the application, for example to maximize droplet adherence to flying insects or adherence to plant foliage, to increase bio-availability, or to control the size of the area being sprayed and the delivery rate per square meter; such care is pointless if the spray droplets change size, possibly unpredictably, following spraying. 
     Water-in-oil emulsions or oil-in-water emulsions are typically used in water-based sprays due to the low solubility of most pesticides in water. Volatile Organic Compound (VOC) regulations, however, have limited the compounds that are available to formulate water-in-oil emulsions suitable for pesticide applications. Thus, there is a significant need to develop further pesticidal formulations with low VOC content. 
     To this end, non-VOC insecticide formulations have been described comprising at least one active ingredient and at least one solvent. See U.S. Patent Publication No. 2016-0242418. 
     It is widely believed that chemical pesticides are of critical importance in maintaining control of diseases spread by mosquitoes and other insects, particularly in developing countries. However, there is growing resistance to the most commonly used chemical pesticides, including pyrethroids, DDT, carbamates, and organophosphates. Thus, it is critical to develop pesticidal formulations that do not rely on traditional chemical pesticides. 
     The solution to this technical problem is provided by the embodiments characterized in the claims. 
     BRIEF SUMMARY OF THE INVENTION 
     The present application relates to spray formulations, especially pesticidal formulations of the sort which may be diluted with water to form a sprayable preparation, for example, a pressure pack (“aerosol”) preparation or a spray, particularly an ultra-low volume (ULV) spray for domestic, horticultural, agricultural, environmental, or industrial use. In particular, the present disclosure relates to pesticidal formulations devoid of Volatile Organic Compounds (VOC). 
     In particular, the present application provides spray formulations comprising at least one solvent, wherein said formulations are essentially free of one or more currently registered pesticide(s). 
     The spray formulations optionally comprise an essential oil, an active ingredient, a humectant, an emulsifier, a surfactant, an anti-foam agent, a preservative and/or water, together with other ingredients such as perfumes, dyes, solids (e.g., to form wettable powders) and thickeners. The active ingredient preferably is an active ingredient eligible for minimum risk exemption regulations of the EPA (40 C.F.R. 152.25(f)(1)). 
     Sprays in accordance with the invention are particularly suitable for spraying buildings, residential or commercial areas, and insect breeding grounds (such as swamps and other tracts of water) with insecticide and for spraying crops with herbicides, insecticides, fungicides, and plant growth regulators. 
     The sprays may be delivered by pumping through a nozzle, especially a sonic nozzle, by pumping over an ultrasonic nebulizer, or via a spinning disc. The droplets may be electro-statically charged, if desired. 
     Suitable solvents are Volatile Organic Compounds (VOC)-exempt or contain no VOCs. Suitable non-VOC solvents include, but are not limited to, acetate esters, methyl esters, citric acid esters such as acetyl-tributyl citrate, isoparaffinic fluids, paraffinic fluids, vegetable oils such as canola oil, cotton seed oil, soybean oil and the like, and mixtures thereof. Suitable VOC-exempt solvents include, but are not limited to, monoethylene, diethylene, triethylene, tetraethylene glycols, and polyethylene glycols such as PEG 300 and above. Preferably, the solvent is a citric acid ester. More preferably, the solvent is acetyl-tributyl citrate. 
    
    
     DETAILED DESCRIPTION 
     Before the subject disclosure is further described, it is to be understood that the disclosure is not limited to the particular embodiments of the disclosure described below, as variations of the particular embodiments may be made and still fall within the scope of the appended claims. It is also to be understood that the terminology employed is for the purpose of describing particular embodiments, and is not intended to be limiting. Instead, the scope of the present disclosure will be established by the appended claims. 
     In this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural reference unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. 
     The term “spray formulation” is defined as a formulation, especially pesticidal formulations, of the sort which may be diluted with water to form a sprayable preparation, for example, a pressure pack (“aerosol”) preparation or a spray, particularly an ultra-low volume (ULV) spray for domestic, horticultural, agricultural, environmental or industrial use. 
     The term “currently registered pesticide” is defined as any pesticide registered with the U.S. Environmental Protection Agency (EPA) as of the filing date of the application. 
     The term “volume mean diameter” or “VmD” is defined as the midpoint droplet size (mean), where half of the volume of spray is in droplets smaller, and half of the volume is in droplets larger than the mean. 
     The terms “VOC-exempt” and “Volatile organic compound-exempt” are used interchangeably throughout this specification and the appended claims and are defined according to the definition under U.S. Environmental Protection Agency (EPA) regulations under 40 C.F.R. 59.203(f). These EPA regulations define a chemical as “VOC-exempt” if it has vapor pressure of less than 0.1 millimeters of mercury (at 20° C.). If the vapor pressure is unknown, a chemical is defined as “VOC-exempt” if it a) consists of more than 12 carbon atoms; or b) has a melting point higher than 20° C. and does not sublime (i.e., does not change directly from a solid into a gas without melting). 
     ULV sprays are generally used in space spray insecticides to treat or fog areas to kill adult mosquitos. Typically, a ULV concentrate comprising an insecticide is diluted and atomized by a ULV fogging machine. The insecticide would then be released from the ground or from the air. Air currents would carry the droplets downwind of the application equipment. The droplets would collide with the insects, coating the insect with a lethal dose of the active ingredient. 
     Water dilutable insecticides and/or ULV concentrates include formulations such as the FFAST™ (an acronym for Film Forming Aqueous Spray Technology) insecticide formulations described in U.S. Pat. Nos. 5,466,458, 5,527,823, and 6,302,161 allow for the use of water as a diluent. These patents are hereby incorporated by reference. 
     It is generally less expensive and more desirable to have the option of using a water-based product. However, at ambient temperatures, conventional water-based sprays tend to evaporate quickly and fail to deliver the insecticide to the target insects or pests efficiently. To overcome this problem in the past, dispersing insecticides in water required the creation of large droplets. However, these large droplets did not drift efficiently and did not reach the target at all. 
     A formulation, such as the FFAST™ formulation, using long chain alcohol molecules to form a protective film around each droplet of insecticide as it leaves the nozzle of the sprayer, allows for the formation of droplets that do not evaporate too quickly and that efficiently deliver the insecticide to the target insect. The incorporation of long chain alcohols into the formulation provides a means of coating the individual droplets of insecticides when mixed with water so as to control the rate of evaporation. This film retards the evaporation of the droplets and they maintain the desired optimum size. 
     The subject disclosure features, in one aspect, spray formulations comprising at least one solvent, wherein said formulations are essentially free of one or more currently registered pesticide(s). In a preferred embodiment, the spray formulations are Volatile Organic Compounds (VOC)-exempt or alternatively, contain no VOCs. The U.S. Environmental Protection Agency (EPA) identifies a VOC as an organic compound that participates in atmospheric photochemical reactions, but makes exceptions for compounds that have negligible photochemical reactivity. VOCs are emitted as gases from certain solids or liquids. They include a variety of chemicals, some of which may have short- and long-term adverse health effects. Conventional emulsified pesticide formulations generally contain 50-90% by weight VOCs. Current regulations from the California Department of Pesticide Regulation and from the U.S. Environmental Protection Agency (EPA) recommend that pesticides are formulated to contain 20% by weight VOC, or less. 
     VOC content may be measured by any method known in the art. Several states, including California, evaluate methods and maintain lists of approved tests available for determining VOC content. One established method of determining the VOC content is a gas chromatographic analysis in accordance with DIN EN ISO 11890-2. 
     Thus, in a preferred embodiment, the spray formulations are low in VOC. In particular, the spray formulations contain ≤16% VOC by weight. In a more preferred embodiment, the spray formulations contain ≤10% VOC by weight, ≤5% VOC by weight, or ≤2.5% VOC by weight. 
     In a more preferred embodiment, the spray formulations are devoid or essentially devoid of VOC by weight. In particular, the spray formulations contain ≤1% VOC by weight. Optionally, the spray formulations contain ≤0.5% VOC by weight, ≤0.25% VOC by weight, ≤0.1% VOC by weight, or ≤0.05% VOC by weight. 
     Suitable solvents are Volatile Organic Compounds (VOC)-exempt or contain no VOCs. Suitable non-VOC solvents include, but are not limited to, acetate esters, methyl esters, citric acid esters such as acetyl-tributyl citrate, isoparaffinic fluids, paraffinic fluids, vegetable oils such as canola oil, cotton seed oil, soybean oil and the like, and mixtures thereof. Suitable VOC-exempt solvents include, but are not limited to, monoethylene, diethylene, triethylene, tetraethylene glycols, and polyethylene glycols such as PEG 300 and above. 
     In some embodiments, the solvent is a citric acid ester. Examples of citric acid esters include, but are not limited to, triethyl citrate (such as Citroflex® 2, Vertellus, Indianapolis, Ind.), tributyl citrate (such as Citroflex® 4, Vertellus, Indianapolis, Ind.), acetyl triethyl citrate (such as Citroflex® A2, Vertellus, Indianapolis, Ind.), acetyl tributyl citrate (such as Citroflex® A4, Vertellus, Indianapolis, Ind.), N-butyryl tri-N-hexyl citrate (such as Citroflex® B6, Vertellus, Indianapolis, Ind.), tri-C12-13 alkyl citrate, tri-C14-15 alkyl citrate, tricaprylyl citrate, triethylhexyl citrate, triisocetyl citrate, triictyldodecyl citrate, triisostearyl citrate, isodecyl citrate, isopropyl citrate, stearyl citrate, dilauryl citrate, and mixtures thereof. The solvent can, optionally, be a mixture of any tri- di- and monoethyl citrates. 
     In a preferred embodiment, the solvent is tributyl citrate. In a more preferred embodiment, the solvent is acetyl tributyl citrate (such as Citroflex® A4, Vertellus, Indianapolis Ind.). 
     The spray formulations optionally comprise an essential oil, an active ingredient, a synergist, a humectant, an emulsifier, a surfactant, an anti-foam agent, a preservative and/or water. The active ingredient preferably is an active ingredient eligible for minimum risk exemption regulations of the EPA (40 C.F.R. 152.25(f)(1)). 
     The spray formulations optionally comprise one or more essential oils. Examples of essential oils include, but are not limited to, rosemary oil, peppermint oil, spearmint oil, thyme oil, clove oil, lemongrass oil, pennyroyal oil, vetiver oil, basil oil, cedar oil,  verbena  oil, garlic oil, geranium oil, rose geranium oil, pine oil, cinnamon oil, catnip oil,  Artemisia vulgaris  oil,  Melaleuca leucadendron  oil,  Pelargonium roseum  oil,  Lavandula angustifolia  oil,  Mentha piperita  oil,  Juniperus virginiana  oil,  Mentha  spp. oil,  eucalyptus  oil, citronella oil,  Cinnamomum zeylanicum  oil,  Cinnamomum  spp. oil,  Cymbopogon citratus  oil,  Lavandula angustifolia  syn. oil  L. officinalis  oil,  Tanacetum vulgare  oil,  Rabdosia melissoides  oil,  Acorus calamus  oil,  Eugenia caryophyllata  oil,  Ocimum  spp. oil,  Gaultheria procumbens  oil,  Cuminum cyminum  oil,  Bunium persicum  oil,  Trachyspermum ammi  oil,  Foeniculum vulgare  oil,  Abelmoschus moschatus  oil,  Cedrus  spp. oil,  Piper  spp. oil,  Ocimum sanctum  oil,  Satureja hortensis  oil,  Thymus serpyllum  oil,  Origanum creticum  oil,  Ageratum conyzoides  oil,  Aegle marmelos  oil,  Lippia alba  oil,  Rosmarinus officinalis  oil, lemon oil, lime oil, citrus oil, rose oil, lavender oil, dill ( Anethum sowa ) oil  Anethum graveolens  oil,  Mentha spicata  oil,  Nepeta cataria  oil, turmeric ( Curcuma longa ) oil, ginger oil, grapefruit oil, orange oil, hyssop oil, sage oil, tansy oil, patchouli oil, sandalwood oil, cypress oil, blue cypress oil, myrrh oil, sweet myrrh oil, neem oil, Alaska yellow cedar ( Chamaecyparis nootkatensis ) oil, Japanese honeysuckle oil, honeysuckle oil, tea tree oil, palmarosa oil, marigold oil,  Tagetes patula  oil, and combinations thereof. The essential oil may be isolated from one or more plant parts, including, but not limited to, leaves, stems, bark, flowers, roots, seeds, and/or fruits. 
     The spray formulations may optionally comprise one or more active components isolated from one or more essential oils. Examples of active components isolated from one or more essential oils include, but are not limited to, eugenol, geraniol, menthol, thymol, carvone, dillapiole, myrcene, α-terpinene, α-phllandrene, limonene, p-cymene, α-pinene, caryophyllene, citronellal, citral, cinnamaldehyde, perillaldehyde, cuminaldehyde, ethyl vanillin, vanillin, camphor, pulegone, menthone, thujone, linalool, nerol, citronellol, terpine-4-ol, borneol, farnesol, nerolidol, phenylethyl alcohol, cinnamic alcohol, carvacrol, anethole, estragole, isoeugenol, safrole, linalyl acetate, neryl acetate, fenchone, citronellyl acetate, 1,8-cineole, asarone, nootkatone, α-phellandrene, α-turmerone, turmerol, α-zingiberene, β-zingiberene, ar-d-curcumene, β-sesquiphellandrene, α-atlantone, nepetalactone, apiol, carveol, verbenone, and verbenol. Further examples of active components isolated from one or more essential oils include, but are not limited to, terpenes (hydrocarbons) such as myrecene, pinene, terpinene, limonene, p-cymene, α- and β-phellandrene etc.; and terpenoids (oxygen containing hydrocarbons) such as acyclic monoterpene alcohols (e.g., geraniol, linalool), monocyclic alcohols (e.g., menthol, 4-carvomenthenol, terpineol, carveol, borneol), aliphatic aldehydes (e.g., citral, citronellal, perillaldehyde), aromatic phenols (e.g., carvacrol, thymol, safrole, eugenol), bicyclic alcohols (e.g., verbenol), monocyclic ketones (e.g., menthone, pulegone, carvone), bicyclic monoterpenic ketones (e.g., thujone, verbenone, fenchone), acids (e.g., citronellic acid, cinnamic acid) and esters (e.g., linalyl acetate). Some essential oils may also contain oxides (e.g., 1,8-cineole), sulfur containing constituents, methyl anthranilate, coumarins, etc. Zingiberene, curcumene, farnesol, sesquiphellandrene, termerone, and nerolidol are some examples of sesquiterpenes (C15) isolated from essential oils. 
     The spray formulations may optionally comprise one or more of the following: castor oil, corn oil, cornmint oil, cottonseed oil, linseed oil, sesame oil, soybean oil, 2-phenylpropionate, citric acid, malic acid, and/or potassium sorbate. 
     The spray formulations optionally comprise an active ingredient. The active ingredient may be a currently registered pesticide such as an acaricide, herbicide, fungicide, plant growth regulator, insect behavior modifier, or biological control agent (e.g. viruses, bacteria, and eggs of parasites). The active ingredient may also be a dye, perfume, bactericide, lubricant, medicament, paint, polish, lacquer (including hair lacquer), textile treatment (including sizes), or other compound to be sprayed in a water-based formulation. 
     If included in the spray formulation, the active ingredient preferably is an active ingredient eligible for minimum risk exemption regulations of the EPA (40 C.F.R. 152.25(f)(1)). A list of active ingredients eligible for minimum risk exemption regulations of the EPA (40 C.F.R. 152.25(f)(1)) is available at epa.gov/minimum-risk-pesticides/active-ingredients-eligible-minimum-risk-pesticide-products. Examples of active ingredients eligible for minimum risk exemption regulations of the EPA (40 C.F.R. 152.25(f)(1)) include, but are not limited to, castor oil, cedarwood oil, cedarwood oil (China), cedarwood oil (Texas), cedarwood oil (Virginia), cinnamon, cinnamon oil, citric acid (2-hydroxypropane-1,2,3-tricarboxylic acid), citronella, citronella oil, cloves, clove oil, corn gluten meal, corn oil, cornmint, cornmint oil, cottonseed oil, dried blood, eugenol (4-allyl-2-methoxyphenol), garlic, garlic oil, geraniol (2E)-3,7-dimethylocta-2,6-dien-1-ol), geranium oil, lauryl sulfate lemongrass oil, linseed oil, malic acid (2-hydroxybutanedioic acid), peppermint, peppermint oil, 2-phenylethyl propionate, potassium sorbate (potassium (2E,4E)-hexa-2,4-dienoate), putrescent whole egg solids, rosemary, rosemary oil, sesame, sesame oil, sodium chloride, sodium lauryl sulfate (sulfuric acid monododecyl ester, sodium salt), soybean oil, spearmint, spearmint oil, thyme, thyme oil, white pepper, and/or zinc. 
     In preferred embodiments, the formulations of the invention are essentially free of currently registered pesticides. In certain embodiments, the spray formulations contain less than 0.1% by weight of one or more currently registered pesticide(s). In a preferred embodiment, the spray formulations contain less than 0.01% by weight of one or more currently registered pesticide(s). In a more preferred embodiment, the spray formulations contain less than 0.001% by weight of one or more currently registered pesticide(s). In a more preferred embodiment, the spray formulations contain less than 0.0001% by weight of one or more currently registered pesticide(s). 
     In some embodiments, the spray formulations of the invention contain less than 0.1% by weight of all currently registered pesticides. In a preferred embodiment, the spray formulations contain less than 0.01% by weight of all currently registered pesticides. In a more preferred embodiment, the spray formulations contain less than 0.001% by weight of all currently registered pesticides. In a more preferred embodiment, the spray formulations contain less than 0.0001% by weight of all currently registered pesticides. 
     If present, the pesticide may be a pyrethroid, an organophosphate, a carbamate, an organochlorine, a lipid amide, a bicyclooctane, a dithiane, a pyrethrin, a pyrethrum, a chloronicotinic, a pyrazole, butenolide, a terpenoid, a fiprole, a tetramic acid derivative (ketoenol), a tetranilliprole, or a biological insecticide. 
     In a preferred embodiment, the spray formulations of the invention contain less than 0.1% by weight of all currently registered pesticides. Currently registered pesticides include, but are not limited to, pyrethroids (such as permethrin, deltamethrin, cypermethrin (including alphamethrin, the allethrins, fenvalerate, transfluthrin, and cyfluthrin), organophosphates (such as ethion, chlorfenvinphos, chlorpyrifos (methyl) or coumaphos), carbamates, organochlorines (such as DDT, dieldrin, dicofol, chlorpropylate, or tetradifon), lipid amides, bicyclooctanes, dithianes, pyrethrins, pyrethrum, chloronicotinics, pyrazoles, butenolides, terpenoids, fiproles, tetramic acid derivatives (ketoenols), tetranilliproles, or biological insecticides. Suitable herbicides include glyphosate. Suitable larvicides (IGRs, biologics) include methoprene,  Bacillus thuringiensis israelensis  (Bti),  Bacillus sphaericus  (Bs), organophosphates (such as temephos), and pyriproxyfen. 
     Currently registered pesticides include one or more pyrethroid. Examples of pyrethroid insecticides include those of the formula (I) 
                         
where R is
 
                         
and n is 0 or 1,
 
R 1  is halo CR3 or CHF2O, R2 is hydrogen or halo, and Z and Z1 are each independently selected from halo, CF3 and methyl, X is hydrogen or halo, and X is H, CN or C═CH
 
     
       
         
         
             
             
         
       
     
     Examples of pyrethroids include, but are not limited to, 3-phenobenzyl-(1RS)-cis,trans-3-(2,2-dichlorovinyl-2,2-di-methyl-cyclopropane-1-carboxylate (permethrin), (RS)-α-cyano-3-phenoxybenzyl-(1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate (cypermethrin) and its individual isomers such as the (1RS) cis isomer (alphamethrin), (S)-α-cyano-3-phenoxybenzyl-(IR)-cis-3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropane-1-carboxylate (deltamethrin), or a reaction mixture comprising two enantiomeric pairs in approximately ratio 2:3 (S)-α-cyano-3-phenoxybenzyl-(IR)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and (R)-α-cyano-3-phenoxybenzyl-(IS)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate with (S)-α=cyano-3-phenoxybenzyl-(IR)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and (R)-α-cyano-3-phenoxybenzyl-(IS)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (beta-cypermethrin), (RS)-α-cyano-3-phenoxybenzyl-(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifiuoro propenyl)-2,2-dimethylcyclopropanecarboxylate (cyhalothrin) and a mixture of its (S)(Z)—(IR)-cis and (R)(Z)—(IS)-cis isomers; (RS)-α-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate (fenvalerate) and the single (S), (S) isomer (esfenvalerate) (RS)-α-cyano-3-phenoxybenzyl (S)-2-(4-difluoromethoxyphenyl)-3-methyl butyrate (flucythinate), (RS)-α-cyano-3-phenoxybenzyl N(2-chloro-α,α,α-trifluoro-p-tolyl)-D-valinate (fluvalinate), (RS)-α-cyano-4-fluoro-3-phenoxybenzyl(IRS)-cis-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (cyfluthrin), (RS)-α-cyano-4-fluoro-3-phenoxybenzyl (IRS)-cis-trans-3-(2-chloro-2(4-chlorophenyl)vinyl)-2,2-dimethylcyclopropanecarboxylate (flumethrin), 2-methylbiphenyl-3-yl-methyl(Z)—(IRS,3RS)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)2,2-dimethylcyclopropanecarboxylate (Bifenthrin); the allethrins, for example (1RS)-3-allyl-2-methyl-4-oxocylopent-2-enyl)cyclopropanecarboxylate (bioallethrin), (1S)-allyl-2-methyl-4-oxocyclopent-2-enyl (1R,3R)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylate (S-bioallethrin), and mixtures of allethrin isomers (esbiothrin); the resmethrins, for example 5-benzyl-3-furylmethyl(IRS-3RS; IRS, 3SR)-2,2-dimethyl-3-(2-methyl-prop-1-enyl)cyclopropanecarboxylate (resmethrin), 5-benzyl-3-furylmethyl (1R,3R)-2,2-dimethyl-3-(2-methyl-prop-1-enyl)cyclopropanecarboxylate (bioresmethrin), and 2,3,5,6-tetrafluorobenzyl (1R,3S)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (transfluthrin), 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl (EZ)-(1RS,3RS;1RS,3SR)-2,2-dimethyl-3-prop-1-enylcyclopropanecarboxylate (metofluthrin), and pyrethroids with a polyfluorobenzyl group. 
     Examples of organophosphate insecticides include, but are not limited to, 0,0-dimethyl-0-3,5,6-trichloro-2-pyridylphosphorothioate (Chloropyri-fos-methyl). 
     Examples of formamidine insecticides include, but are not limited to, N-methyl bis(2,4-xylylaminomethyl)amine (Amitraz). Examples of thiazole anthelmintics include, but are not limited to, 2,3,5,6-tetrahydro-6-phenylimidazo[2,1-b]thiazole (levamisole). 
     Examples of fungicides include, but are not limited to, tributyl tin oxide. 
     Examples of pyrazole insecticides include, but are not limited to, 3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide (cyantraniliprole). 
     Examples of fiprole insecticides include, but are not limited to, 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile (fipronil) and 5-amino-1-[2,6-dichloro-4-trifluoromethyl)phenyl]-4-[(ethyl)-sulfinyl]-1H-pyrazole-3-carbonitrile (ethiprole). 
     Examples of tetramic acid derivatives include, but are not limited to, cis-3-(2,5-dimethlyphenyl)-8-methoxy-2-oxo-1-azaspiro[4.5]dec-3-en-4-yl-ethyl carbonate (suspirotetramat) and 2-oxo-3-(2,4,6-trimethylphenyl)-1-oxaspiro[4,4]non-3-en-4-yl 3,3-dimethylbutanoate (spiromesifen). 
     Examples of butenolides include, but are not limited to, 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one (flupyradifurone [Sivanto®]). 
     The formulations of the invention may contain one or more synergists. A synergist is defined as a chemical that does not possess inherent pesticidal activity, but instead promotes or enhances the effectiveness of pesticides when combined. Examples of synergists include, but are not limited to, sesame oil synergists such as sesamin, sesamolin, sesamex, and safrole, bucarpolate, dietholate, jiajizengxiaolin, octachlorodipropyl ether, piperonyl butoxide (PBO), piperonyl cyclonene, piprotal, propyl isome, sesame, ground sesame plant, sesamin, sesamolin, sesamex, safrole, sulfoxide, tribufos, and zengxiaoan. 
     The formulation of the invention may contain one or more emulsifiers. The emulsifier may be any suitable compound or mixture of compounds. Cationic emulsifiers can be used, but they tend to irritate the users&#39; eyes. Anionic emulsifiers such as calcium dodecyl benzene sulphate (CDBS) or sodium di-isopropyl naphthalene sulphonate (SDNS) can also be used, but these are often not as effective at stabilizing the emulsion. Preferably, the emulsifier is a non-ionic compound, or mixture of non-ionic compounds, having an HLB (hydrophilic/lipophilic balance of 8-18. Suitable compounds include polyoxyethylene stearyl ethers (PSE), polyoxyethylene monolaurates (PEM), polyoxyethylene mono-oleates (PMO), sorbitan mono-oleate (SMO), nonylphenol ethoxylate (NPE), polyethylene glycol (PEG) and blends of oleyl ethoxylate (10 mole) and PEG20 glyceryl oleate (OE/PGO). 
     In a preferred embodiment, the emulsifier is polyoxyethylene (10) oleyl ether, polyoxyethylene (20) stearyl ether, ethoxylated castor oil, or polyoxyethylene (20) sorbitan monooleate. 
     The formulations of the invention may contain one or more surfactants. Examples of surfactants include, but are not limited to, an anionic surfactant such as sodium lauryl sulfate or lauryl sulfate, a nonionic surfactant, or an organo-silicone surfactant. 
     The anti-foam agent may be any suitable compound or mixture of compounds. Exemplary compounds include Silcolapse 426R or Silcolapse 432 (i.e. polyorganosiloxane aqueous emulsion). 
     Constituents may be present in 100% by volume oil phase. Alternatively, the oil phase may comprise up to 45% by volume of the formula and the water phase may comprise up to 55% by volume of the formula wherein all other components are dissolved/dispersed in both phases. In a preferred embodiment, the oil phase is approximately 38% by volume of the formulation and the water phase is approximately 62% by volume of the formulation wherein all other constituents are dissolved/dispersed in both the oil and water phase. 
     The formulations of the instant invention may be used, for example, to control or prevent pest infestation. Thus, the invention comprises a method for controlling and/or preventing pest infestation comprising administering the formulation to an area susceptible to pest infestation. 
     Examples of pests that may be controlled by the formulations of the invention include, but are not limited to, mosquitos, flies, and other public health pests, including, but not limited to cockroaches, bedbugs, sand flies, and reduviidae. Additional examples of pests that may be controlled by the formulations of the invention include, but are not limited to, stored product pests and rural hygiene pests. The formulations of the invention may also be used to control turf, ornamental, and greenhouse pests. 
     Examples of the aforementioned pests include, but are not limited to insects from the phylum Arthropoda, especially from the class Arachnida, for example,  Acarus  spp.,  Aceria sheldoni, Aculops  spp.,  Aculus  spp.,  Amblyomma  spp.,  Amphitetranychus viennensis, Argas  spp.,  Boophilus  spp.,  Brevipalpus  spp.,  Bryobia graminum, Bryobia praetiosa, Centruroides  spp.,  Chorioptes  spp.,  Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor  spp.,  Eotetranychus  spp.,  Epitrimerus pyri, Eutetranychus  spp.,  Eriophyes  spp.,  Glycyphagus domesticus, Halotydeus destructor, Hemitarsonemus  spp.,  Hyalomma  spp.,  Ixodes  spp.,  Latrodectus  spp.,  Loxosceles  spp.,  Metatetranychus  spp.,  Neutrombicula autumnalis, Nuphersa  spp.,  Oligonychus  spp.,  Ornithodorus  spp.,  Ornithonyssus  spp.,  Panonychus  spp.,  Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes  spp.,  Rhipicephalus  spp.,  Rhizoglyphus  spp.,  Sarcoptes  spp., 
     from the order or the class Collembola, for example,  Onychiurus armatus;    
     from the class Diplopoda, for example,  Blaniulus guttulatus;    
     from the class Insecta, e.g. from the order Blattodea, for example,  Blattella asahinai, Blattella germanica, Blatta orientalis, Leucophaea maderae, Panchlora  spp.,  Parcoblatta  spp.,  Periplaneta  spp.,  Supella longipalpa;    
     from the order Coleoptera, for example,  Acalymma vittatum, Acanthoscelides obtectus, Adoretus  spp.,  Agelastica alni, Agriotes  spp.,  Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum, Anoplophora  spp.,  Anthonomus  spp.,  Anthrenus  spp.,  Apion  spp.,  Apogonia  spp.,  Atomaria  spp.,  Attagenus  spp.,  Bruchidius obtectus, Bruchus  spp.,  Cassida  spp.,  Cerotoma trifurcata, Ceutorrhynchus  spp.,  Chaetocnema  spp.,  Cleonus mendicus, Conoderus  spp.,  Cosmopolites  spp.,  Costelytra zealandica, Ctenicera  spp.,  Curculio  spp.,  Cryptolestes ferrugineus, Cryptorhynchus lapathi, Cylindrocopturus  spp.,  Dermestes  spp.,  Diabrotica  spp.,  Dichocrocis  spp.,  Dicladispa armigera, Diloboderus  spp.,  Epilachna  spp.,  Epitrix  spp.,  Faustinus  spp.,  Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychus arator, Heteronyx  spp.,  Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypomeces squamosus, Hypothenemus  spp.,  Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius  spp.,  Lema  spp.,  Leptinotarsa decernlineata, Leucoptera  spp.,  Lissorhoptrus oryzophilus, Lixus  spp.,  Luperodes  spp.,  Lyctus  spp.,  Megascelis  spp.,  Melanotus  spp.,  Meligethes aeneus, Melolontha  spp.,  Migdolus  spp.,  Monochamus  spp.,  Naupactus xanthographus, Necrobia  spp.,  Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus  spp.,  Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga  spp.,  Phyllophaga helleri, Phyllotreta  spp.,  Popillia japonica, Premnotrypes  spp.,  Prostephanus truncatus, Psylliodes  spp.,  Ptinus  spp.,  Rhizobius ventralis, Rhizopertha dominica, Sitophilus  spp.,  Sitophilus oryzae, Sphenophorus  spp.,  Stegobium paniceum, Stemechus  spp.,  Symphyletes  spp.,  Tanymecus  spp.,  Tenebrio molitor, Tenebrioides mauretanicus, Tribolium  spp.,  Trogoderma  spp.,  Tychius  spp.,  Xylotrechus  spp.,  Zabrus  spp.; 
     from the order Diptera, for example,  Aedes  spp.,  Agromyza  spp.,  Anastrepha  spp.,  Anopheles  spp.,  Asphondylia  spp.,  Bactrocera  spp.,  Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chironomus  spp.,  Chrysomyia  spp.,  Chrysops  spp.,  Chrysozona pluvialis, Cochliomyia  spp.,  Contarinia  spp.,  Cordylobia anthropophaga, Cricotopus sylvestris, Culex  spp.,  Culicoides  spp.,  Culiseta  spp.,  Cuterebra  spp.,  Dacus oleae, Dasyneura  spp.,  Delia  spp.,  Dermatobia hominis, Drosophila  spp.,  Echinocnemus  spp.,  Fannia  spp.,  Gasterophilus  spp.,  Glossina  spp.,  Haematopota  spp.,  Hydrellia  spp.,  Hydrellia griseola, Hylemya  spp.,  Hippobosca  spp.,  Hypoderma  spp.,  Liriomyza  spp.,  Lucilia  spp.,  Lutzomyia  spp.,  Mansonia  spp.,  Musca  spp.,  Oestrus  spp.,  Oscinella frit, Paratanytarsus  spp.,  Paralauterborniella subcincta, Pegomyia  spp.,  Phlebotomus  spp.,  Phorbia  spp.,  Phormia  spp.,  Piophila casei, Prodiplosis  spp.,  Psila rosae, Rhagoletis  spp.,  Sarcophaga  spp.,  Simulium  spp.,  Stomoxys  spp.,  Tabanus  spp.,  Tetanops  spp.,  Tipula  spp.; 
     from the order Heteroptera, for example,  Anasa tristis, Antestiopsis  spp.,  Boisea  spp.,  Blissus  spp.,  Calocoris  spp.,  Campylomma livida, Cavelerius  spp.,  Cimex  spp.,  Collaria  spp.,  Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus  spp.,  Euschistus  spp.,  Eurygaster  spp.,  Heliopeltis  spp.,  Horcias nobilellus, Leptocorisa  spp.,  Leptocorisa varicornis, Leptoglossus phyllopus, Lygus  spp.,  Macropes excavatus, Miridae, Monalonion atratum, Nezara  spp.,  Oebalus  spp.,  Pentomidae, Piesma quadrata, Piezodorus  spp.,  Psallus  spp.,  Pseudacysta persea, Rhodnius  spp.,  Sahlbergella singularis, Scaptocoris castanea, Scotinophora  spp.,  Stephanitis nashi, Tibraca  spp.,  Triatoma  spp.; 
     from the order Homoptera, for example,  Acizzia acaciaebaileyanae, Acizzia dodonaeae, Acizzia uncatoides, Acrida turrita, Acyrthosipon  spp.,  Acrogonia  spp.,  Aeneolamia  spp.,  Agonoscena  spp.,  Aleyrodes proletella, Aleurolobus barodensis, Aleurothrixus floccosus, Allocaridara malayensis, Amrasca  spp.,  Anuraphis cardui, Aonidiella  spp.,  Aphanostigma piri, Aphis  spp.,  Arboridia apicalis, Arytainilla  spp.,  Aspidiella  spp.,  Aspidiotus  spp.,  Atanus  spp.,  Aulacorthum solani, Bemisia tabaci, Blastopsylla occidentalis, Boreioglycaspis melaleucae, Brachycaudus helichrysi, Brachycolus  spp.,  Brevicoryne brassicae, Cacopsylla  spp.,  Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes  spp.,  Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chondracris rosea, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus  spp.,  Cryptomyzus ribis, Cryptoneossa  spp.,  Ctenarytaina  spp.,  Dalbulus  spp.,  Dialeurodes citri, Diaphorina cirri, Diaspis  spp.,  Drosicha  spp.,  Dysaphis  spp.,  Dysmicoccus  spp.,  Empoasca  spp.,  Eriosoma  spp.,  Erythroneura  spp.,  Eucalyptolyma  spp.,  Euphyllura  spp.,  Euscelis bilobatus, Ferrisia  spp.,  Geococcus coffeae, Glycaspis  spp.,  Heteropsylla cubana, Heteropsylla spinulosa, Homalodisca coagulata, Hyalopterus arundinis, Icerya  spp.,  Idiocerus  spp.,  Idioscopus  spp.,  Laodelphax striatellus, Lecanium  spp.,  Lepidosaphes  spp.,  Lipaphis erysimi, Macrosiphum  spp.,  Macrosteles facifrons, Mahanarva  spp.,  Melanaphis sacchari, Metcalflella  spp.,  Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus  spp.,  Nasonovia ribisnigri, Nephotettix  spp.,  Nettigoniella spectra, Nilaparvata lugens, Oncometopia  spp.,  Orthezia praelonga, Oxya chinensis, Pachypsylla  spp.,  Parabemisia myricae, Paratrioza  spp.,  Parlatoria  spp.,  Pemphigus  spp.,  Peregrinus maidis, Phenacoccus  spp.,  Phloeomyzus passerinii, Phorodon humuli, Phylloxera  spp.,  Pinnaspis aspidistrae, Planococcus  spp.,  Prosopidopsylla flava, Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus  spp.,  Psyllopsis  spp.,  Psylla  spp.,  Pteromalus  spp.,  Pyrilla  spp.,  Quadraspidiotus  spp.,  Quesada gigas, Rastrococcus  spp.,  Rhopalosiphum  spp.,  Saissetia  spp.,  Scaphoideus titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata  spp.,  Sogatella furcifera, Sogatodes  spp.,  Stictocephala festina, Siphoninus phillyreae, Tenalaphara malayensis, Tetragonocephela  spp.,  Tinocallis caryaefoliae, Tomaspis  spp.,  Toxoptera  spp.,  Trialeurodes vaporariorum, Trioza  spp.,  Typhlocyba  spp.,  Unaspis  spp.,  Viteus vitifolii, Zygina  spp.; 
     from the order Hymenoptera, for example,  Acromyrmex  spp.,  Athalia  spp.,  Atta  spp.,  Diprion  spp.,  Hoplocampa  spp.,  Lasius  spp.,  Monomorium pharaonis, Sirex  spp.,  Solenopsis invicta, Tapinoma  spp.,  Urocerus  spp.,  Vespa  spp.,  Xeris  spp.: 
     from the order Isopoda, for example,  Armadillidium vulgare, Oniscus asellus, Porcellio scaber;    
     from the order Isoptera, for example,  Coptotermes  spp.,  Comitermes cumulans, Cryptotermes  spp.,  Incisitermes  spp.,  Microtermes obesi, Odontotermes  spp.,  Reticulitermes  spp.; 
     from the order Lepidoptera, for example,  Achroia grisella, Acronicta major, Adoxophyes  spp.,  Aedia leucomelas, Agrotis  spp.,  Alabama  spp.,  Amyelois transitella, Anarsia  spp.,  Anticarsia  spp.,  Argyroploce  spp.,  Barathra brassicae, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola  spp.,  Cacoecia  spp.,  Caloptilia theivora, Capua reticulana, Carpocapsa pomonella, Carposina niponensis, Cheimatobia brumata, Chilo  spp.,  Choristoneura  spp.,  Clysia ambiguella, Cnaphalocerus  spp.,  Cnaphalocrocis medinalis, Cnephasia  spp.,  Conopomorpha  spp.,  Conotrachelus  spp.,  Copitarsia  spp.,  Cydia  spp.,  Dalaca noctuides, Diaphania  spp.,  Diatraea saccharalis, Earias  spp.,  Ecdytolopha aurantium, Elasmopalpus lignosellus, Eldana saccharina, Ephestia  spp.,  Epinotia  spp.,  Epiphyas postvittana, Etiella  spp.,  Eulia  spp.,  Eupoecilia ambiguella, Euproctis  spp.,  Euxoa  spp.,  Feltia  spp.,  Galleria mellonella, Gracillaria  spp.,  Grapholitha  spp.,  Hedylepta  spp.,  Helicoverpa  spp.,  Heliothis  spp.,  Hofmannophila pseudospretella, Homoeosoma  spp.,  Homona  spp.,  Hyponomeuta padella, Kakivoria flavofasciata, Laphygma  spp.,  Laspeyresia molesta, Leucinodes orbonalis, Leucoptera  spp.,  Lithocolletis  spp.,  Lithophane antennata, Lobesia  spp.,  Loxagrotis albicosta, Lymantria  spp.,  Lyonetia  spp.,  Malacosoma neustria, Maruca testulalis, Mamstra brassicae, Melanitis leda, Mocis  spp.,  Monopis obviella, Mythimna separata, Nemapogon cloacellus, Nymphula  spp.,  Oiketicus  spp.,  Oria  spp.,  Orthaga  spp.,  Ostrinia  spp.,  Oulema oryzae, Panolis flammea, Parnara  spp.,  Pectinophora  spp.,  Perileucoptera  spp.,  Phthorimaea  spp.,  Phyllocnistis citrella, Phyllonorycter  spp.,  Pieris  spp.,  Platynota stultana, Plodia interpunctella, Plusia  spp.,  Plutella xylostella, Prays  spp.,  Prodenia  spp.,  Protoparce  spp.,  Pseudaletia  spp.,  Pseudaletia unipuncta, Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoeniobius  spp.,  Scirpophaga  spp.,  Scirpophaga innotata, Scotia segetum, Sesamia  spp.,  Sesamia inferens, Sparganothis  spp.,  Spodoptera  spp.,  Spodoptera praefica, Stathmopoda  spp.,  Stomopteryx subsecivella, Synanthedon  spp.,  Tecia solanivora, Thermesia gemmatalis, Tinea cloacella, Tinea pellionella, Tineola bisselliella, Tortrix  spp.,  Trichophaga tapetzella, Trichoplusia  spp.,  Tryporyza incertulas, Tuta absoluta, Virachola  spp.; 
     from the order Orthoptera or Saltatoria, for example,  Acheta domesticus, Dichroplus  spp.,  Gryllotalpa  spp.,  Hieroglyphus  spp.,  Locusta  spp.,  Melanoplus  spp.,  Schistocerca gregaria;    
     from the order Phthiraptera, for example,  Damalinia  spp.,  Haematopinus  spp.,  Linognathus  spp.,  Pediculus  spp.,  Ptirus pubis, Trichodectes  spp.; 
     from the order Psocoptera for example  Lepinatus  spp.,  Liposcelis  spp.; 
     from the order Siphonaptera, for example,  Ceratophyllus  spp.,  Ctenocephalides  spp.,  Pulex irritaris, Tunga penetrans, Xenopsylla cheopsis;    
     from the order Thysanoptera, for example,  Anaphothrips obscurus, Baliothrips biformis, Drepanothrips reuteri, Enneothrips flavens, Frankliniella  spp.,  Heliothrips  spp.,  Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips  spp.,  Taeniothrips cardamomi, Thrips  spp.; 
     from the order Zygentoma (=Thysanura), for example,  Ctenolepisma  spp.,  Lepisma saccharina, Lepismodes inquilinus, Thermobia domestica;    
     from the class Symphyla, for example,  Scutigerella  spp.; 
     pests from the phylum Mollusca, especially from the class  Bivalvia , for example,  Dreissena  spp., and from the class Gastropoda, for example,  Arion  spp.,  Biomphalaria  spp.,  Bulinus  spp.,  Deroceras  spp.,  Galba  spp.,  Lymnaea  spp.,  Oncomelania  spp.,  Pomacea  spp.,  Succinea  spp.; 
     animal pests being nematodes from the phylums Plathelminthes and Nematoda, for example,  Ancylostoma duodenale, Ancylostoma ceylanicum, Ancylostoma braziliensis, Ancylostoma  spp.,  Ascaris  spp.,  Brugia malayi, Brugia timori, Bunostomum  spp.,  Chabertia  spp.,  Clonorchis  spp.,  Cooperia  spp.,  Dicrocoelium  spp.,  Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola  spp.,  Haemonchus  spp.,  Heterakis  spp.,  Hymenolepis nana, Hyostrongulus  spp.,  Loa, Nematodirus  spp.,  Oesophagostomum  spp.,  Opisthorchis  spp.,  Onchocerca volvulus, Ostertagia  spp.,  Paragonimus  spp.,  Schistosomen  spp.,  Strongyloides fuelleborni, Strongyloides stercoralis, Strongyloides  spp.,  Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus  spp.,  Trichuris trichura, Wuchereria bancrofti;    
     phytoparasitic pests being nematodes from the phylum Nematoda, for example,  Aphelenchoides  spp.,  Bursaphelenchus  spp.,  Ditylenchus  spp.,  Globodera  spp.,  Heterodera  spp.,  Longidorus  spp.,  Meloidogyne  spp.,  Pratylenchus  spp.,  Radopholus  spp.,  Trichodorus  spp.,  Tylenchulus  spp.,  Xiphinema  spp.,  Helicotylenchus  spp.,  Tylenchorhynchus  spp.,  Scutellonema  spp.,  Paratrichodorus  spp.,  Meloinema  spp.,  Paraphelenchus  spp.,  Aglenchus  spp.,  Belonolaimus  spp.,  Nacobbus  spp.,  Rotylenchulus  spp.,  Rotylenchus  spp.,  Neotylenchus  spp.,  Paraphelenchus  spp.,  Dolichodoras  spp.,  Hoplolaimus  spp.,  Punctodera  spp.,  Criconemella  spp.,  Quinisulcius  spp.,  Hemicycliophora  spp.,  Hirschmaniella  spp.,  Anguina  spp.,  Subanguina  spp.,  Hemicriconemoides  spp.,  Psilenchus  spp.,  Pseudohalenchus  spp.,  Criconemoides  spp.,  Cacopauras  spp. 
     Examples of areas that are susceptible to pest infestation which may be treated with the formulations of the invention include, but are not limited to, complex canopies. A complex canopy is defined as an area that is difficult to penetrate with typical pesticide formulations. Examples of complex canopies include, but are not limited to, dense vegetation and/or complex environments. 
     In an additional embodiment, the formulations of the instant invention can be used as a fumigant. Areas which may be treated according to this embodiment include areas of habitation. Examples of areas of habitation include, but are not limited to, indoor livestock facilities, outdoor livestock facilities, product storage areas, housing, office spaces, retail spaces, warehouses, and shipping containers. 
     The formulations of the instant invention are preferably wide-area space sprays applied via ULV to control mosquitoes, flies, and other public health pests. Preferably, the formulations of the instant invention can be applied via truck, backpack blower, drone, or helicopter. Examples of wide-area spaces include, but are not limited to, urban environments, greenhouses, warehouses, grain storage facilities, stables, farms, food production facilities, agricultural areas, and fields. 
     Formulations of the invention have been observed to provide significantly superior control of pests when applied via ULV. Specifically, it was discovered that formulations of the invention provide exceptional bio-efficacy, measured by mortality, in the absence of currently registered pesticides. 
     In a preferred embodiment, application of the formulations of the invention via ULV provides a total average droplet density of ≥0.3 drops/mm 2 /fl oz of applied product. In a more preferred embodiment, application of the formulations of the invention via ULV provides a total average droplet density of ≥0.4 drops/mm 2 /fl oz of applied product. In a more preferred embodiment, application of the formulations of the invention via ULV provides a total average droplet density of ≥0.5 drops/mm 2 /fl oz of applied product. In a more preferred embodiment, application of the formulations of the invention via ULV provides a total average droplet density of ≥0.7 drops/mm 2 /fl oz of applied product. In a more preferred embodiment, application of the formulations of the invention via ULV provides a total average droplet density of ≥1 drop/mm 2 /fl oz of applied product. 
     In an additional preferred embodiment, application of the formulations of the invention via ULV provides a variance in droplet density over a distance of 300 feet of 0.1 or less. In a more preferred embodiment, application of the formulations of the invention via ULV provides a variance in droplet density over a distance of 300 feet of 0.01 or less. In a more preferred embodiment, application of the formulations of the invention via ULV provides a variance in droplet density over a distance of 300 feet of 0.001 or less. In a more preferred embodiment, application of the formulations of the invention via ULV provides a variance in droplet density over a distance of 300 feet of 0.0005 or less. 
     The following Examples describe exemplary embodiments of the invention. These Examples should not be interpreted to encompass the entire breadth of the invention. 
     EXAMPLES 
     Example 1: Efficacy of Non-VOC Solvent Formulation Applied Via Hand-Held ULV Sprayer Against  Aedes aegypti    
     The efficacy of a non-VOC solvent formulation of the invention was evaluated using an electric, hand-held ULV sprayer against laboratory-reared  Aedes aegypti . The non-VOC solvent formulation of the invention (Formulation 1) was applied at a rate of 37 ml/min from a distance of 50 ft. This experiment was performed in duplicate (Exp 1 &amp; 2). Control cages were held up-wind of the application and were exposed to the same environmental conditions but received no treatment. 
     Mortality was assessed at three time points: 15 minutes following treatment; 50 minutes following treatment; and 24 hours following treatment. The findings are presented below in Table 1. 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                   
                   
                 Time after 
                   
                   
               
               
                 Product 
                 Solvent 
                 Application 
                 Live 
                 Dead 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Formulation 1 
                 Acetyl tributyl 
                 15 
                 min 
                 0 
                 63 
               
               
                 (Exp 1) 
                 citrate 
                 50  
                 min 
                 0 
                 63 
               
               
                   
                   
                 24 
                 hr 
                 0 
                 63 
               
               
                 Formulation 1 
                 Acetyl tributyl 
                 15 
                 min 
                 2 
                 28 
               
               
                 (Exp 2) 
                 citrate 
                 50 
                 min 
                 1 
                 29 
               
               
                   
                   
                 24 
                 hr 
                 0 
                 30 
               
               
                 Control 
                 N/A 
                 15 
                 min 
                 20 
                 0 
               
               
                   
                   
                 50 
                 min 
                 20 
                 0 
               
               
                   
                   
                 24 
                 hr 
                 20 
                 0 
               
               
                   
               
            
           
         
       
     
     As illustrated in the above table, a non-VOC formulation of the invention displayed 100% efficacy within 24 hours after application despite the absence of active ingredient. 
     This experiment was repeated as described above except a gas-powered, hand-held ULV sprayer was used to apply the formulations and different concentrations of acetyl tributyl citrate were tested. The findings are presented below in Tables 2 and 3. 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 2 
               
               
                   
               
               
                   
                   
                 Time after 
                   
                   
               
               
                 Product 
                 Concentration 
                 Application 
                 Live 
                 Dead 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Formulation 1 
                 100% acetyl  
                 15 
                 min 
                 0 
                 28 
               
               
                 (Exp 1) 
                 tributyl citrate 
                 60 
                 min 
                 0 
                 28 
               
               
                   
                   
                 24 
                 hr 
                 0 
                 28 
               
               
                 Formulation 1 
                 100% acetyl  
                 15 
                 min 
                 1 
                 25 
               
               
                 (Exp 2) 
                 tributyl citrate 
                 60 
                 min 
                 0 
                 26 
               
               
                   
                   
                 24 
                 hr 
                 0 
                 26 
               
               
                 Control 
                 N/A 
                 15 
                 min 
                 25 
                 0 
               
               
                   
                   
                 60 
                 min 
                 25 
                 0 
               
               
                   
                   
                 24 
                 hr 
                 24 
                 1 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 3 
               
               
                   
               
               
                   
                   
                 Time after 
                   
                   
               
               
                 Product 
                 Concentration 
                 Application 
                 Live 
                 Dead 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Formulation 1 
                 32% acetyl  
                 15 
                 min 
                 4 
                 26 
               
               
                 (Exp 1) 
                 tributyl citrate 
                 60 
                 min 
                 1 
                 29 
               
               
                   
                   
                 24 
                 hr 
                 0 
                 30 
               
               
                 Formulation 1 
                 32% acetyl  
                 15 
                 min 
                 5 
                 20 
               
               
                 (Exp 2) 
                 tributyl citrate 
                 60 
                 min 
                 2 
                 23 
               
               
                   
                   
                 24 
                 hr 
                 0 
                 25 
               
               
                 Control 
                 N/A 
                 15  
                 min 
                 22 
                 0 
               
               
                   
                   
                 60 
                 min 
                 22 
                 0 
               
               
                   
                   
                 24 
                 hr 
                 22 
                 0 
               
               
                   
               
            
           
         
       
     
     Table 2 replicates the studies from the initial experiment illustrated in Table 1. As in the previous study, 100% mortality was noted within 24 hours. The findings of Table 3 demonstrate that a 32% by volume acetyl tributyl citrate in an aqueous formulation results in 100% mortality within 24 hours. 
     Example 2: Efficacy of Non-VOC Solvent Formulation Applied Directly Against  Culex quinquefasciatus  and  Aedes aegypti    
     The efficacy of a non-VOC solvent formulation of the invention was evaluated using a pump-sprayer against  Culex quinquefasciatus  and  Aedes aegypti . The non-VOC solvent formulation of the invention comprising acetyl tributyl citrate (Formulation 1) was applied at a concentration of either 15.75 mg/ml or 31.5 mg/ml from a distance of approximately 15 cm. Controls were sprayed with water. The experiment was replicated five times and ten insects were sprayed per replicate. 
     Percentage knock-down and/or mortality was determined at three time points: 30 minutes following treatment; 1 hour following treatment; and 24 hours following treatment. The findings are presented below in Tables 4 and 5. 
     
       
         
           
               
               
             
               
                   
                 TABLE 4 
               
             
            
               
                   
                   
               
               
                   
                 % knock down and/or mortality of  Culex quinquefasciatus  (out of 10 
               
               
                   
                 per replicate) after direct spray treatment 
               
            
           
           
               
               
               
               
            
               
                   
                 Formulation 1 
                 Formulation 1 
                 Control 
               
               
                   
                 31.5 mg/ml* 
                 15.75 mg/ml* 
                 — 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 efficacy after 
                 1 
                 2 
                 3 
                 4 
                 5 
                 1 
                 2 
                 3 
                 4 
                 5 
                 1 
                 2 
                 3 
                 4 
                 5 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 30 minutes 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                  1 hour 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 24 hour mortality 
                 10 
                 20 
                 70 
                 30 
                 50 
                 10 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                   
               
               
                 *Concentration of acetyl tributyl citrate in space spray 
               
            
           
         
       
     
     
       
         
           
               
               
             
               
                   
                 TABLE 5 
               
             
            
               
                   
                   
               
               
                   
                 % knock down and/or mortality of  Aedes aegypti  (out of 10 per 
               
               
                   
                 replicate) after direct spray treatment: 
               
            
           
           
               
               
               
               
            
               
                   
                 Formulation 1 
                 Formulation 1 
                 Control 
               
               
                   
                 31.5 mg/ml* 
                 15.75 mg/ml* 
                 — 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 efficacy after 
                 1 
                 2 
                 3 
                 4 
                 5 
                 1 
                 2 
                 3 
                 4 
                 5 
                 1 
                 2 
                 3 
                 4 
                 5 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 30 minutes 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                  1 hour 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 24 hour mortality 
                 60 
                 10 
                 40 
                 50 
                 50 
                 0 
                 10 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                   
               
               
                 *Concentration of acetyl tributyl citrate in space spray 
               
            
           
         
       
     
     The above data confirm that non-VOC formulations comprising acetyl tributyl citrate are effective at killing both  Aedes aegypti  and  Culex quinquefasciatus.    
     Further studies were conducted using acetyl tributyl citrate as described in Table 6. 
     
       
         
           
               
               
             
               
                   
                 TABLE 6 
               
             
            
               
                   
                   
               
               
                   
                 % knock down and/or mortality of  Aedes aegypti  (out of 10 per 
               
               
                   
                 replicate) after direct spray treatment: 
               
            
           
           
               
               
               
               
            
               
                   
                 Citroflex A-4 
                   
                 Citroflex A-4 
               
               
                   
                 Many spray 
                 Citroflex A-4 
                 One spray push 
               
               
                   
                 pushes pure 
                 One spray push pure 
                 Citroflex 1:1 with tap 
               
               
                   
                 Citroflex A4 (1 ml) 
                 Citroflex A4 (1 ml) 
                 water 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 efficacy after 
                 1 
                 2 
                 3 
                 4 
                 5 
                 1 
                 2 
                 3 
                 4 
                 5 
                 1 
                 2 
                 3 
                 4 
                 5 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                  1 hour 
                 100 
                   
                 100 
                   
                 100 
                   
               
               
                 24 hour 
                 100 
                   
                 100 
                   
                 100 
               
               
                 mortality 
               
               
                   
               
            
           
         
       
     
     Example 3: Residual Efficacy of Non-VOC Solvent Formulation Applied Against  Culex quinquefasciatus    
     The residual efficacy of a non-VOC solvent formulation of the invention was evaluated against  Culex quinquefasciatus . The non-VOC solvent formulation of the invention comprising acetyl tributyl citrate (Formulation 1) was applied to either tissue or glazed tiles at a concentration of either 15.75 mg/ml or 31.5 mg/ml (1.12 ml per surface; 225 cm 2  tile/tissue). Positive controls were treated with Bay Bay fly, which is a mixture of octamethylcyclotetrasiloxan (D4) (75% by volume) and decamethylcyclopentasiloxan (D5) (25% by volume). The experiment was replicated four times and ten insects were sprayed per replicate. 
     Percentage knock-down and/or mortality was determined at three time points: 30 minutes following treatment; 1 hour following treatment; and 24 hours following treatment. The findings are presented below in Tables 7 and 8. 
     
       
         
           
               
               
             
               
                   
                 TABLE 7 
               
             
            
               
                   
                   
               
               
                   
                 Residual efficacy on treated tissues: % knock down and/or mortality 
               
               
                   
                 of  Culex quinquefasciatus  (out of 10 per replicate) 
               
            
           
           
               
               
               
               
            
               
                   
                 Formulation 1 
                 Formulation 1 
                   
               
               
                   
                 31.5 mg/ml 
                 15.75 mg/ml 
                 Bay Bay fly 
               
               
                 efficacy 
                 1.12 ml/225 cm 2   
                 1.12 ml/225 cm 2   
                 1.12 ml/225 cm 2   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 after 
                 1 
                 2 
                 3 
                 4 
                 5 
                 1 
                 2 
                 3 
                 4 
                 5 
                 1 
                 2 
                 3 
                 4 
                 5 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 30 minutes 
                 0 
                 0 
                 0 
                 0 
                   
                 10 
                 10 
                 0 
                 0 
                   
                 50 
                 100 
                 50 
                 60 
                   
               
               
                  1 hour 
                 0 
                 0 
                 0 
                 0 
                   
                 10 
                 0 
                 20 
                 0 
                   
                 100 
                 100 
                 100 
                 100 
               
               
                 24 hour 
                 0 
                 0 
                 0 
                 0 
                   
                 0 
                 0 
                 20 
                 0 
                   
                 100 
                 100 
                 100 
                 90 
               
               
                 mortality 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
             
               
                   
                 TABLE 8 
               
             
            
               
                   
                   
               
               
                   
                 Residual efficacy on treated glazed tiles: % knock down and/or 
               
               
                   
                 mortality of  Culex quinquefasciatus  (out of 10 per replicate) 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 Formulation 1 
                 Formulation 1 
                   
               
               
                   
                   
                 31.5 mg/ml 
                 15.75 mg/ml 
                 Bay Bay fly 
               
               
                 test 
                 efficacy 
                 1.12 ml/225 cm 2   
                 1.12 ml/225 cm 2   
                 1.12 ml/225 cm 2   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 point 
                 after 
                 1 
                 2 
                 3 
                 4 
                 5 
                 1 
                 2 
                 3 
                 4 
                 5 
                 1 
                 2 
                 3 
                 4 
                 5 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 30 minutes 
                 0 
                 0 
                 0 
                 0 
                   
                 0 
                 30 
                 0 
                 0 
                   
                 0 
                 0 
                 0 
                 0 
                   
               
               
                   
                  1 hour 
                 0 
                 0 
                 0 
                 0 
                   
                 0 
                 0 
                 0 
                 0 
                   
                 0 
                 0 
                 0 
                 0 
               
               
                   
                 24 hour 
                 0 
                 0 
                 0 
                 0 
                   
                 0 
                 0 
                 0 
                 0 
                   
                 0 
                 0 
                 0 
                 0 
               
               
                   
                 mortality 
               
               
                   
               
            
           
         
       
     
     The above data confirm that there is no residual activity of non-VOC formulations comprising acetyl tributyl citrate. 
     All references cited in this specification are herein incorporated by reference as though each reference was specifically and individually indicated to be incorporated by reference. The citation of any reference is for its disclosure prior to the filing date and should not be construed as an admission that the present disclosure is not entitled to antedate such reference by virtue of prior invention. 
     It will be understood that each of the elements described above, or two or more together may also find a useful application in other types of methods differing from the type described above. Without further analysis, the foregoing will so fully reveal the gist of the present disclosure that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this disclosure set forth in the appended claims. The foregoing embodiments are presented by way of example only; the scope of the present disclosure is to be limited only by the following claims.