US 2010O297260A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0297260 A1 Wilson et al. (43) Pub. Date: Nov. 25, 2010

(54) PESTICIDE COMPOSITIONS EXHIBITING Related U.S. Application Data ENHANCED ACTIVITY (60) Provisional application No. 61/214,965, filed on Apr. (76) Inventors: Stephen L. Wilson, Indianapolis, 30, 2009. IN (US); Lei Liu, Carmel, IN (US); Publication Classification James D. Thomas, Fishers, IN (51) Int. Cl. (US); Raymond E. Boucher, JR. AOIN 59/6 (2006.01) Lebanon, IN (US); James E. AOIN 37/18 (2006.01) Dripps, Carmel, IN (US); Margaret S. Kempe, Greenfield, AOIP 7/04 (2006.01) IN (US) (52) U.S. Cl...... 424/641; 514/4.5; 424/647 (57) ABSTRACT Correspondence Address: Pest controlling compositions exhibiting enhanced pesticidal Krieg DeVault LLP activity levels are disclosed. In one embodiment, a composi Suite 2800, One Indiana Square tion includes at least one pesticide, at least one transition Indianapolis, IN46204-2079 (US) metal salt and at least one proteinaceous material. In this embodiment, the composition exhibits enhanced pesticidal (21) Appl. No.: 12/768,084 activity levels compared to a composition dissimilar only in not having the at least one transition metal salt and the at least (22) Filed: Apr. 27, 2010 one proteinaceous material. US 2010/0297260 A1 Nov. 25, 2010

PESTICIDE COMPOSITIONS EXHIBITING for the at least one pesticide, transition metal salt and pro ENHANCED ACTIVITY teinaceous material are contemplated. 0007. In another embodiment, a composition includes CROSS REFERENCE TO RELATED from about 8% to about 15% by weight of spinetoram, from APPLICATIONS about 40% to about 60% by weight of a proteinaceous mate rial, and from about 25% to about 40% by weight of a tran 0001. The subject application claims priority to U.S. Pro sition metal salt. In one aspect of this embodiment, the tran visional Application No. 61/214,965 filed Apr. 30, 2009, the sition metal salt includes iron (III) sulfate and the contents of which are incorporated herein by reference in proteinaceous material includes egg albumen. their entirety. 0008. In yet another embodiment, a method includes applying to a locus where control is desired an insect-inacti FIELD OF THE INVENTION Vating amount of a pesticide composition. Still, further 0002. The invention disclosed in this document is related embodiments, forms, features, aspects, benefits, objects, and to the field of pesticides and their use in controlling pests. advantages of the present invention shall become apparent from the detailed description and examples provided. BACKGROUND OF THE INVENTION DETAILED DESCRIPTION OF THE INVENTION 0003 Pests cause millions of human deaths around the world each year. Furthermore, there are more than ten thou 0009 Throughout this document, all temperatures are sand species of pests that cause losses in agriculture. These given in degrees Celsius, and all percentages are weight per agricultural losses amount to billions of U.S. dollars each centages unless otherwise stated. year. Termites cause damage to various structures such as 0010 Pesticide compositions exhibiting increased stabil homes. These termite damage losses amount to billions of ity and enhanced pesticidal activity are described in this docu U.S. dollars each year. As a final note, many stored food pests ment. More particularly, in one or more embodiments, the eat and adulterate stored food. These stored food losses pesticide compositions exhibit enhanced residual pesticidal amount to billions of U.S. dollars each year, but more impor activity. A pesticide is herein defined as any compound which tantly, deprive people of needed food. shows some pesticidal or biocidal activity, or otherwise par 0004. Many pesticide compositions have been developed ticipates in the control or limitation of pest populations. Such over time to destroy pests and alleviate the damages they compounds include fungicides, insecticides, nematocides, cause. These compositions are often applied to the environ miticides, termiticides, rodenticides, molluscides, arthro ment in which the insects or other pests live or where their podicides, herbicides, biocides, as well as pheromones and eggs are present, including the air Surrounding them, the food attractants and the like. they eat, or objects which they contact. Several of these com 0011 Examples of pesticides that can be included in the positions are Vulnerable to chemical and physical degradation compositions described herein include, but are not limited to, when applied to these environments. If these types of degra antibiotic insecticides, macrocyclic lactone insecticides (for dation occur, the pesticidal activity of the pesticides can be example, avermectin insecticides, milbemycin insecticides, adversely affected, commonly necessitating an increase in the and spinosyn insecticides), arsenical insecticides, botanical concentration at which the pesticides are applied and/or more insecticides, carbamate insecticides (for example, benzofura frequent applications of the pesticides. As a result, user costs nyl methylcarbamate insecticides, dimethylcarbamate insec and the costs to consumers can escalate. Therefore, a need ticides, oxime carbamate insecticides, and phenyl methylcar exists for new pesticide compositions that exhibit increased bamate insecticides), diamide insecticides, desiccant stability and enhanced activity compared to existing pesticide insecticides, dinitrophenol insecticides, fluorine insecticides, compositions when, for example, the pesticide compositions fonnamidine insecticides, fumigant insecticides, inorganic are applied to an environment to control pests. insecticides, insect growth regulators (for example, chitin synthesis inhibitors, juvenile hormone mimics, juvenile hor SUMMARY OF THE INVENTION mones, moulting hormone agonists, moulting hormones, moulting inhibitors, precocenes, and other unclassified insect 0005. The present invention concerns novel pesticide growth regulators), nereistoxin analogue insecticides, nicoti compositions and their use in controlling insects and certain noid insecticides (for example, nitroguanidine insecticides, other invertebrates. In one embodiment, a composition nitromethylene insecticides, and pyridylmethylamine insec includes at least one pesticide, at least one metal salt and at ticides), organochlorine insecticides, organophosphorus least one proteinaceous material. In this embodiment, the insecticides, oxadiazine insecticides, oxadiazolone insecti composition exhibits enhanced pesticidal activity levels com cides, phthalimide insecticides, pyrazole insecticides, pyre pared to a composition dissimilar only in not having the at throid insecticides, pyrimidinamine insecticides, pyrrole least one metal salt and the at least one proteinaceous mate insecticides, tetramic acid insecticides, tetronic acid insecti rial. In one form, the at least one pesticide is a photo-labile cides, thiazole insecticides, thiazolidine insecticides, thio pesticide. In another form, the at least one pesticide is a urea insecticides, urea insecticides, as well as, other unclas macrocyclic lactone insecticide. sified insecticides. 0006. In a more particular form, the at least one pesticide 0012 Some of the particular insecticides that can be is a spinosyn, such as spinetoram or spinosad, the at least one employed in the compositions described in this document metal salt is a transition metal salt Such as a transition metal include, but are not limited to, the following: 1,2-dichloro acetate, acetylacetonate, nitrate, Sulfate, carbonate or halide, propane, 1.3 dichloropropene, abamectin, acephate, acetami including chloride, fluoride, bromide and iodide, and the at prid, acethion, acetoprole, acrinathrin, acrylonitrile, alany least one proteinaceous material is egg albumen, whey, gela carb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, tin or Zein. However, it should be appreciated that alternatives allyxycarb, alpha-cype ethrin, alpha-endosulfan, amidithion, US 2010/0297260 A1 Nov. 25, 2010

aminocarb, amiton, amitraz, anabasine, athidathion, aza naftalofos, naled, naphthalene, nicotine, nifluridide, niten dirachtin, azamethiphos, azinphos-ethyl, azinphosmethyl, pyram, nithiazine, nitrilacarb, novaluron, noviflumuron, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, omethoate, oxamyl, Oxydemeton-methyl, oxydeprofos, oxy benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, disulfoton, para-dichlorobenzene, parathion, parathion-me bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, thyl, penfluron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phos bioresmethrin, bistrifluron, borax, boric acid, boric acid, bro met, phosnichlor, phosphamidon, phosphine, phoxim, mfenVinfos, bromocyclen, bromo-DDT, bromophos, bro phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, mophosethyl, bufencarb, buprofezin, butacarb, butathiofos, pirimiphos-methyl, potassium arsenite, potassium thiocyan butocarboxim, butonate, butoxycarboxim, cadusafos, cal ate, pp'-DDT, prallethrin. precocene I, precocene II, pre cium arsenate, calcium polysulfide, camphechlor, carbano cocene III, primidophos, profenofos, profluthrin, promacyl, late, carbaryl, carbofuran, carbon disulfide, carbon tetrachlo promecarb, propaphos, propetamphos, propoXur, prothi ride, carbophenothion, carbosulfan, cartap, dathion, prothiofos, prothoate, protrifenbute, pyraclofos, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyre chlordimefonn, chlorethoxyfos, chlorfenapyr, chlorfenvin thrin II, pyridaben, pyridalyl pyridaphenthion, pyriflu phos, chlorfluaZuron, chlormephos, chloroform, chloropi quinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, crin, chlorphoxim, chlorpraZophos, chlorpyrifos, chlorpyri quassia, quinalphos, quinalphosmethyl, quinothion, rafox foS-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin anide, resmethrin, rotenone, ryania, Sabadilla, Schradan, sel II, cismethrin, cloethocarb, closantel, clothianidin, copper amectin, Silafluofen, silica gel, sodium arsenite, Sodium fluo acetoarsenite, copper arsenate, copper naphthenate, copper ride, sodium hexafluorosilicate, sodium thiocyanate, oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, sophamide, spinetoram, spinosad, spiromesifen, spirotetra crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, mat, Sulcofuron, Sulfluramid, Sulfotep, Sulfuryl fluoride, Sul cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cyper profos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, methrin, cyphenothrin, cyromazine, cythioate, DDT, decar tebufenpyrad, tebupirimfos, teflubenZuron, tefluthrin, teme bofuran, deltamethrin, demephion, demephion-O, deme phos, TEPP, terallethrin, terbufos, tetrachloroethane, tetra phion-S, demeton, demeton-methyl, demeton-O, demeton chlorvinphos, tetramethrin, theta-cypermethrin, thiacloprid, O-methyl, demeton-S, demeton-S-methyl, demeton-S- thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodi methylsulphon, diafenthiuron, dialifos, diatomaceous earth, carb, thiofanox, thiometon, thiosultap, thuringiensin, tolfen diazinon, dicapthon, dichlofenthion, dichlorvos, dicresyl pyrad, tralomethrin, transfluthrin, transpermethrin, triarath dicrotophos, dicyclanil, dieldrin, diflubenZuron, dilor, dime ene, triazamate, triaZophos, trichlorfon, trichlorimetaphos-3. fluthrin, dimefox, dimetan, dimethoate, dimethrin, dimeth trichloronat, trifenofos, triflumuron, trimethacarb, triprene, ylvinphos, dimetilan, dinex, dinoprop, dinosam, dinotefuran, vamidothion, vaniliprole. XMC, xylylcarb, Zeta-cyper diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfo methrin, Zolaprofos, and C-ecdysone. ton, dithicrofos, d-limonene, DNOC, doramectin, ecdyster one, emamectin, EMPC, empenthrin, endosulfan, endothion, 0013 Additionally, it is contemplated that any combina endrin, EPN, epolfenonane. eprinomectin, esfenvalerate, eta tion of the above insecticides can be employed in the compo phos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethop sitions described herein. For more information consult rophos, ethyl formate, ethyl-DDD, ethylene dibromide, eth COMPENDIUM OF PESTICIDE COMMON NAMES ylene dichloride, ethylene oxide, etofenprox, etrimfos, EXD, located at http://www.alanwood.net/pesticides/index.html. famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, Also consult “THE PESTICIDE MANUAL 14th Edition, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxy edited by CD S Tomlin, copyright 2006 by British Crop carb, fempirithrin, fempropathrin, fensulfothion, fenthion, Production Council. fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendia 0014 Various pesticides are susceptible to chemical and mide, flucofuron, flucycloxuron, flucythrinate, flufenerim, physical degradation in the presence of certain environmental flufenoxuron, flufenprox, fluvalinate, fonofos, formetanate, influences, such as heat and/or light. Pesticides that are Sus formothion, formparanate, foSmethilan, fospirate, fosthietan, ceptible to degradation with respect to the latter of these furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, influences are commonly referred to as “photo-labile.” With halfenprox, halofenozide, HCH, HEOD, heptachlor, hep respect to at least some photo-labile pesticides, it is believed tenophos, heterophos, hexaflumuron, HHDN, hydramethyl that their degradation can be attributed to a reaction with non, hydrogen cyanide, hydroprene, hyduincarb, imidaclo singlet oxygen. Examples of pesticides that are reactive with prid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, singlet oxygen include, but are not limited to, certain olefins, isobenzan, isocarbophos, isodrin, isofenphos, isoprocarb, aromatics, phenols, naphthols, furans, pyrans and other het isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I. erocycles containing oxygen; pyrroles, oxazoles, imidazoles, jasmolin II, jodfenphos, juvenile hormone I, juvenile hor indoles and other heterocycles containing nitrogen; aliphatic, mone II, juvenile hormone III, kelevan, kinoprene, lambda alicyclic and aromatic amines; amino acids, peptides and cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, proteins; and Sulfur containing compounds such as mercap lirimfos, lufenuron, lythidathion, malathion, malonoben, tans and Sulfides; and the like. Further details regarding the maZidox, mecarbam, mecarphon, menazon, mephosfolan, determination of whether a pesticide is reactive with singlet mercurous chloride, meSulfenfos, metaflumizone, methacri oxygen are provided in International Patent Publication No. fos, methamidophos, methidathion, methiocarb, methocroto WO 2007/053760. It should be appreciated that any one or phos, methomyl, methoprene, methoxychlor, methoxy combination of the aforementioned photo-labile, singlet oxy fenozide, methyl bromide, methylchloroform, methylene gen reactive pesticides could be included in the compositions chloride, metofluthrin, metolcarb, metoxadiaZone, described herein. mevinphos, mexacarbate, milbemectin, milbemycin oxime, 00.15 More particular examples of photo-labile, singlet mipafox, mirex, monocrotophos, morphothion, moxidectin, oxygen reactive pesticides that could be included either alone US 2010/0297260 A1 Nov. 25, 2010

or in combination with each other in the compositions and iodides. More particular examples of transition metal described herein include, but are not limited to, natural prod acetates include, but are not limited to, Zinc acetate, ferrous ucts which are microorganisms, microbial products, and (iron (II)) acetate, ferric (iron (III)) acetate, cobalt(II) acetate materials derived or extracted from plants, animals, or min and cupric (copper (II)) acetate. For transition metal acety eral-bearing rocks. These natural products include products lacetonates, more particular but non-limiting examples derived from naturally derived soil dwelling organisms such include cuprous (copper (I)) acetylacetonate, cupric (copper as actinomycete bacteria Such as, for example, macrocyclic (II)) acetylacetonate, nickel (II) acetylacetonate and Zinc lactone insecticides. One exemplary macrocyclic lactone acetylacetonate. More particular examples of transition metal insecticide includes avermectins and derivatives thereof. Such nitrates include, but are not-limited to, Zinc nitrate, cupric as abamectin, doramectin, emamectin, eprinomectin, iver (copper(II)) nitrate, manganese (II) nitrate, ferric (iron (III)) mectin and Selamectin. Another exemplary macrocyclic lac nitrate, cobalt(II) nitrate and nickel(II) nitrate. Non-limiting tone insecticide includes milbemycins and derivatives examples of transition metal Sulfates include Zinc sulfate, thereof. Such as lepimectin, milbemectin, milbemycin Oxime ferrous (iron(II)) sulfate, ferric (iron(III)) sulfate, manganese and moxidectin. Yet another exemplary macrocyclic lactone (II) sulfate, cobalt(II) sulfate, nickel(II) sulfate, and cupric insecticide includes spinosyns, such as spinosad, and deriva (copper (II)) sulfate. A few particular but non-limiting tives thereof Such as Synthetically produced spinetoram as examples of transition metal carbonates include Zinc carbon disclosed in U.S. Pat. Nos. 5,227,295; 5,670,364; 5,591,606: ate, manganese (II) carbonate, iron carbonate, nickel(II) car 6,001,981; 6,143,526; 6,455,504; 6,585,990; 6,919,464; bonate, cobalt(II) carbonate and cupric (copper(II)) carbon 5,362,634;5,539,089; and 5,202.242, each of which is hereby ate. More particular examples of transition metal fluorides incorporated herein by reference in its entirety. Other natural include, but are not limited to, cuprous (copper (I)) fluoride, products include Sabadilla or Veratrine, pyrethrum or pyre cupric (copper (II)) fluoride, Zinc fluoride, manganese (II) thrin, neem oil orazadirachtin, rotenone, ryania or ryanodine, fluoride, manganese (III) fluoride and ferric (iron (III)) fluo Bacillus thuringiensis (B. t.), Bacillus subtilis, pheromones, ride. Non-limiting examples of transition metal chlorides natural attractants and the like. Other pesticides that could be include Zinc chloride, cuprous (copper (I)) chloride, cupric included in the compositions described herein can include (copper (II)) chloride, manganese (II) chloride, nickel (II) synthetically produced pesticides which are reactive toward chloride, cobalt(II) chloride, ferrous (iron (II)) chloride and singlet oxygen. Examples include, but are not limited to ferric (iron (III)) chloride. With respect to transition metal indoxacarb, imazalil and fempropimorph. In addition to the bromides, a few examples include, but are not limited to, Zinc foregoing, it should be appreciated that the compositions bromide, cuprous (copper (I)) bromide, cupric (copper (II)) described herein could also include at least one pesticide bromide, cobalt (II) bromide, ferrous (iron (II)) bromide, which is reactive with singlet oxygen and at least one other ferric (iron(III)) bromide, manganese(II) bromide and nickel pesticide which is not reactive with singlet oxygen or other (II) bromide. A few more particular but non-limiting wise photo-labile. examples of transition metal iodides include manganese (II) 0016. In one embodiment, a composition includes at least iodide, nickel(II) iodide, cuprous (copper(I)) iodide and Zinc one or a mixture of the aforementioned pesticides, at least one iodide. Additionally, it is contemplated that any combination metal salt and at least one proteinaceous material. In this of the above transition metal salts can be employed in the embodiment, the composition exhibits enhanced pesticidal compositions described herein. activity compared to a composition dissimilar only in not 0018. In one or more embodiments, it is contemplated that having the metal salt and the proteinaceous material. For the at least one transition metal salt is water soluble. Non example, it is contemplated that the activity or half-life of the limiting examples of water-soluble transition metal salts composition is extended and therefore the same activity can include Zinc chloride, Zinc iodide, Zinc nitrate, Zinc bromide, be achieved with a lower amount of the composition when Zinc sulfate, Zinc acetate, cupric (copper(II)) chloride, cupric compared to a composition dissimilar only in not having the (copper II)) bromide, cuprous (copper (I)) bromide, cupric metal salt and the proteinaceous material. Additionally or (copper (II)) nitrate, cupric (copper (II)) acetate, nickel (II) alternatively, it is contemplated that improved pesticidal con nitrate, nickel (II) bromide, nickel (II) chloride, nickel (II) trol over time is achieved with the composition including the iodide, nickel (II) sulfate, cobalt(II) nitrate, cobalt(II) sul metal salt and the proteinaceous material when compared to a fate, cobalt(II) acetate, cobalt(II) bromide, cobalt(II) chlo composition dissimilar only in not having the metal salt and ride, ferrous (iron (II)) chloride, ferric (iron (III)) chloride, the proteinaceous material. ferrous (iron (II)) sulfate, ferric (iron (III)) sulfate, ferrous 0017. As used herein, the term “metal salt” refers to a (iron (II)) acetate, ferric (iron (III)) nitrate, ferrous (iron (II)) compound in which the hydrogen or hydrogens of an acid bromide, manganese (II) sulfate and manganese (II) chloride. is/are replaced by a metal while retaining the same organic or 0019. As used herein, the term “proteinaceous material' is inorganic moiety as the acid. By way of non-limiting used to describe a material, composition or compound that is example, organic or inorganic moieties that can form part of defined by a protein, includes at least one protein or is a basic a metal salt include acetate, acetylacetonate, nitrate, Sulfate, element of a protein. In one form, the proteinaceous material carbonate and halides, such as chloride, bromide, fluoride and is a water-soluble protein. Further non-limiting examples of iodide. In one or more than one of the more particular embodi proteinaceous materials include albumin, such as egg albu ments described in this document, the metal salt can be a men or bovine serum albumin (BSA); casein: gelatin: Zein; a transition metal salt. For the purposes of this document, Zinc whey composition, Such as a mixture of lactose and whey is considered to be a transition metal. Non-limiting examples protein; whey protein and amino acids such as cysteine, of transition metal salts include transition metal acetates, methionine, trytophan, histidine, and tyrosine. transition metal acetylacetonates, transition metal nitrates, 0020. The metal salt and proteinaceous material are typi transition metal Sulfates, transition metal carbonates and tran cally present within the compositions described in this docu sition metal halides, including chlorides, fluorides, bromides ment in an activity enhancing amount. An activity enhancing US 2010/0297260 A1 Nov. 25, 2010

amount is an amount which increases the half life of the material and from about 20% to about 50% by weight of the composition, or alternatively will enable the composition to metal salt. In still another embodiment, a composition achieve the same control of pests at a level which is less than includes from about 8% to about 15% by weight of the pes the amount required for the same pesticidal protection or ticide, from about 40% to about 60% by weight of the pro control of the composition in the absence of the metal salt and teinaceous material and from about 25% to about 40% by the proteinaceous material. In other words, the metal salt and weight of the metal salt. the proteinaceous material will either reduce the rate required 0024. Still, it should be appreciated that alternative values for protection or extend the residuality of the composition. for the weight percentages of the pesticide, proteinaceous 0021. In one embodiment, a composition includes a ratio, material and metal salt are contemplated. For example, in one by weight, between the metal salt and the pesticide between embodiment, it is contemplated that a composition may about 1:10 and about 20:1, between the proteinaceous mate include between about 0.1% and about 50% by weight of the rial and the pesticide between about 1:1 and about 20:1 and pesticide, between about 15% and about 90% by weight of the between the proteinaceous material and the metal salt proteinaceous material and between about 5% and about 80% between about 1:10 and about 20:1. In another embodiment, by weight of the metal salt. Still, in another embodiment, it is a composition includes a ratio, by weight, between the metal contemplated that a composition may include between about salt and the pesticide between about 1:2 and about 10:1, 0.1% and about 75% by weight of the pesticide, between between the proteinaceous material and the pesticide between about 5% and about 95% by weight of the proteinaceous about 2:1 and about 10:1 and between the proteinaceous material and between about 1% and about 90% by weight of material and the metal salt between about 1:5 and about 10:1. the metal salt. In yet another embodiment, a composition includes a ratio, by 0025. The compositions described above can be prepared weight, between the metal salt and the pesticide from about and provided in any suitable manner and also include other 1:1 to about 6:1, between the proteinaceous material and the components, further details of which will be provided below. pesticide from about 3:1 to about 8:1 and between the pro In one particular form, the pesticide, proteinaceous material, teinaceous material and the metal salt from about 1:2 to about metal salt, water and any other components, if present, are 4:1. In still another embodiment, a composition includes a mixed together, homogenized and provided as a liquid com ratio, by weight, between the metal salt and the pesticide from position. The liquid composition may then be spray dried to about 2:1 to about 4:1, between the proteinaceous material provide a solid composition which may be in a powder or gr and the pesticide from about 4:1 to about 6:1 and between the anular fonn, just to name a few possibilities. During the spray proteinaceous material and the metal salt from about 1:1 to drying, the liquid composition is at least partially dehydrated about 2:1. In yet another embodiment, a composition includes or dried, with Such dehydration or drying resulting in the a ratio, by weight, between the metal salt and the pesticide conversion of the liquid composition to the Solid composition between about 1:10 and about 20:1, between about 1:2 and which includes a smaller percentage by weight of water than about 10:1, from about 1:1 to about 6:1 or from about 2:1 to the liquid composition. In one or more forms, the spray drying about 4:1; between the proteinaceous material and the pesti will remove all or substantially all of the water from the liquid cide between about 1:1 and about 20:1, between about 2:1 and composition as it is converted to the Solid composition. How about 10:1, from about 3:1 to about 8:1 or from about 4:1 to ever, it should be appreciated that residual water may be about 6:1; and between the proteinaceous material and the present in one or more forms of the solid composition. metal salt between about 1:10 and about 20:1, between about 0026. For example, in one form, the solid composition 1:5 and about 10:1, from about 1:2 to about 4:1 or from about includes between about 0.001% to about 20% by weight of 1:1 to about 2:1. water after the spray drying. In yet another form, the Solid 0022. It should be appreciated however that alternative composition includes from about 0.001% to about 15% by values for the weight ratios between the metal salt and the weight of water after the spray drying. In still another fowl, pesticide, the proteinaceous material and the pesticide and the the solid composition includes from about 0.001% to about proteinaceous material and the metal salt are contemplated. 10% by weight of water after the spray drying. In another For example, in one embodiment, it is contemplated that a form, the solid composition includes from about 0.001% to composition may include a ratio, by weight, between the about 5% by weight of water after the spray drying. In yet metal salt and the pesticide between about 1:100 and about another form, the Solid composition includes from about 100:1, between the proteinaceous material and the pesticide 0.001% to about 4% by weight of water after the spray drying. between about 1:100 and about 100:1 and between the pro Still, in another form the solid composition includes from teinaceous material and the metal salt between about 1:100 about 0.001% to about 2% by weight of water after the spray and about 100:1. In another embodiment, it is contemplated drying. In another form, the Solid composition includes from that a composition may include a ratio, by weight, between about 0.001% to about 1% by weight of water after the spray the metal salt and the pesticide between about 1:50 and about drying. However, it should be appreciated that alternatives 50:1, between the proteinaceous material and the pesticide values for the weight percentage of water in the Solid com between about 1:50 and about 50:1 and between the proteina position after the spray drying are contemplated. ceous material and the metal salt between about 1:50 and 0027. Accordingly, in one embodiment, a method includes about 50:1. providing a liquid composition that includes at least one 0023. In still another embodiment, a composition includes pesticide, at least one proteinaceous material, at least one from about 1% to about 30% by weight of the pesticide, from metal salt and water, and spray drying the liquid composition about 25% to about 75% by weight of the proteinaceous to provide a solid composition. In one particular form of this material and from about 10% to about 60% by weight of the embodiment, the spray drying includes Substantially remov metal salt. In another embodiment, a composition includes ing all of the water from the liquid composition as it is con from about 5% to about 25% by weight of the pesticide, from verted to the solid composition. While not previously dis about 35% to about 65% by weight of the proteinaceous cussed, any other Volatile materials besides water, if present US 2010/0297260 A1 Nov. 25, 2010 in the liquid composition, will typically be entirely or sub Cryptolestes ferrugineus (rusty grain beetle), Cryptolestes stantially removed as the liquid composition is converted to pusillus (flat grain beetle), Cryptolestes turcicus (Turkish the solid composition during the spray drying. However, it is grain beetle), Ctenicera spp. (wireworms), Curculio spp. contemplated that residual volatile materials other than water (weevils), Cyclocephala spp. (grubs), Cylindrocpturus could be present in the Solid composition after the spray adspersus (Sunflower Stern weevil), Deporaus marginiatus drying. Additionally, the pesticide, proteinaceous material (mango leaf-cutting weevil), Dermestes lardarius (larder and metal salt are generally not volatile and will generally not beetle), Dermestes maculates (hide beetle), Diabrotica spp. be affected by the spray drying. Thus, it should be appreciated (chrysolemids), Epilachna varivestis (Mexican bean beetle), that the Solid composition after spray drying will include Faustinus tubae, Hylobius pales (pales weevil), Hypera spp. ratios by weight between the pesticide and the proteinaceous (weevils), Hypera postica (alfalfa weevil), Hyperdoes spp. material, the pesticide and the metal salt, and the metal salt (Hyperodes weevil), Hypothenemus hampei (coffee berry and proteinaceous material that are the same as or Substan beetle), Ips spp. (engravers), Lasioderma serricorne (ciga tially equivalent to the ratios by weight between these ingre rette beetle), Leptinotarsa decemlineata (Colorado potato dients in the liquid composition. beetle), Liogeny's fiscus, Liogenys suturalis, Lissorhoptrus Oryzophilus (rice water weevil), Lyctus spp. (wood beetles/ Pests powder post beetles), Maecolaspis joliveti, Megascelis spp., 0028. In one or more additional embodiments, the inven Melanotus communis, Melligethes spp., Melligethes aeneus tion disclosed in this document can be used to control pests. (blossom beetle), Melolontha melolontha (common Euro 0029. In one embodiment, the invention disclosed in this pean cockchafer), Oberea brevis, Oberea linearis, Oryctes document can be used to control pests of the Phylum Nema rhinoceros (date palm beetle), Oryzaephilus mercator (mer toda. chant grain beetle), Oryzaephilus Surinamensis (sawtoothed 0030. In another embodiment, the invention disclosed in grain beetle), Otiorhynchus spp. (weevils), Oulema melano this document can be used to control pests of the Phylum pus (cereal leaf beetle), Oulema myzae, Pantomorus spp. Arthropoda. (weevils), Phyllophaga spp. (May/June beetle), Phyllophaga 0031. In another embodiment, the invention disclosed in cuyabana, Phyllotreta spp. (chrysomelids), Phynchites spp., this document can be used to control pests of the Subphylum Popillia japonica (Japanese beetle), Prostephanus truncates Chelicerata. (larger grain borer), Rhizopertha dominica (lesser grain 0032. In another embodiment, the invention disclosed in borer), Rhizotrogus spp. (Eurpoean chafer), Rhynchophorus this document can be used to control pests of the Class Arach spp. (weevils), Scolytus spp. (wood beetles). Shenophorus nida. spp. (Billbug), Sitona lineatus (pea leaf weevil), Sitophilus 0033. In another embodiment, the invention disclosed in spp. (grain weevils), Sitophilus granaries (granary weevil), this document can be used to control pests of the Subphylum Sitophilus Oryzae (rice weevil), Stegobium paniceum (drug Myriapoda. store beetle), Tribolium spp. (flour beetles), Tribolium casta 0034. In another embodiment, the invention disclosed in neum (red flour beetle), Tribolium confilsum (confused flour this document can be used to control pests of the Class Sym beetle), Trogoderma variabile (warehouse beetle), and phyla. Zabrus tenebioides. 0035. In another embodiment, the invention disclosed in 0038. In another embodiment, the invention disclosed in this document can be used to control pests of the Subphylum this document can be used to control Dermaptera (earwigs). Hexapoda. 0039. In another embodiment, the invention disclosed in 0036. In another embodiment, the invention disclosed in this document can be used to control Dictyoptera (cock this document can be used to control pests of the Class roaches). A non-exhaustive list of these pests includes, but is Insecta. not limited to, Blattella germanica (German cockroach), 0037. In another embodiment, the invention disclosed in Blatta Orientalis (oriental cockroach), Parcoblatta pennyl this document can be used to control Coleoptera (beetles). A vanica, Periplaneta americana (American cockroach), non-exhaustive list of these pests includes, but is not limited Periplaneta australoasiae (Australian cockroach), Periplan to, Acanthoscelides spp. (weevils), Acanthoscelides Obtectus eta brunnea (brown cockroach), Periplaneta fuliginosa (common bean weevil), Agrilus planipennis (emerald ash (Smokybrown cockroach), PyncOselus suminamensis (Suri borer), Agriotes spp. (wireworms). Anoplophora glabripen nam cockroach), and Supella longipalpa (brownbanded nis (Asian longhorned beetle), Anthonomus spp. (weevils), cockroach). Anthonomus grandis (boll weevil), Aphidius spp., Apion spp. 0040. In another embodiment, the invention disclosed in (weevils), Apogonia spp. (grubs), Ataenius spretulus (Black this document can be used to control Diptera (true flies). A Turgrass Ataenius), Atomaria linearis (pygmy mangold non-exhaustive list of these pests includes, but is not limited beetle), Aulacophore spp., Bothy noderes punctiventris (beet to, Aedes spp. (mosquitoes), Agromyza frontella (alfalfa root weevil), Bruchus spp. (weevils), Bruchus pisorum (pea blotch leafminer), Agromyza spp. (leaf miner flies), Anas weevil), Cacoesia spp., Callosobruchus maculatus (Southern trepha spp. (fruit flies), Anastrepha suspensa (Caribbean fruit cowpea weevil), Carpophilus hemipteras (dried fruit beetle), fly). Anopheles spp. (mosquitoes), Batrocera spp. (fruit flies), Cassida vittata, Cerosterna spp., Cerotoma spp. (chry Bactrocera cucurbitae (melon fly), Bactrocera dorsalis (ori Someids), Cerotoma trifurcata (bean leaf beetle), Ceutorhyn ental fruit fly), Ceratitis spp. (fruit flies), Ceratitis capitata chus spp. (weevils), Ceutorhynchus assimilis (cabbage seed (Mediterranea fruit fly), Chrysops spp. (deer flies), pod weevil), Ceutorhynchus napi (cabbage curculio), Cochliomyia spp. (screwworms), Contarinia spp. (Gall Chaetocnema spp. (chrysomelids), Colaspis spp. (soil midges), Culex spp. (mosquitoes), Dasineura spp. (gall beetles), Conoderus scalaris, Conoderus stigmosus, midges), Dasineura brassicae (cabbage gall midge), Delia Conotrachelus menuphar (plum curculio), Cotinus initidis spp., Delia platura (seedcorn maggot), Drosophila spp. (vin (Green June beetle), Crioceris asparagi (asparagus beetle), egar flies), Fannia spp. (filth flies), Fannia canicularis (little US 2010/0297260 A1 Nov. 25, 2010 house fly), Fannia scalaris (latrine fly), Gasterophilus intes Planococcus spp. (mealybugs), Pseudococcus spp. (mealy tinalis (horse botfly), Gracillia perseae, Haematobia irritans bugs), Pseudococcus brevipes (pine apple mealybug), Ouad (horn fly), Hvlemyia spp. (root maggots), Hypoderma linea raspidiotus perniciosus (San Jose scale), Rhapalosiphun tum (common cattle grub), Liriomyza spp. (leafminer flies), spp. (aphids), Rhapalosiphum maida (corn leaf aphid), Liriomyza brassica (serpentine leafminer), Mellophagus Ovi Rhapalosiphum padi (oat bird-cherry aphid), Saissetia spp. nus (sheep ked), Musca spp. (muscid flies), Musca autumna (scales), Saissetia oleae (black scale), Schizaphis graminum lis (face fly), Musca domestica (house fly), Oestrus Ovis (greenbug), Sitobion avenae (English grain aphid), Sogatella (sheep bot fly), Oscinella frit (frit fly), Pegomyia betae (beet fircifera (white-backed planthopper). Therioaphis spp. leafminer), Phorbia spp., Psila rosae (carrotrust fly), Rhago (aphids), Toumeyella spp. (scales), Toxoptera spp. (aphids), letis cerasi (cherry fruit fly), Rhagoletis pomonella (apple Trialeurodes spp. (whiteflies), Trialeurodes vaporariorum maggot), Sitodiplosis mosellana (orange wheat blossom (greenhouse whitefly), Trialeurodes abutiloneus (banded midge), Stomoxys calcitrans (stable fly), Tabanus spp. (horse wing whitefly). Unaspis spp. (scales), Unaspis vanonensis flies), and Tipula spp. (crane flies). (arrowhead scale), and Zulia entreriana. 0041. In another embodiment, the invention disclosed in 0043. In another embodiment, the invention disclosed in this document can be used to control Hemiptera (true bugs). A this document can be used to control Hymenoptera (ants, non-exhaustive list of these pests includes, but is not limited wasps, and bees). A non-exhaustive list of these pests to. Acrosternum hilare (green Stink bug), Blissus leucopterus includes, but is not limited to, Acromyrrmex spp., Athalia (chinch bug), Calocoris norvegicus (potato mind), Cimex rosae, Atta spp. (leafcutting ants), Camponotus spp. (carpen hemipterus (tropical bedbug), Cimex lectularius (bed bug), ter ants), Diprion spp. (sawflies). Formica spp. (ants), Iri Dagbertus fasciatus, Dichelops furcatus, Dysdercus suturel domyrmex humilis (Argentine ant), Monomorium ssp., Mono lus (cotton stainer), Edessa meditabunda, Eurygaster maura morium minumum (little black ant), Monomorium pharaonis (cereal bug), Euschistus heros, Euschistus servus (brown (Pharaoh ant), Neodiprion spp. (sawflies), Pogonomyrmex Stink bug), Helopeltis antonii, Helopeltis theivora (tea blight spp. (harvester ants), Polistes spp. (paper wasps), Solenopsis plantbug), Lagynotomus spp. (Stink bugs), Leptocorisa Ora spp. (fire ants), Tapoinoma sessile (odorous house ant), Tet torius, Leptocorisa varicornis, Lygus spp. (plant bugs), Lygus ranomorium spp. (pavementants), Vespula spp. (yellowjack hesperus (western tarnished plant bug), Maconellicoccus hir ets), and Xvlocopa spp. (carpenter bees). sutus, Neurocolpus longirostris, Nezara viridula (Southern 0044. In another embodiment, the invention disclosed in green Stink bug), Phytocoris spp. (plant bugs), Phytocoris this document can be used to control Isoptera (termites). A Californicus, Phytocoris relativus, Piezodorus guildingi, non-exhaustive list of these pests includes, but is not limited Poecilocapsus lineatus (fourlined plant bug), Psallus vaccini to, Coptotermes spp., Coptotermes curvignathus, Coptoter cola, Pseudacy.sta perseae, Scaptocoris Castanea, and Tri mes frenchii, Coptotermes formosanus (Formosan Subterra atoma spp. (bloodsucking conenose bugs/kissing bugs). nean termite), Cornitermes spp. (nasute termites), Cryptoter 0042. In another embodiment, the invention disclosed in mes spp. (drywood termites), Heterotermes spp. (desert this document can be used to control Homoptera (aphids, Subterranean termites), Heterotermes aureus, Kalotermes scales, whiteflies, leafhoppers). A non-exhaustive list of these spp. (drywood termites). Incistitermes spp. (drywood ter pests includes, but is not limited to, Acrythosiphon pisum (pea mites), Macrotermes spp. (fungus growing termites), Mar aphid), Adelges spp. (adelgids), Aleurodes proletella (cab ginitermes spp. (drywood termites), Microcerotermes spp. bage whitefly), Aleurodicus disperses, Aleurothrixus flocco (harvester termites), Microtermes obesi, Procornitermes sus (woolly whitefly), Aluacaspis spp., Amrasca biguitella spp., Reticulitermes spp. (Subterranean termites), Reticuliter biguitella, Aphrophora spp. (leafhoppers), Aonidiella aurantii mes banyulensis, Reticulitermes grassei, Reticulitermes (California red scale), Aphis spp. (aphids), Aphis gossypii ilavipes (eastern Subterranean termite), Reticulitermes (cotton aphid), Aphis pomi (apple aphid), Aulacorthum Solani hageni, Reticulitermes hesperus (western Subterranean ter (foxglove aphid), Bemisia spp. (whiteflies), Bemisia argenti mite), Reticulitermes Santonensis, Reticulitermes speratus, folii, Bemisia tabaci (sweetpotato whitefly), Brachycolus Reticulitermes tibialis, Reticulitermes virginicus, Schedorhi noxius (Russian aphid), Brachycorynella asparagi (aspara notermes spp., and Zootermopsis spp. (rotten-wood termites). gus aphid), Brevennia rehi, Brevicoryne brassicae (cabbage 0045. In another embodiment, the invention disclosed in aphid), Ceroplastes spp. (scales), Ceroplastes rubens (red this document can be used to control Lepidoptera (moths and wax scale), Chionaspis spp. (scales), Chrysomphalus spp. butterflies). A non-exhaustive list of these pests includes, but (scales), Coccus spp. (scales), Dysaphis plantaginea (rosy is not limited to, Achoea Janata, Adoxophyes spp., Adoxo apple aphid), Empoasca spp. (leafhoppers), Eriosoma lani phyes Orana, Agrotis spp. (cutworms), Agratis ipsilon (black gerum (woolly apple aphid), Icerva purchasi (cottony cush cutworm), Alabama argillacea (cotton leafworm), Amorbia ion scale), Idioscopus initidulus (mango leafhopper), Laodel cunearta, Amyelosis transitella (navel orangeworm), Ana phax striatellus (Smaller brown planthopper), Lepidosaphes camptodes defectaria, Anarsia lineatella (peach twig borer), spp., Macrosiphum spp., Macrosiphum euphorbiae (potato Anomis Sabulijera (jute looper), Anticarsia gemmatalis (vel aphid), Macrosiphum granarium (English grain aphid), Mac vetbean caterpillar), Archips argyrospila (fruit tree leafrol rosiphum rosae (rose aphid), Macrosteles quadrilineatus (as ler), Archips rosana (rose leafroller), Argyrotaenia spp. (tor ter leafhopper), Mahanarva fimbiolata, Metopolophium tricid moths), Argyrotaenia citrana (orange tortrix), dirhodun (rose grain aphid), Micas longicornis, Myzus per Autographa gamma, Bonagota Cranaodes, Borbo cinnara sicae (green peach aphid), Nephotettix spp. (leafhoppers), (rice leaf folder), Bucculatrix thurberiella (cotton leaf perfo Nephotettix cinctipes (green leafhopper), Nilaparvata lugens rator), Caloptilia spp. (leaf miners), Capua reticulana, Car (brown planthopper), Parlatoria pergandii (chaff scale), Par posina niponensis (peach fruit moth), Chilo spp., Chlumetia latoria Ziziphi (ebony scale), Peregrinus maidis (corn delpha transversa (mango shoot borer), Choristoneura rosaceana cid), Philaenus spp. (spittlebugs), Phylloxera vitifoliae (oblique banded leaf roller), Chrysodeixis spp., Cnaphalo (grape phylloxera), Physokermes piceae (spruce bud scale), cerus medinalis (grass leafroller), Colias spp., Compomorpha US 2010/0297260 A1 Nov. 25, 2010

cramerella, Cossus eOssus (carpenter moth), Crambus spp. 0047. In another embodiment, the invention disclosed in (Sod webworms), Cydia funebrana (plum fruit moth), Cydia this document can be used to control Orthoptera (grasshop molesta (oriental fruit moth), Cydia nignicana (pea moth), pers, locusts, and crickets). A non-exhaustive list of these Cydia pomonella (codling moth), Darna diducta, Diaphania pests includes, but is not limited to, Anabrus simplex (Mor spp. (stem borers), Diatraea spp. (stalk borers), Diatraea mon cricket), Gryllotalpidae (mole crickets), Locusta migra saccharalis (Sugarcane borer), Diatraea graniosella (South toria, Melanoplus spp. (grasshoppers), Microcentrum ret wester corn borer), Earias spp. (bollworms), Earias insulata inerve (angular winged katydid), Pterophylla spp. (kaydids), (Egyptian bollworm), Earias vitella (rough northern boll chistocerca gregaria, Scudderia fitreata (fork tailed bush worm), Ecdytopopha aurantianum, Elasmopalpus lignosel katydid), and Valanga nigricorni. lus (lesser cornstalk borer), Epiphysia's postruttana (light 0048. In another embodiment, the invention disclosed in brown apple moth), Ephestia spp. (flour moths), Ephestia this document can be used to control Phthiraptera (Sucking cautella (almond moth), Ephestia elutella (tobbaco moth), lice). A non-exhaustive list of these pests includes, but is not Ephestia kuehniella (Mediterranean flour moth), Epimeces limited to, Haematopinus spp. (cattle and hog lice), Linog spp., Epinotia aporema, Erionota thrax (banana skipper), nathus Ovillus (sheep louse), Pediculus humanus capitis (hu Eupoecilia ambiguella (grape berry moth), Euxoa auxiliaris man body louse), Pediculus humanus humanus (human body (army cutworm), Feltia spp. (cutworms), Gortyna spp. (stem lice), and Pthirus pubis (crab louse). borers), Grapholita molesta (oriental fruit moth), Hedylepta 0049. In another embodiment, the invention disclosed in indicata (bean leaf webber), Helicoverpa spp. (noctuid this document can be used to control Siphonaptera (fleas). A moths), Helicoverpa armigera (cotton bollworm), Helicov non-exhaustive list of these pests includes, but is not limited erpa zea (bollworm./corn earworm), Heliothis spp. (noctuid to, Ctenocephalides canis (dog flea), Ctenocephalides felis moths), Heliothis virescens (tobacco budworm), Hellula (cat flea), and Pulex irritans (human flea). undalis (cabbage webworm), Indarbela spp. (root borers), 0050. In another embodiment, the invention disclosed in Keiferia lycopersicella (tomato pinworm), Leucinodes this document can be used to control Thysanoptera (thrips). A Orbonalis (eggplant fruit borer), Leucoptera malifoliella, non-exhaustive list of these pests includes, but is not limited Lithocollectis spp., Lobesia botrana (grapefruit moth), Loxia to, Frankliniella fisca (tobacco thrips), Frankliniella occi grotis spp. (noctuid moths), Loxagrotis albicosta (western dentalis (western flower thrips), Frankliniella Shultzei Fran bean cutworm), Lymantria dispar (gypsy moth), Lyonetia Kliniella williamsi (corn thrips), Heliothrips haemorrhaidalis clerkella (apple leaf miner), Mahasena corbetti (oil palm (greenhouse thrips), Riphiphorothrips cruentatus, Scirto bagworm), Malacosoma spp. (tent caterpillars), Mamestra thrips spp., Scirtothrips citri (citrus thrips), Scirtothrips dor brassicae (cabbage armyworm), Maruca testulalis (bean pod salis (yellow tea thrips), Taeniothrips rhopalantennalis, and borer), Metisa plana (bagworm), Mythinna unipuncta (true Thrips spp. armyworm), Neoleucinodes elegantalis (Small tomato borer), 0051. In another embodiment, the invention disclosed in Nymphula depunctalis (rice caseworm), Operophthera bru this document can be used to control Thysanura (bristletails). mata (winter moth), Ostrinia nubilalis (European corn A non-exhaustive list of these pests includes, but is not lim borer), Oxydia vesulia, Pandemis cerasana (common currant ited to, Lepisma spp. (silverfish) and Thermobia spp. (fir tortrix), Pandemis heparana (brown apple tortrix), Papilio ebrats). demodocus, Pectinophora gossypiella (pink bollworm), 0052. In another embodiment, the invention disclosed in Peridroma spp. (cutworms), Peridroma saucia (variegated this document can be used to control Acarina (mites and cutworm), Perileucoptera coffeella (white coffee leafminer), ticks). A non-exhaustive list of these pests includes, but is not Phthorimaea operculella (potato tuber moth), Phyllocnisitis limited to, Acarapsis woodi (tracheal mite of honeybees), citrella, Phyllonorycter spp. (leafminers), Pieris rapae (im Acarus spp. (food mites), Acarus siro (grain mite), Aceria ported cabbageworm), Plathypena scabra, Plodia interpunc mangiferae (mango bud mite), Aculops spp., Aculops lyco tella (Indian meal moth), Plutella xylostella (diamondback persici (tomato russet mite), Aculops pelekasi, Aculus pelle moth), Polychrosis viteana (grape berry moth), Prays kassi, Aculus Schlechtendali (apple rust mite), Amblyomma endocarpa, Prays oleae (olive moth), Pseudaletia spp. (noc americanum (lone startick), Boophilus spp. (ticks), Brevipal tuid moths), Pseudaletia unipunctata (armyworm), pus Obovatus (privet mite), Brevipalpus phoenicis (red and Pseudoplusia includens (soybean looper), Rachiplusia nu, black flat mite), Demodex spp. (mange mites), Dermacentor Scirpophaga incertulas, Sesamia spp. (stemborers), Sesamia spp. (hard ticks), Dermacentor variabilis (american dog inferens (pink rice Stein borer), Sesamia nonagrioides, Setora tick), Dermatophagoides pteronyssinus (house dust mite), nitens, Sitotroga cerealella (Angoumois grain moth), Spar Eotetranycus spp., Eotetranychus carpini (yellow spider ganothis pilleriana, Spodoptera spp. (armyworms), mite), Epitimerus spp., Eriophyes spp., Ixodes spp. (ticks), Spodoptera exigua (beet armyworm), Spodoptera fugiperda Metatetranycus spp., Notoedres cati, Oligonychus spp., Oli (fall armyworm), Spodoptera oridania (Southern army gonychus coffee, Oligonychus ilicus (Southern red mite), worm), Synanthedon spp. (root borers). Theela basilides, Panonychus spp., Panonychus citri (citrus red mite), Panony Thermisia gemmatalis, Tineola bisselliella (webbing clothes chus ulmi (European red mite), Phylocoptruta oleivora (cit moth), Trichoplusia ni (cabbage looper), Tuta absoluta, rus rust mite), Polyphagotarisonemun latus (broad mite), Rhi Yponomeuta spp., Zeuzera coffeae (red branch borer), and picephalus sanguineus (brown dog tick), Rhizoglyphus spp. Zeuzera pyrina (leopard moth). (bulb mites), Sarcoptes scabiei (itch mite), Tegolophus per 0046. In another embodiment, the invention disclosed in seaflorae, Tetranychus spp., Tetranychus urticae (twospotted this document can be used to control Mallophaga (chewing spider mite), and Varroa destructor (honeybee mite). lice). A non-exhaustive list of these pests includes, but is not 0053. In another embodiment, the invention disclosed in limited to, Bovicola Ovis (sheep biting louse), Menacanthus this document can be used to control Nematoda (nematodes). stramineus (chicken body louse), and Menopon gallinea A non-exhaustive list of these pests includes, but is not lim (common hen house). ited to, Aphelenchoides spp. (bud and leaf & pine wood nema US 2010/0297260 A1 Nov. 25, 2010

todes), Belonolaimus spp. (sting nematodes), Criconemella alkylbenzenesulfonates, alkyl Sulfates, and nonionic Surfac spp. (ring nematodes), Dirofilaria immitis (dog heartworm), tants such as ethylene oxide adducts of alkyl phenols. Dity lenchus spp. (stem and bulb nematodes), Heterodera spp. 0060 Emulsifiable concentrates comprise a convenient (cyst nematodes), Heterodera zeae (corn cyst nematode), concentration of a pesticide composition dissolved in a car Hirschmanniella spp. (root nematodes), Hoplolaimus spp. rier that is either a water miscible solvent or a mixture of (lance nematodes), Meloidogyne spp. (root knot nematodes), water-immiscible organic solvent and emulsifiers. Useful Meloidogyne incognita (root knot nematode). Onchocerca organic solvents include aromatics, especially Xylenes and volvulus (hook-tail worm), Pratylenchus spp. (lesion nema petroleum fractions, especially the high-boiling naphthalenic todes), Radopholus spp. (burrowing nematodes), and Roty and olefinic portions of petroleum Such as heavy aromatic lenchus reniformis (kidney-shaped nematode). naphtha. Other organic solvents may also be used, such as the 0054. In another embodiment, the invention disclosed in terpenic solvents including rosin derivatives, aliphatic this document can be used to control Symphyla (symphy ketones such as cyclohexanone, and complex alcohols such as lans). A non-exhaustive list of these pests includes, but is not 2-ethoxyethanol. Suitable emulsifiers for emulsifiable con limited to, Scutigerella immaculata. centrates are chosen from conventional anionic and nonionic 0055 For more detailed information consult “HAND Surfactants. BOOK OF PEST CONTROL THE BEHAVIOR, LIFE 0061 Aqueous Suspensions comprise Suspensions of HISTORY AND CONTROL OF HOUSEHOLDPESTS” by water-insoluble pesticide compositions dispersed in an aque Arnold Mallis, 9th Edition, copyright 2004 by GIE Media ous carrier. Suspensions are prepared by finely grinding the Inc. pesticide composition and vigorously mixing it into a carrier comprised of water and Surfactants. Ingredients, such as inor Mixtures ganic salts and synthetic or natural gums, may also be added, to increase the density and viscosity of the aqueous carrier. It 0056. The compositions disclosed in this document can is often most effective to grind and mix the pesticide compo also be used, for reasons of economy, chemical and physical sition at the same time by preparing the aqueous mixture and stability, and synergy, with acaricides, algicides, antifeedants, homogenizing it in an implement such as a sand mill, ball avicides, bactericides, bird repellents, chemosterilants, fun mill, or piston-type homogenizer. gicides, herbicide Safeners, herbicides, insect attractants, 0062 Pesticide compositions may also be applied as insect repellents, mammal repellents, mating disrupters, mol granular formulations that are particularly useful for applica luscicides, other insecticides, other pesticides, plant activa tions to the soil. Granular formulations contain the pesticide tors, plant growth regulators, rodenticides, synergists, defo composition dispersed in a carrier that comprises clay or a liants, desiccants, disinfectants, semiochemicals, and similar Substance. Such formulations are usually prepared by Virucides (these categories not necessarily mutually exclu dissolving the pesticide composition in a suitable solvent and sive). applying it to a granular carrier which has been pre-formed to the appropriate particle size, in the range of from about 0.5 to Formulations 3 mm. Such formulations may also be formulated by making 0057 The compositions described in this document may a dough or paste of the carrier and pesticide composition and also be provided with phytologically-acceptable inert ingre crushing and drying to obtain the desired granular particle dients to provide or complement a carrier and can be formu size. lated into, for example, baits, concentrated emulsions, dusts, 0063 Dusts containing a pesticide composition are pre emulsifiable concentrates, fumigants, gels, granules, pared by intimately mixing the pesticide composition in pow microencapsulations, seed treatments, Suspension concen dered form with a suitable dusty agricultural carrier, such as trates, Suspoemulsions, tablets, water soluble liquids, water kaolin clay, ground Volcanic rock, and the like. Dusts can be dispersible granules or dry flowables, wettable powders, and applied as a seed dressing, or as a foliage application with a ultra low volume solutions. dust blower machine. 0058 For further information on formulation types see 0064. It is equally practical to apply a pesticide composi CATALOGUE OF PESTICIDE FORMULATION TYPES tion in the form of a solution in an appropriate organic Sol AND INTERNATIONAL CODING SYSTEM Technical vent, usually petroleum oil. Such as the spray oils, which are Monograph n2, 5th Edition by CropLife International widely used in agricultural chemistry. (2002). 0065 Pesticide compositions can also be applied in the 0059 Pesticide compositions can be frequently applied as form of an aerosol formulation. In Such formulations, the aqueous Suspensions or emulsions prepared from concen pesticide composition is dissolved or dispersed in a carrier, trated formulations of Such compositions. Such water which is a pressure-generating propellant mixture. The aero soluble, water-suspendable, or emulsifiable formulations are Sol formulation is packaged in a container from which the either solids, usually known as wettable powders, or water mixture is dispensed through an atomizing valve. dispersible granules, or liquids usually known as emulsifiable 0.066 Pesticide baits are formed when the pesticide com concentrates, or aqueous Suspensions. Wettable powders, position is mixed with food oran attractant or both. When the which may be compacted to form water dispersible granules, pests eat the bait they also consume the pesticide composi comprise an intimate mixture of the pesticide composition, a tion. Baits may take the form of granules, gels, flowable carrier, and Surfactants. The carrier is usually chosen from powders, liquids, or Solids. They may be used in or around among the attapulgite clays, the montmorillonite clays, the pest harborages. diatomaceous earths, or the purified silicates. Effective sur 0067 Fumigants are pesticides that have a relatively high factants, which can comprise from about 0.5% to about 10% vapor pressure and hence can exist as a gas in Sufficient of the wettable powder, are found among Sulfonated lignins, concentrations to kill pests in Soil or enclosed spaces. The condensed naphthalenesulfonates, naphthalenesulfonates, toxicity of the fumigant is proportional to its concentration US 2010/0297260 A1 Nov. 25, 2010 and the exposure time. They are characterized by a good 0074. A dispersing agent is a substance which adsorbs capacity for diffusion and act by penetrating the pest's respi onto the surface of particles and helps to preserve the state of ratory system or being absorbed through the pest's cuticle. dispersion of the particles and prevents them from reaggre Fumigants are applied to control stored product pests under gating. Dispersing agents are added to agrochemical formu gas proofsheets, in gas sealed rooms or buildings or in special lations to facilitate dispersion and Suspension during manu chambers. facture, and to ensure the particles redisperse into water in a 0068. Oil solution concentrates are made by dissolving a spray tank. They are widely used in wettable powders, Sus pesticide composition in a solvent that will hold the pesticide pension concentrates and water-dispersible granules. Surfac composition in solution. Oil Solutions of a pesticide compo tants that are used as dispersing agents have the ability to sition usually provide faster knockdown and kill of pests than adsorb strongly onto a particle Surface and provide a charged other formulations due to the solvents themselves having or steric barrier to reaggregation of particles. The most com pesticidal action and the dissolution of the waxy covering of monly used surfactants are anionic, non-ionic, or mixtures of the integument increasing the speed of uptake of the pesti the two types. For wettable powder formulations, the most cide. Other advantages of oil solutions include better storage common dispersing agents are sodium lignoSulphonates. For stability, better penetration of crevices, and better adhesion to Suspension concentrates, very good adsorption and stabiliza greasy Surfaces. tion are obtained using polyelectrolytes, such as Sodium 0069. Another embodiment is an oil-in-water emulsion, naphthalene Sulphonate formaldehyde condensates. wherein the emulsion comprises oily globules which are each Tristyrylphenol ethoxylate phosphate esters are also used. provided with a lamellar liquid crystal coating and are dis Non-ionics such as alkylarylethylene oxide condensates and persed in an aqueous phase, wherein each oily globule com EO-PO block copolymers are sometimes combined with prises at least one compound which is agriculturally active, anionics as dispersing agents for Suspension concentrates. In and is individually coated with a monolamellar or oligola recent years, new types of very high molecular weight poly mellar layer comprising: (1) at least one non-ionic lipophilic meric Surfactants have been developed as dispersing agents. Surface-active agent, (2) at least one non-ionic hydrophilic These have very long hydrophobic backbones and a large Surface-active agent and (3) at least one ionic Surface-active number of ethylene oxide chains forming the teeth of a agent, wherein the globules having a mean particle diameter comb surfactant. These high molecular weight polymers of less than 800 nanometers. Further information on the can give very good long-term stability to Suspension concen embodiment is disclosed in U.S. patent publication trates because the hydrophobic backbones have many anchor 20070027034 published Feb. 1, 2007, having patent applica ing points onto the particle Surfaces. Examples of dispersing tion Ser. No. 1 1/495,228. For ease of use this embodiment agents used in agrochemical formulations are: Sodium ligno will be referred to as “OIWE. Sulphonates; Sodium naphthalene Sulphonate formaldehyde 0070 For further information consult “INSECT PEST condensates; tristyrylphenol ethoxylate phosphate esters; ali MANAGEMENT 2nd Edition by D. Dent, copyright CAB phatic alcohol ethoxylates; alky ethoxylates; EO-PO block International (2000). Additionally, for more detailed informa copolymers; and graft copolymers. tion consult “HANDBOOK OF PEST CONTROL THE 0075 An emulsifying agent is a substance which stabi BEHAVIOR, LIFE HISTORY AND CONTROL OF lizes a Suspension of droplets of one liquid phase in another HOUSEHOLD PESTS” by Arnold Mallis, 9th liquid phase. Without the emulsifying agent the two liquids (0071 Edition, copyright 2004 by GIE. Media Inc. would separate into two immiscible liquid phases. The most commonly used emulsifier blends contain alkylphenol or ali Other Formulation Components phatic alcohol with 12 or more ethylene oxide units and the 0072 Generally, when the compositions disclosed in this oil-soluble calcium salt of dodecylbenzene sulphonic acid. A document are used in a formulation, such formulation can range of hydrophile-lipophile balance (“HLB) values from 8 also contain other components. These components include, to 18 will normally provide good stable emulsions. Emulsion but are not limited to, (this is a non-exhaustive and non stability can sometimes be improved by the addition of a mutually exclusive list) wetters, spreaders, Stickers, pen small amount of an. EO-PO block copolymer surfactant. etrants, buffers, sequestering agents, drift reduction agents, 0076 A solubilizing agent is a surfactant which will form compatibility agents, anti-foam agents, cleaning agents, rhe micelles in water at concentrations above the critical micelle ology agents, stabilizers, dispersing agents and emulsifiers. A concentration. The micelles are then able to dissolve or solu few components are described forthwith. bilize water-insoluble materials inside the hydrophobic part 0073. A wetting agent is a substance that when added to a of the micelle. The types of surfactants usually used for solu liquid increases the spreading or penetration power of the bilization are non-ionics: Sorbitan monooleates; Sorbitan liquid by reducing the interfacial tension between the liquid monooleate ethoxylates; and methyl oleate esters. and the Surface on which it is spreading. Wetting agents are 0077 Surfactants are sometimes used, either alone or with used for two main functions in agrochemical formulations: other additives Such as mineral or vegetable oils as adjuvants during processing and manufacture to increase the rate of to spray-tank mixes to improve the biological performance of wetting of powders in water to make concentrates for soluble the pesticide on the target. The types of Surfactants used for liquids or Suspension concentrates; and during mixing of a bioenhancement depend generally on the nature and mode of product with water in a spray tank to reduce the wetting time action of the pesticide. However, they are often non-ionics of wettable powders and to improve the penetration of water Such as: alky ethoxylates; linear aliphatic alcohol ethoxy into water-dispersible granules. Examples of wetting agents lates; aliphatic amine ethoxylates. used in wettable powder, Suspension concentrate, and water 0078 Organic solvents are used mainly in the formulation dispersible granule formulations are: sodium lauryl Sulphate: of emulsifiable concentrates, ULV formulations, and to a Sodium dioctyl Sulphosuccinate; alkyl phenol ethoxylates; lesser extent granular formulations. Sometimes mixtures of and aliphatic alcohol ethoxylates. Solvents are used. The first main groups of solvents are ali US 2010/0297260 A1 Nov. 25, 2010 phatic paraffinic oils such as kerosene or refined paraffins. I0084. The locus to which a pesticide composition is The second main group and the most common comprises the applied can be any locus inhabited by a pest, for example, aromatic solvents such as Xylene and higher molecular Vegetable crops, fruit and nut trees, grape vines, ornamental weight fractions of C9 and C10 aromatic solvents. Chlori plants, domesticated animals, the interior or exterior Surfaces nated hydrocarbons are useful as cosolvents to prevent crys of buildings, and the Soil around buildings. Controlling pests tallization of pesticides when the formulation is emulsified generally means that pest populations, activity, or both, are into water. Alcohols are sometimes used as cosolvents to reduced in a locus. This can come about when: pest popula increase solvent power. tions are repulsed from a locus; when pests are incapacitated 0079. Thickeners or gelling agents are used mainly in the in or around a locus; or pests are exterminated, in whole or in formulation of Suspension concentrates, emulsions and Sus part, in or around a locus. Of course a combination of these poemulsions to modify the rheology or flow properties of the results can occur. Generally, pest populations, activity, or liquid and to prevent separation and settling of the dispersed both are desirably reduced more than fifty percent, preferably particles or droplets. Thickening, gelling, and anti-settling more than 90 percent. agents generally fall into two categories, namely water-in I0085 Generally, with baits, the baits are placed in the soluble particulates and water-soluble polymers. It is possible ground where, for example, termites can come into contact to produce Suspension concentrate formulations using clays with the bait. Baits can also be applied to a surface of a and silicas. Examples of these types of materials, include, but building, (horizontal, Vertical, or Slanted, Surface) where, for are limited to, montmorillonite, e.g. bentonite; magnesium example, ants, termites, cockroaches, and flies, can come into aluminum silicate; and attapulgite. Water-soluble polysac contact with the bait. charides have been used as thickening-gelling agents for I0086. Because of the unique ability of the eggs of some many years. The types of polysaccharides most commonly pests to resist pesticide compositions repeated applications used are natural extracts of seeds and seaweeds are synthetic derivatives of cellulose. Examples of these types of materials may be desirable to control newly emerged larvae. include, but are not limited to, guar gum, locust bean gum, I0087 Systemic movement of pesticides in plants may be carrageenam; alginates; methyl cellulose; sodium carboxym utilized to control pests on one portion of the plant by apply ethyl cellulose (SCMC); hydroxyethyl cellulose (HEC). ing the pesticide composition to a different portion of the Other types of anti-settling agents are based on modified plant. For example, control of foliar-feeding insects can be starches, polyacrylates, polyvinyl alcohol and polyethylene controlled by drip irrigation or furrow application, or by oxide. Another good anti-settling agent is xanthan gum. treating the seed before planting. Seed treatment can be 0080 Microorganisms cause spoilage of formulated prod applied to all types of seeds, including those from which ucts. Therefore preservation agents are used to eliminate or plants genetically transformed to express specialized traits reduce their effect. Examples of such agents include, but are will germinate. Representative examples include those not limited to: propionic acid and its sodium salt; Sorbic acid expressing proteins toxic to invertebrate pests, such as Bacil and its sodium or potassium salts; benzoic acid and its sodium lus thuringiensis or other insecticidal toxins, those expressing salt; p-hydroxybenzoic acid sodium salt; methyl p-hydroxy herbicide resistance, such as “Roundup Ready’ seed, or those benzoate; and 1,2-benzisothiazalin-3-one (BIT). with 'stacked foreign genes expressing insecticidal toxins, 0081. The presence of surfactants, which lower interfacial herbicide resistance, nutrition-enhancement or any other ben tension, often causes water-based formulations to foam dur eficial traits. Furthermore, such seed treatments with the ing mixing operations in production and in application invention disclosed in this document can further enhance the through a spray tank. In order to reduce the tendency to foam, ability of a plant to better withstand stressful growing condi anti-foam agents are often added either during the production tions. This results in a healthier, more vigorous plant, which stage or before filling into bottles. Generally, there are two can lead to higher yields at harvest time. types of anti-foam agents, namely silicones and non-sili I0088. It should be readily apparent that the invention can cones. Silicones are usually aqueous emulsions of dimethyl be used with plants genetically transformed to express spe polysiloxane while the non-silicone anti-foam agents are cialized traits, such as Bacillus thuringiensis or other insec water-insoluble oils, such as octanol and nonanol, or silica. In ticidal toxins, or those expressing herbicide resistance, or both eases, the function of the anti-foam agent is to displace those with 'stacked' foreign genes expressing insecticidal the surfactant from the air-water interface. toxins, herbicide resistance, nutrition-enhancement or any 0082 For further information see “CHEMISTRY AND other beneficial traits. TECHNOLOGY OF AGROCHEMICAL FORMULA 0089. The invention disclosed in this document is suitable TIONS' edited by D. A. Knowles, copyright 1998 by Kluwer for controlling endoparasites and ectoparasites in the Veteri Academic Publishers. Also see 'INSECTICIDES IN AGRI nary medicine sector or in the field of animal keeping. CULTURE AND ENVIRONMENT RETROSPECTS 0090 Compositions are applied in a known manner, such AND PROSPECTS’ by A. S. Perry, I. Yamamoto, I. Ishaaya, as by oral administration in the form of for example, tablets, and R. Perry, copyright 1998 by Springer-Verlag. capsules, drinks, granules, by dermal application in the form of for example, dipping, spraying, pouring on, spotting on, Applications and dusting, and by parenteral administration in the form of for example, an injection. 0083. The actual amount of a pesticide composition to be 0091. The invention disclosed in this document can also be applied to loci of pests is generally not critical and can readily employed advantageously in livestock keeping, for example, be determined by those skilled in the art. In general, concen cattle, sheep, pigs, chickens, and geese. Suitable formulations trations from about 0.01 grams of pesticide per hectare to are administered orally to the animals with the drinking water about 5000 grams of pesticide per hectare are expected to or feed. The dosages and formulations that are suitable provide good control. depend on the species. US 2010/0297260 A1 Nov. 25, 2010

0092. Before a pesticide composition can be used or sold 01.00 Isocratic elution: 20% A/80% B commercially, such composition undergoes lengthy evalua 01.01 Flow: 1.0 mL/minute tion processes by various governmental authorities (local, 0102 Injection volume: 10.0 LL regional, state, national, international). Voluminous data (0103) Detector: UV (a 250 nm. requirements are specified by regulatory authorities and must 01.04 Run Time: 20 minutes be addressed through data generation and Submission by the 0105 Integrator: Agilent EZChrom Elite data acquisi product registrant or by another on the product registrant's tion system, or equivalent behalf. These governmental authorities then review such data Based on the results of the liquid chromatography, the weight and if a determination of safety is concluded, provide the percentage of the pure spinetoram component of each of the potential user or seller with product registration approval. spinetoram products used in Examples A-D was calculated. Thereafter, in that locality where the product registration is The weight percentage of impurities was then calculated by granted and Supported. Such user or seller may use or sell Such Subtracting the weight percentage of the pure spinetoram pesticide. component from 100. The weight percentage of spinetoram impurities in each of Examples A-D, based from these calcu Examples lations, is provided below. 0093. The following examples are for illustration pur Example A poses and are not to be construed as limiting the invention disclosed in this document to only the embodiments disclosed 0106 A liquid composition including spinetoram, egg in these examples. albumen and Zinc acetate, among other ingredients, was pre pared according to the following. Spinetoram, Reax(R) 88A, a Example Compositions dispersant commercially available from MeadWestvaco Cor poration, P.O. Box 118005, Charleston, S.C. 29423, 0094. Example compositions A-D described below each Geroponr) SDS, a surfactant commercially available from include spinetoram. Spinetoram is a mixture of 50-90% (2R, Rhodia, Inc., 8 Cedar Brook Drive, Cranbury N.J., 08512, and 3aR.5aR,5bS.9S,13S, 14R,16aS,16bR)-2-(6-deoxy-3-O- a balance of water to provide a Suspension concentrate having ethyl-2,4-di-O-methyl-O-L-mannopyranosyloxy)-13-(2R, 25-50% w/w of spinetoram were mixed together. The result 5S,6R)-5-(dimethylamino)tetrahydro-6-methylpyran-2- ing mixture was milled in an Eiger MiniMotormill media mill yloxy)-9-ethyl-2,3,3a.4.5.5a.5b,6,9,10,11,12,13,14, 16a, from Eiger Machinery, Inc., 888 East Belvidere Road, Gray 16b-hexadecahydro-14-methyl-1H-as-indaceno.3,2-d slake, Ill., 60030, to a particle size of 1-10 um volume oxacyclododecine-7, 15-dione and 50-10% (2R.3aR.5aS, weighted mean diameter). The particle size was measured 5bS,9S,13S, 14R, 16aS,16b5)-2-(6-deoxy-3-O-ethyl-2,4-di using a Malvern Mastersizer 2000 laser diffraction particle O-methyl-O-L-mannopyranosyloxy)-13-(2R,5S,6R)-5- analyzer from Malvern Instruments Ltd., Enigma Business (dimethylamino)tetrahydro-6-methylpyran-2-yloxy-9- Park, Grovewood Road, Malvern, Worcestershire WR14 ethyl-2,3,3a.5a5b,6,9,10,11,12,13,14,16a, 16b 1XZ, tetradecahydro-4, 14-dimethyl-1H-as-indaceno.3.2-d 0107 United Kingdom. After milling, egg albumen from oxacyclododecine-7, 15-dione. Spinetoram is synthetically Grade II chicken egg whites from Sigma Aldrich Corpora derived from a natural product and is typically accompanied tion, 3050 Spruce St., St. Louis, Mo., 63.103 and Zinc acetate by various impurities. Accordingly, for each of the composi dihydrate, 98+% from Sigma Aldrich Corporation, were tions prepared below in Examples A-D, an assay was per added to the mixture under agitation. The total Solids concen formed on the spinetoram used to determine the presence of tration of the mixture was adjusted in the range of 20-50% by impurities. weight by adding water, and the pH was adjusted to 6-9 with 0095 For each assay, a calibration stock solution sample ammonia Solution as appropriate. The mixture was then was prepared by adding approximately 43 mg of an analyti homogenized with a Silverson L4RTA homogenizer from cally standard form of spinetoram with 10.0 mL of purified Silverson Machines Inc., 355 Chestnut St., East Long water into a 125 mL glassjar. The glassjar was gently Swirled meadow, Mass., 01028, for about 15-30 minutes. The weight until the spinetoram was dispersed into the purified water. percentages for each of the foregoing ingredients, based on 100.0 mL of methanol was then added to the water/spineto the total weight of the composition exclusive of water, are ram mixture in the glass jar. A second solution was prepared provided in Table 1. Table 1 also provides the weight percent by adding 10 mL of purified water and approximately 50 mg age of spinetoram impurities in the composition based on the of the spinetoram product used in each of Examples A-D to a values determined by the assay procedure described above. 125 mL glass jar. The glass jar was gently Swirled until the spinetoram dispersed into the purified water. 100.0 mL of TABLE 1 methanol was then added to the mixture. Each sample was then analyzed using liquid chromatography performed with Example A the following instrumentation and under the following con Ingredients Wt. 90 ditions: 0096 Chromatograph: Agilent (formally Hewlett Pack Spinetoram 1O.O Spinetoram impurities 1.47 ard) model 1100 or equivalent Egg Albumen 50.75 (0097. Column: Phenomenex Luna, C8(2) 3 um, 150 Zinc Acetate 33.4 mx4.6 mm column Reax (R) 88A 3.65 (0098 Mobile Phase A: water with 2 g/L ammonium Geropon (R) SDS 0.73 acetate, pH adjusted to 5.5 with acetic acid (0099 Mobile Phase B: acetonitrile/methanol (80:20, 0108. The liquid composition was then spray-dried using a v:v) Buchi(R) Model 190 bench top spray dryer from Buchi Cor US 2010/0297260 A1 Nov. 25, 2010

poration, 19 Lukens Drive, Suite 400, New Castle, Del. Grade II chicken egg whites from Sigma Aldrich Corporation 19720, at about a 300-400 ml/hr feed rate, 4-6 bar nozzle and ferric sulfate-hydrate, 97% from pressure, 115-140°C. inlet temperature and 50-100° C. outlet I0121 Sigma Aldrich Corporation were added to the mix temperature to provide a solid composition. It is believed that ture under agitation. The total solids concentration of the the spray drying process removes all or Substantially all of the mixture was adjusted in the range of 20-50% by weight by water and other Volatile ingredients from the liquid compo adding water, and the pH was adjusted to 6-9 with ammonia sition as it is converted to the Solid composition. Since none of Solution as appropriate. The mixture was then homogenized the ingredients in Example A apart from the water is believed with a Silverson L4RTA homogenizer for about 15-30 min to be volatile, it is contemplated that the solid composition utes. The weight percentages for each of the foregoing ingre includes weight percentages for each of the ingredients that dients, based on the total weight of the composition exclusive substantially correspond to those provided in Table 1. How of water, are provided in Table 2. Table 2 also provides the ever, since the Solid composition was later used for bio weight percentage of spinetoram impurities in the composi efficacy experiments, an assay was performed to determine its tion based on the values determined by the assay procedure proportion by weight of pure spinetoram so appropriate con described above. centrations for testing could be prepared. 0109 For this assay procedure, a calibration stock solution TABLE 2 sample was prepared by adding approximately 43 mg of an analytically standard form of spinetoram with 10.0 mL of Example B purified water into a 125 mL glassjar. The glassjar was gently Ingredients Wt. 90 swirled until the spinetoram was dispersed into the purified water. 100.0 mL of methanol was then added to the water/ Spinetoram 1O.O Spinetoram impurities 1.47 spinetoram mixture in the glass jar. A second solution was Egg Albumen 50.75 prepared by adding 10 mL of purified water and approxi Iron (III) sulfate 33.4 mately 130 mg of the Solid composition to a 125 mL glassjar. Reax (R) 88A 3.65 The glass jar was gently Swirled until the Solid composition Geropon (R) SDS 0.73 dispersed into the purified water. 100.0 mL of methanol was then added to the mixture and the mixture was shaken for at 0.122 The liquid composition was then spray-dried using a least about 5 minutes on a mechanical shaker. An aliquot of Buchi(R) Model 190 bench top spray dryer from Buchi. Cor the mixture was then filtered through a 0.45), tin nylon syringe poration at about a 300-400 ml/hr feed rate, 4-6 bar nozzle filter, with the first few filtered drops being discarded, and the pressure, 115-140°C. inlet temperature and 50-100° C. outlet remaining filtrate providing a sample for liquid chromatog temperature to provide a solid composition. It is believed that raphy. Each sample was then analyzed using liquid chroma the spray drying process removes all or Substantially all of the tography performed with the following instrumentation and water and other Volatile ingredients from the liquid compo under the following conditions: sition as it is converted to the Solid composition. Since none of 0110 Chromatograph: Agilent (formally Hewlett Pack the ingredients in. Example Bapart from the water is believed ard) model 1100 or equivalent to be volatile, it is contemplated that the solid composition 0111 Column: Phenomenex Luna, C8(2) 3 um, 150 includes weight percentages for each of the ingredients that mx4.6 mm column substantially correspond to those provided in Table 2. How 0112 Mobile Phase A: water with 2 g/L ammonium ever, since the solid composition was later used for bio acetate, pH adjusted to 5.5 with acetic acid efficacy experiments, an assay was performed to determine its 0113 Mobile Phase B: acetonitrile/methanol (80:20, proportion by weight of pure spinetoram so appropriate con v:v) centrations for testing could be prepared. The assay was per 0114 Isocratic elution: 20% A/80% B formed according to the procedure described above with 0115 Flow: 1.0 mL/minute respect to Example A and the weight percentage of the pure 0116. Injection volume: 10.0 LL spinetoram component for the solid composition was calcu 0117 Detector: UV (a) 250 nm. lated to be 9.4%. 0118 Run Time: 20 minutes 0119 Integrator: Agilent EZChrom Elite data acquisi Example C tion system, or equivalent 0123. A liquid composition including spinetoram, egg Based on the results of the liquid chromatography, the weight albumen and cupric (copper(II)) acetate, among other ingre percentage of the pure spinetoram component for the Solid dients, was prepared according to the following. Spinetoram, composition was calculated to be 10.0%. Reax(R 88A, GeroponR SDS and a balance of water to pro Example B vide a suspension concentrate having 25-50% w/w of spin etoram were mixed together. The resulting mixture was 0120 A liquid composition including spinetoram, egg milled in an Eiger MiniMotormill media mill to a particle size albumen and ferric (iron (III)) sulfate, among other ingredi of 1-10 um (volume weighted mean diameter). The particle ents, was prepared according to the following. Spinetoram, size was measured using a Malvern Mastersizer 2000 laser Reax(R 88A, GeroponR SDS and a balance of water to pro diffraction particle analyzer. After milling, egg albumen from vide a suspension concentrate having 25-50% w/w of spin Grade II chicken egg whites from Sigma Aldrich Corporation etoram were mixed together. The resulting mixture was and cupric acetate-monohydrate from Sigma Aldrich Corpo milled in an Eiger MiniMotormill media mill to a particle size ration were added to the mixture under agitation. The total of 1-10 um (volume weighted mean diameter). The particle Solids concentration of the mixture was adjusted in the range size was measured using a Malvern Mastersizer 2000 laser of 20-50% by weight by adding water, and the pH was diffraction particle analyzer. After milling, egg albumen from adjusted to 6-9 with ammonia Solution as appropriate. The US 2010/0297260 A1 Nov. 25, 2010

mixture was then homogenized with a Silverson L4RTA weight percentage of spinetoram impurities in the composi homogenizer for about 15-30 minutes. The weight percent tion based on the values determined by the assay procedure ages for each of the foregoing ingredients, based on the total described above. weight of the composition exclusive of water, are provided in Table 3. Table 3 also provides the weight percentage of spin TABLE 4 etoram impurities in the composition based on the values determined by the assay procedure described above. Example D Ingredients Wt. 90 TABLE 3 Spinetoram 1O.O Example C Spinetoram impurities 1.47 Egg Albumen 50.75 Ingredients Wt. 90 Zinc carbonate 33.4 Reax (R) 88A 3.65 Spinetoram 1O.O Geropon SDS 0.73 Spinetoram impurities 1.47 Egg Albumen 50.75 Copper(II) acetate 33.4 0.126 The liquid composition was then spray-dried using a Reax (R) 88A 3.65 Buchi(R) Model 190 bench top spray dryer from Buchi Cor Geropon SDS 0.73 poration at about a 300-400 ml/hr feed rate, 4-6 bar nozzle pressure, 115-140°C. inlet temperature and 50-100° C. outlet 0124. The liquid composition was then spray-dried using a temperature to provide a solid composition. It is believed that Buchi(R) Model 190 bench top spray dryer from Buchi Cor the spray drying process removes all or Substantially all of the poration at about a 300-400 ml/hr feed rate, 4-6 bar nozzle water and other Volatile ingredients from the liquid compo pressure, 115-140°C. inlet temperature and 50-100° C. outlet sition as it is converted to the Solid composition. Since none of temperature to provide a solid composition. It is believed that the ingredients in Example Dapart from the water is believed the spray drying process removes all or Substantially all of the to be volatile, it is contemplated that the solid composition water and other Volatile ingredients from the liquid compo includes weight percentages for each of the ingredients that sition as it is converted to the Solid composition. Since none of substantially correspond to those provided in Table 4. How the ingredients in Example Capart from the water is believed ever, since the solid composition was later used for bio to be volatile, it is contemplated that the solid composition efficacy experiments, an assay was performed to determine its includes weight percentages for each of the ingredients that proportion by weight of pure spinetoram so appropriate con substantially correspond to those provided in Table 3. How centrations for testing could be prepared. The assay was per ever, since the Solid composition was later used for bio formed according to the procedure described above with efficacy experiments, an assay was performed to determine its respect to Example A and the weight percentage of the pure proportion by weight of pure spinetoram so appropriate con spinetoram component for the solid composition was calcu centrations for testing could be prepared. The assay was per lated to be 11.9%. formed according to the procedure described above with respect to Example A and the weight percentage of the pure Bio-Efficacy Testing spinetoram component for the Solid composition was calcu lated to be 10.7%. I0127 Biological efficacy experiments were conducted according to the following parameters. A spinetoram control Example D Solution was prepared utilizing Delegate R, a water-dispers ible granule formulation of spinetoram commercially avail 0125. A liquid composition including spinetoram, egg able from Dow AgroSciences LLC, 9330 Zionsville Road, albumen and Zinc carbonate, among other ingredients, was Indianapolis, Ind., 46268, in water to obtain a spinetoram prepared according to the following. Spinetoram, Reax(R) concentration in solution of 125 ppm. Test solutions were also 88A, Geroponr) SDS and a balance of water to provide a prepared utilizing the solid compositions of Examples A-D suspension concentrate having 25-50% w/w of spinetoram (Example A-D solutions) in water to obtain a spinetoram were mixed together. The resulting mixture was milled in an concentration in each solution of 125 ppm. These solutions, Eiger Mini Motormill media mill to a particle size of 1-10 um plus a water-only control, were applied to potted pepper (volume weighted mean diameter). The particle size was plants (Capsicum annuum) using a Mandel track sprayer measured using a Malvern Mastersizer 2000 laser diffraction calibrated to deliver the equivalent of 200 L/Ha of spray. particle analyzer. After milling, egg albumen from Grade II Treated plants were allowed to dry and then were aged out chicken egg whites from Sigma Aldrich Corporation and Zinc doors in natural Sunlight or under a set of lamps emitting carbonate in the form of zinc carbonate RAC from Brugge ultraviolet light at levels comparable to natural Sunlight. At mann Chemical U.S., 15 Reese Avenue, Suite 200, Newtown the appropriate time after treatment, i.e., at 3, 6, 11 and 14 Square, Pa., 19073, were added to the mixture under agita days after treatment, 2.5 cm diameter disks were cut from tion. The total solids concentration of the mixture was treated leaves. One leaf disk was placed in each well of a 32 adjusted in the range of 20-50% by weight by adding water, well plastic tray, which also contained a thin layer of agar to and the pH was adjusted to 6-9 with ammonia solution as provide moisture. There were 8 replicate disks per treatment. appropriate. The mixture was then homogenized with a Sil Each well was infested with three second instar beet army verson L4RTA homogenizer for about 15-30 minutes. The worm. (Spodoptera exigua) larvae, and the well was sealed weight percentages for each of the foregoing ingredients, with plastic film. Larvae were held in an environmental cham based on the total weight of the composition exclusive of ber at 25°C./40 percent relative humidity. At 48 hours after water, are provided in Table 4. Table 4 also provides the infestation, the larvae were graded for mortality. A larva was US 2010/0297260 A1 Nov. 25, 2010 14 considered dead if it could not move after being prodded, and 2. The composition of claim 1, wherein the at least one the percent mortality (percent control) was calculated. pesticide is a photo-labile pesticide. 0128 Table 5 below provides the percent control of the 3. The composition of claim 1, wherein the at least one insect associated with the spinetoram control solution relative pesticide is a reactive with singlet oxygen. to an untreated standard. For Example A-D solutions, Table 5 4. The composition of claim 1, wherein the at least one provides the improvement in percent control relative to the pesticide is a macrocyclic lactone insecticide. spinetoram control Solution (i.e., (percent control by 5. The composition of claim 1, wherein the at least one Example A-D solutions)-(percent control by spinetoram con pesticide is a spinosyn selected from the group consisting of trol solution). Table 5 also provides the average improvement spinetoram and spinosad. over the spinetoram control solution which was calculated by 6. The composition of claim 1, which includes a ratio by Summing the individual improvements for each of the days weight between the at least one transition metal salt and the at relative to the control and then dividing by the number of least one pesticide from about 1:1 to about 6:1, a ratio by measurementS. weight between the at least one proteinaceous material and

TABLE 5

3 4 5 6 7 9 10 11 13 14 Average Solution DAT DAT DAT DAT DAT DAT DAT DAT DAT DAT DAT Improvement Spinetoram 79 67 8 — O Control Solution Example A 17 -8 17 — 8 8 Solution Example B 4 12 63 — 42 30 Solution Example C 17 21 46 — 46 32 Solution Example D 8 21 13 — 13 14 Solution

0129. The headings in this document are for convenience the at least one pesticide from about 3:1 to about 8:1, and a only and must not be used to interpret any portion thereof. ratio by weight between the at least one proteinaceous mate 0130. Any theory, mechanism of operation, proof, or find rial and the at least one transition metal salt from about 1:2 to ing stated herein is meant to further enhance understanding of about 4:1. the present invention and is not intended to make the present invention in any way dependent upon Such theory, mecha 7. The composition of claim 1, wherein the transition metal nism of operation, proof, or finding. It should be understood in the transition metal salt is selected from the group consist that while the use of the word preferable, preferably or pre ing of Zinc, iron, copper and manganese. ferred in the description above indicates that the feature so 8. The composition of claim 1, wherein the at least one described may be more desirable, it nonetheless may not be transition metal salt is selected from the group consisting of a necessary and embodiments lacking the same may be con transition metal acetate, a transition metal acetylacetonate, a templated as within the scope of the invention, that scope transition metal nitrate, a transition metal sulfate, a transition being defined by the claims that follow. In reading the claims metal halide and a transition metal carbonate. it is intended that when words such as “a”“an,”“at least one.” “at least a portion” are used there is no intention to limit the 9. The composition of claim 1, wherein the at least one claim to only one item unless specifically stated to the con proteinaceous material is selected from the group consisting trary in the claim. Further, when the language "at least a of egg albumen, whey, gelatin and Zein. portion' and/or “a portion' is used the item may include a 10. The composition of claim 9, wherein the at least one portion and/or the entire item unless specifically stated to the transition metal salt is selected from the group consisting of contrary. While the invention has been illustrated and iron (III) sulfate, copper (II) acetate, Zinc acetate and Zinc described in detail in the drawings and foregoing description, carbonate. the same is to be considered as illustrative and not restrictive in character, it being understood that only the selected 11. The composition of claim 10, wherein the at least one embodiments have been shown and described and that all proteinaceous material is egg albumen. changes, modifications and equivalents that come within the 12. A composition, comprising from about 8% to about spirit of the invention as defined herein or by any of the 15% by weight of spinetoram, from about 40% to about 60% following claims are desired to be protected. by weight of a proteinaceous material, and from about 25% to What is claimed is: about 40% by weight of a transition metal salt. 1. A composition, comprising at least one pesticide, at least 13. The composition of claim 12, wherein the transition one transition metal salt and at least one proteinaceous mate metal salt is selected from the group consisting of iron (III) rial, wherein the composition exhibits enhanced pesticidal Sulfate, copper (II) acetate, Zinc acetate and Zinc carbonate. activity levels compared to a composition dissimilar only in 14. The composition of claim 13, wherein the proteina not having the at least one transition metal salt and the at least ceous material is selected from the group consisting of egg one proteinaceous material. albumen, whey, gelatin and Zein. US 2010/0297260 A1 Nov. 25, 2010

15. The composition of claim 12, wherein the transition and a ratio by weight between the proteinaceous material and metal salt includes iron (III) sulfate and the proteinaceous the transition metal salt from about 1:1 to about 2:1. material includes egg albumen. 17. A method of controlling insects which comprises 16. The composition of claim 12, which includes a ratio by applying to a locus where control is desired an insect-inacti weight between the transition metal salt and spinetoram from Vating amount of a composition according to claim 12. about 2:1 to about 4:1, a ratio by weight between the proteina ceous material and spinetoram from about 4:1 to about 6:1, c c c c c