H:Vbr\Interovn\NRPortbl\DCC\RBR\5889560 I.doc-12/12/2013 1 "HERBICIDAL OIL-IN-WATER EMULSION COMPOSITIONS COMPRISING 2 BROADLEAF WEEDS IN TURFGRASS" 3 4 This application is a divisional application of Australian Application 5 No. 2007308682 the specification and drawings of which as originally filed are 6 incorporated herein in their entirety by reference. 7 8 FIELD OF THE INVENTION 9 The invention relates to herbicidal compositions and in particular to 10 herbicidal oil-in-water emulsions that reduce the effective amount of herbicide 11 required for the control of broadleaf weeds in turfgrass, while being substantially 12 non-phytotoxic to turfgrass. 13 14 BACKGROUND OF THE INVENTION 15 The use of oils as herbicide adjuvants is a well established practice 16 in agriculture for improvement of weed control applications through better 17 coverage and penetration of the active ingredient on the leaf surface of the target 18 weed. In many cases, this permits some degree of reduction in the rate of 19 herbicide required, which is particularly desired for synthetic herbicides that are 20 toxic to humans and the environment. Oil-based herbicide adjuvants are often 21 formulated as an herbicidal "emulsifiable concentrate" consisting of a 75-95 wt% 22 hydrocarbon oil or solvent with the balance being emulsifier, and to which the 23 herbicide is added. In use, the herbicidal emulsifiable concentrate is diluted with 24 water to form an oil-in-water emulsion which is then sprayed onto the target area 25 at an appropriate rate. 26 While most oil-based herbicidal adjuvants have been directed to the 27 control of grassy weeds in crops, little has been done with respect to the use of 28 such adjuvants for the control of broadleaf (dicotyledous) weeds in turfgrass. In 29 one study by McCowan (McCowan, F.H. "Turf Herbicide Rx: Add Oil" April, 1968), 30 it was found that the addition of Sunspray Oil 11E (a mixture of refined 1 WO 2008/049192 PCT/CA2007/001762 1 paraffin oil and emulsifier at 98:2 wt%, respectively; available from Sunoco, Inc. 2 Philadelphia PA, USA) to certain herbicides resulted in equal or better weed 3 control in turfgrass when delivered at a rate of 2 gallons of oil per acre. 4 However, the herbicide oil combination also resulted in a significant increase in 5 toxicity to the turfgrass in some cases. Overall, Applicant believes McCowan's 6 findings were not conclusive with respect to the selectivity, effectiveness and 7 phytotoxicity of various herbicide-oil combinations. To the inventor's knowledge, 8 there are currently no high-oil-content herbicide compositions that selectively kill 9 broadleaf weeds on the market for use on turfgrass. 10 Wide use of selective herbicides like 2,4-D (2,4 11 dichlorophenoxyacetic acid), Mecoprop (MCPP or methylchlorophenoxypropionic 12 acid) and dicamba (3,6-dichloro-o-anisic acid) for controlling broadleaf weed in 13 turfgrass throughout the world are controversial. The International Agency for 14 Research on Cancer has classified the entire family of phenoxy-type herbicides, 15 and particularly 2-4D, as potentially carcinogenic. Mecoprop and dicamba are 16 suspected of being human teratogens. In the interest of public safety, regulatory 17 bodies such as US EPA and Health Canada PMRA have been making label 18 improvements aimed primarily at exposure reduction of 2,4-D and other 19 herbicides to environments. 20 Control of broadleaf weeds remains a major problem in turfgrass 21 throughout the world. Further, public concerns related to human health and 22 safety as well as the impact on environments resulting from the application of 23 such herbicides, continue to arise. There is, therefore, a need in the art for 24 improved herbicidal compositions for controlling broadleaf weeds in turfgrass 25 that present a reduced risk to humans and to the environment. 2 H:Vbr\Introvn\NRPortbl\DCC\RBR\8729749_I.docx-27/10/2015 1 SUMMARY OF THE INVENTION 2 Embodiments of the invention provide an herbicidal composition having 3 an amount of active ingredient significantly reduced from known prescribed label 4 rates used for conventional herbicides. The novel compositions demonstrate a 5 significantly increased herbicidal efficacy for controlling broadleaf weeds in turfgrass 6 while being substantially non-phytotoxic to the turfgrass. 7 Embodiments of the invention enable use of known herbicides at much 8 lower active ingredient (A.I.) rates while showing at least equivalent broadleaf weed 9 control in turfgrass when compared to prescribed label rates, typically expressed as 10 the A.I. per unit area. 11 Embodiments of the invention are also directed to a method of 12 controlling broadleaf weeds in turfgrass while being substantially non-phytotoxic to 13 turfgrass, which comprises treating the locus thereof with an effective amount of the 14 novel herbicidal composition. As an additional feature, embodiments of the novel 15 herbicidal composition have been found to control insects, such as sod webworms 16 and fall armyworms, in turfgrass. 17 Therefore in one aspect, the invention provides a selective herbicidal 18 composition provided as an oil-in-water emulsion, comprising: a broadleaf herbicide 19 which is an auxin mimic-type herbicide in an effective amount, wherein the effective 20 amount is from about 10% to about 50% of a herbicidally effective rate for application 21 to turfgrass when the broadleaf herbicide is used alone; an oil and emulsifier mixture 22 having a ratio of oil to emulsifier that is from about 95:5 wt% to about 50:50 wt%, 23 wherein the oil comprises paraffinic oil; and water, wherein when applied to turfgrass, 24 the composition demonstrates broadleaf herbicidal activity and is substantially non 25 phytotoxic to turfgrass. 3 H:Vbr\Introvn\NRPortbl\DCC\RBR\8729749_I.docx-27/10/2015 1 Another aspect provides an emulsion-forming selective broadleaf 2 herbicide concentrate comprising: a broadleaf herbicide which is an auxin mimic-type 3 herbicide in an effective amount, wherein the effective amount is from about 10% to 4 about 50% of a herbicidally effective rate for application to turfgrass when the 5 broadleaf herbicide is used alone, and an oil-emulsifier mixture having a ratio of oil to 6 emulsifier from about 50:50 wt% to about 95:5 wt%, wherein when diluted in water as 7 an oil-in-water emulsion for spray application to turfgrass the diluted concentrate 8 demonstrates broadleaf herbicidal activity and is substantially non-phytotoxic to 9 turfgrass. 10 Still another aspect provides a method of preparing an oil-in-water 11 emulsion having selective herbicidal efficacy comprising: preparing an emulsion 12 forming broadleaf herbicide which is an auxin mimic-type herbicide concentrate by 13 combining one or more said broadleaf herbicides in an effective amount, wherein the 14 effective amount is from about 10% to about 50% of a herbicidally effective rate for 15 application to turfgrass when the broadleaf herbicide is used alone, and an oil 16 emulsifier mixture having a ratio of oil to emulsifier from about 95:5 wt% to about 17 50:50 wt%; and combining the emulsion-forming broadleaf herbicide concentrate with 18 water sufficient to dilute the oil-emulsifier from about 5 wt% to about 35 wt% for 19 forming an oil-in-water emulsion for application to turfgrass at a total spray volume of 20 from about 60 to about 120 gal/acre, the oil-in water emulsion having broadleaf 21 herbicidal activity and substantially non-phytotoxic to turfgrass. 22 Yet another aspect provides a method for delivering a selective 23 herbicide to turfgrass to control broadleaf weeds with substantially no phytotoxicity to 24 the turfgrass comprising: preparing an oil-in-water emulsion comprising: an oil 25 emulsifier mixture having a ratio of oil to emulsifier from about 95:5 wt% to about 4 H:Vbr\Intrwovn\NRPortbl\DCC\RBR\8740040 L.docx-28/10/2015 1 50:50 wt%; water; and a broadleaf herbicide which is an auxin mimic-type herbicide 2 in an effective amount, wherein the effective amount is from about 10% to about 50% 3 of a herbicidally effective rate for application to turfgrass when the broadleaf herbicide 4 is used alone, and applying the oil-in-water emulsion to turfgrass by spraying, wherein 5 the oil-in-water emulsion applied to the turfgrass by spraying comprises from about 5 6 wt% to about 35 wt% of the oil and emulsifier. 7 Exemplary herbicides contemplated for use in embodiments of the 8 invention are the auxin mimic-type herbicides which include such herbicides as 9 KILLEX@ and TRIMEC@. 10 4a WO 2008/049192 PCT/CA2007/001762 1 BRIEF DESCRIPTION OF THE DRAWINGS 2 Figure 1 is a graphical representation of the effect of KILLEX@ 3 formulations according to embodiments of the invention, as described in 4 Example 3, over time. 5 6 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 7 As used herein, the term "control" generally refers to killing, 8 inhibition of proliferation, or otherwise diminishing the occurrence of plants. 9 Further, the terms "turfgrass" or "grass" generally refer to grasses 10 that are periodically cut or mowed to provide a groundcover for various utility, 11 recreational or aesthetic purposes. Exemplary turfgrasses include Fescues, 12 Rye, Bent, Bahia, St. Augustine, Centipede, Kentucky bluegrass, Zoysia Native 13 Grasses (e.g., Buffalo grass, Blue Grama and Wheatgrasses), Seashore 14 Paspalum, Carpet Grass, Buffo, and Beach Grass. Such grasses are typically 15 found in locations such as parks, golf courses, sports fields, sod farms, 16 roadsides, and lawns for housing residences, commercial sites, and institutional 17 grounds. 18 Examples of "broadleaf weeds" include, but are not limited to, 19 bedstraw, bindweed (field), birdsfoot trefoil, black medic, blackseed plantain, 20 blueweed, broad-leaved plantain, burdock, buttercup, canada thistle, chickweed, 21 chicory, clover, common chickweed, daisy fleabane, dandelion, devil's paint 22 brush (hawkweed), dock (curled), english daisy, fall dandelion (fall hawkbit), 23 grass leaved stitchwort, ground ivy, heal-all, henbit, knotweed, kochia, lamb's 24 quarters, mallow, mouse-ear chickweed, mustards, narrow-leaved plantain, ox 25 eye daisy, peppergrass, pigweed, pineapple weed, poison ivy, prostrate 5 WO 2008/049192 PCT/CA2007/001762 1 pigweed, purslane, ragweed, russian thistle, sandwort (thyme-leaved), sheep 2 sorrel, shepherd'spurse, smartweed (green), sow thistle, speedwell (purslane 3 leaved), spotted spurge, stitchwort, stonecrop (mossy), veronica (thyme-leaved), 4 wild lettuce, yellow hawkweed brambles, buckhorn plantain, bull thistle, carolina 5 geranium, cocklebur, crudweed, evening primrose, false dandelion, fleabane, 6 florida pusley, frenchweed poison oak, hawkweed, honeysuckle, jimsonweed, 7 kudzu, little starwort, morning glory, oxalis (yellow woodsorrel), pennywort, 8 plantains (narrow, buckhorn, broadleaf), poorjoe, povertyweed, soliva, 9 spreadwell (annual), spurge, sumac, vervain, vetch, violet, wild aster, wild 10 blackberry, wild carrot, wild garlic, wild geranium, wild onion, wild radish, wild 11 raspberry and yarrow. 12 In embodiments of the invention, the herbicidal composition 13 comprises a highly saturated oil, an emulsifier, and a broadleaf herbicide, 14 provided as an oil-in-water emulsion (0/W emulsion) for ready-to-use 15 applications or as an emulsifiable herbicidal concentrate which is thereafter 16 diluted in water for application as the O/W emulsion. 17 In embodiments of the invention, the active ingredients (A.I.) of an 18 herbicide selected to control broadleaf weeds are present in the oil-in-water 19 emulsion in a range of from about a 50% reduction, compared to known 20 prescribed label rates, to about a 90% reduction, compared to known prescribed 21 label rates. The oil and emulsifier in the oil-emulsifier mixture are present in a 22 weight ratio of about 95:5 wt% to about 50:50 wt%. The oil-emulsifier mixture is 23 present in the total O/W emulsion at about 5% to about 35% by weight which is 24 contemplated to be delivered in a total spray volume of about 60 to about 120 25 gallons of O/W emulsion per acre of turfgrass. 6 WO 2008/049192 PCT/CA2007/001762 1 In embodiments of the invention the oil-emulsifier mixture is 2 present in the total oil-in-water emulsion at about 10% to about 30%. 3 In embodiments of the invention the oil-emulsifier mixture 4 comprises a ratio of oil to emulsifier of from about 85:15 wt% to about 90:10 5 wt%. The inventors have found that an oil-emulsifier mixture having less than 6 about 5% of emulsifier does not significantly increase herbicidal efficacy, even 7 when used at 30% in the O/W emulsion. 8 In embodiments of the invention, exemplary herbicides comprise 9 auxin mimic or growth regulator type herbicides, which include the phenoxy-type 10 herbicides, such as 2,4-D, 2,4-DB, 24-DP, benzoic acid-type herbicides, such as 11 dicamba and MCPA and other aromatic acid herbicides such as clopyralid, 12 fluroxypyr, picloram and quinclorac. 13 It is particularly contemplated that the herbicide used is either 14 KILLEX@ (Scott Canada, Mississauga, Ontario) or TRIMEC@ (PBI/GORDON 15 Corporation, Kansas City, Missouri), both of which are combinations of 2,4-D 16 Mecoprop and dicamba. In embodiments of the invention, KILLEXR or 17 TRIMEC@ are used in a total herbicide active ingredient to oil-emulsifier mixture 18 ratio of about 1:50 to about 1:750 by weight. 19 In the case of KILLEX® or TRIMEC@, the 2,4-D may be in the form 20 of an acid, a salt or an ester, such as 2,4-D acid, 2,4-D sodium salt, 2,4-D diethyl 21 amine, 2,4-D dimethylamine salt, 2,4-D isopropyl acid, 2,4-D triisopropyl acid, 22 2,4-D butoxyethyl ester, 2,4-D ethylhexyl ester or 2,4-D isopropyl ester. The 23 Mecoprop may be in the form of an acid, a salt or an ester, such as MCPP acid, 24 potassium salt, dimethylamine salt, diethanolamine salt or isooctyl ester. The 25 Dicamba may be in the form of an acid, a dimethylamine or a sodium salt. 7 WO 2008/049192 PCT/CA2007/001762 1 Oils used in the composition are highly saturated oils. Typically, the 2 oils are either synthetic or produced using conventional refining techniques such 3 as solvent extraction, severe and mild hydrocracking or hydrotreating or 4 hydrofining and have a viscosity in the range of about 6cSt to about 34cSt at 5 40'C (ASTM 445). Embodiments of the invention utilize paraffinic or isoparaffinic 6 oils. 7 In embodiments of the invention, isoparaffinic oils are selected to 8 have a carbon number distribution in the range of about C16 to about C35 and is 9 highly refined to have an aromatic content of less than about 10wt% and in 10 embodiments of the invention less than about 5wt%. In embodiments of the 11 invention an isoparaffinic oil having substantially no aromatics is selected. 12 As compared to "light oils" such as SOLVESSO T M 150 (available 13 from ExxonMobil) or kerosene, the inventors believe heavier isoparaffinic oils 14 evaporate less quickly from the leaf surface and do not cause severe cell 15 membrane disruption and therefore provide a better opportunity for the O/W 16 emulsion to spread and for the herbicide therein to penetrate the leaf surface 17 effectively. 18 Emulsifiers are selected to have minimal toxicological risk, such as 19 those included on the Environmental Protection Agency's List 3 or 4 Inert (other) 20 Pesticide Ingredients in Pesticide Products. Appropriate emulsifiers are selected 21 to have sufficient solvency in the oil phase such as described in US Patent 22 6,515,031 to Applicant, the entirety of which is incorporated herein by reference. 23 In embodiments of the invention, suitable emulsifiers also include 24 ethoxylated alcohols having primary C5 - C20 carbon chains with an average of 25 about 2 to about 7 ethoxylation groups and alkyl phenol ethoxylates, including 8 WO 2008/049192 PCT/CA2007/001762 1 but not limited to dodecyl phenol ethoxylates, nonyl phenol ethoxylates and the 2 like. 3 Commercial preparations, whether prepared as ready-to-use 4 compositions or as emulsifiable concentrates, may further contain such 5 additional ingredients as are known to one of skill in the art, such as 6 preservatives to extend the shelf-life stability. In embodiments of the invention, a 7 small amount of preservative, such as methylchloroisothiazolinone in 8 combination with methylisothiazolinone (KATHON@ CG/ICP available from 9 Rohm and Haas) is added, typically at less than 2.25 ppm of active ingredient. 10 The O/W emulsions to be sprayed on turfgrass are typically 11 prepared using high shear mixing equipment such as a Polytron@ Homogenizer 12 (available from Kinematica Inc., Newark, NJ, USA). Preparation using high shear 13 equipment results in stable emulsions which can then be applied to the turfgrass 14 using conventional spraying equipment and techniques. 15 As shown in the examples below, the unique combinations of oil 16 and emulsifier in the emulsions act to reduce the amount of active ingredient of 17 the herbicide, particularly KILLEX@ and TRIMEC@, required to kill broadleaf 18 weeds in turfgrass as compared to conventional aqueous solutions of the same 19 herbicides. The compositions as shown result in a lack of detectable 20 phytotoxicity when the O/W emulsion is used at a total spray volume of about 60 21 120 gal /acre. 22 One of skill in the art would understand that embodiments of the 23 invention using other herbicides such as listed above would similarly result in a 24 significant reduction of the amount of active ingredient of the herbicide required 25 to control broadleaf weeds in turf grass. 9 WO 2008/049192 PCT/CA2007/001762 1 Further, Applicant has noted that embodiments of the invention are 2 effective in controlling insects such as tropical sod webworm and fall armyworm 3 when applied to turfgrass. 4 5 EXAMPLE 6 General Materials and Methods 7 8 Materials 9 The oils, emulsifiers and herbicides shown in Tables 1, 2 and 3 10 were used as indicated in the examples. 11 Table 1 Oils Oil Component Source N65DW Synthetic isoparaffinic oil Petro-Canada* 12 *Calgary AB, Canada 13 14 15 Table 2 - Emulsifiers 1 6 .. ..... ------ ------------------ Emulsifier Components Source AL3313 Polyoxyethyene lauryl ether, C 10 to C 16 alcohol Uniqema* ethoxylates, and glycerol oleate Atplus 300F Non ionic surfactant blends Uniqema* 17 *New Castle, DE, USA 10 WO 2008/049192 PCT/CA2007/001762 1 Table 3. Herbicides 2 ---- --- --- ----- ------------- --------------- Herbicide Component Source KILLEX@ 2,4-D, dimethylamine @ 190 g/l Scott Canada* (2,4-dicholorophenoxyacetic acid, dimethylamine salt) Mecoprop-p, Dimethylamine @ 100 g/l, (2-(2-Methyl-4-chlorophenoxy)propionic acid, dimethylamine salt) Dicamba, Dimethylamine @ 18 g/l (Benzoic acid 3, 6-dichloro-2-methoxy-, dimethylamine salt) TRIMEC@ 2,4-D, dimethylamine @ 25.93 % PB/Gordon** Classic (2,4-dicholorophenoxyacetic acid, dimethylamine salt) Mecoprop-p, Dimethylamine @ 13.85 % (2-(2-Methyl-4-chlorophenoxy)propionic acid, dimethylamine salt) Dicamba, Dimethylamine @ 2.76 % (Benzoic acid 3, 6-dichloro-2-methoxy-, dimethylamine salt) TRIMEC@ 2,4-D, dimethylamine @ 18.74% PB1/Gordon** Southern (2,4-dicholorophenoxyacetic acid, dimethylamine salt) Mecoprop-p, Dimethylamine @ 17.37% (2-(2-Methyl-4-chlorophenoxy)propionic acid, dimethylamine salt) Dicamba, Dimethylamine @ 3.85% (Benzoic acid 3, 6-dichloro-2-methoxy-, dimethylamine salt) 3 * Mississauga, Ontario 4 ** Kansas City, Missouri 5 6 Methods 7 Preparation and use of aqueous KILLEX@) and TRIMEC@ formulations 8 Conventional aqueous KILLEX@ solutions were prepared by 9 diluting KILLEX® in water as appropriate for use at the label rate ("KILLEX 10 100%", 0.59 gal/acre) and at a reduced rate ("KILLEX 12.5%", 0.074gal/acre, 11 WO 2008/049192 PCT/CA2007/001762 1 87.5% reduction). In particular," KILLEX 100%" was used at the label rate of 0.59 2 gal/acre in sufficient water (approximately 107 gal/acre). "KILLEX 12.5%" was 3 used at a reduced rate of 0.074 gal/acre in sufficient water (approximately 107 4 gal/acre). 5 TRIMEC@Classic solutions were prepared by diluting 6 TRIMEC@Classic in water as appropriate for use at the label rate ("TRIMEC 7 100%", 0.5 gal/acre) and at a reduced rate ("TRIMEC 12.5%", 0.0625gal/acre), 8 each used at a spray volume of about 62 gallons per acre. 9 TRIMEC@Southern solutions were prepared by diluting 10 TRIMEC®Southern in water as appropriate for use at the label rate of 0.19 11 gal/acre ("TRIMEC@Southern 100%") and at a reduced rate of 0.0625 gal/acre 12 ("TRIMEC@Southern 33%"), each used at a spray volume of about 62 gallons 13 per acre. 14 15 Preparation and use of KILL EX@ or TRIMEC@ oil-in-water emulsion formulations 16 KILLEX® or TRIMEC@ O/W emulsions were generally prepared by 17 tank-mixing the components using high shear equipment such as a Polytron® 18 Homogenizer (available from Kinematica Inc., Newark, NJ, USA) so as to 19 produce a stable emulsion for application to turfgrass. 20 Various compositions of oil, emulsifier, herbicide and water were 21 prepared, according to embodiments of the invention, varying the oil and 22 emulsifier at 10%, 20% or 30% by weight of the total solution as shown in the 23 examples below. The O/W emulsions were used at a rate of from about 62 24 gal/acre to about 107 gal/acre. 12 WO 2008/049192 PCT/CA2007/001762 1 Testinog of KILLEX@ and TRIMEC@ formulations 2 KILLEX® or TRIMEC@ formulations according to the various 3 examples were applied to 2m x 2m plots of turfgrass. Turfgrass tested at the 4 University of Guelph, Ontario, Canada predominantly comprised perennial 5 ryegrass, with some Kentucky bluegrass and other perennial grasses. Turfgrass 6 tested at Michigan State University, MI, USA comprised a mixture of Kentucky 7 blue grass, rye grass and tall fescue grass. Turfgrass tested at University of 8 Florida, FL, USA comprised bahia grass and St. Augustine grass. The 9 formulations were applied using standard spray procedures, as is known in the 10 art. 11 For measuring the effect of the KILLEX® and TRIMEC@ 12 formulations on the control of broadleaf weeds, the number of dandelions, 13 clovers, dollarweeds or pusley present in each plot was counted before and after 14 treatment with KILLEX@ or TRIMEC@ formulations. 15 For measuring phytotoxic effects of the KILLEX@ or TRIMEC@ 16 formulations on the turfgrass, the turfgrass was analyzed by visual rating 17 accompanied by instrumental assessment using a chlorophyll meter. 18 19 EXAMPLE 2 20 Effects of KILLEX@ dosage and an 0/W emulsion of KILLEX@ on dandelions 21 This example demonstrates the effect of aqueous KILLEX@ 22 formulations on dandelion counts when used at the label rate (0.59 gal/acre) and 23 a reduced rate (12.5%, 0.074 gal/acre, 87.5% reduction), as well as the effect of 24 an O/W emulsion formulation containing 30% by weight of oil plus emulsifier on 25 the efficacy of KILLEX@ at the reduced rate. The KILLEX@ formulations were 13 WO 2008/049192 PCT/CA2007/001762 1 prepared and tested as described in Example 1, with the O/W emulsions being 2 applied at a rate of 107 gal /acre. The results are shown below in Table 4. 3 4 Table 4 5 Dndelion (%cover)- 21 days after treatment KILLEX@ PCI Oil-emulsifier Dandelion Sample %cover Gal/acre Oil emulsifier (21DAA) Control (untreated) (none) (none) (none) 14.0 KILLEX 100% 0.59 (none) (none) 5.0 (label rate) KILLEX 12.5% 0.074 (none) (none) 12.8 KILLEX 12.5% + 0.074 85 wt% N65DW 15 wt% A13313 3.5 PCI 30% 6 *DAA - days after application 7 The results shown in Table 4 demonstrate that KILLEX@, 8 formulated as an O/W emulsion according to an embodiment of the invention, 9 has increased efficacy with reduced herbicide and therefore lower levels of 10 KILLEX® can be used to control dandelions. 11 12 EXAMPLE 13 Effect of ILLEX@ O/W emulsion over time on dandelions 14 This example demonstrates the effect of KILLEX® O/W emulsion 15 over time on dandelion counts in turfgrass. KILLEX® was used at a rate of 16 0.074 gal/acre in an O/W emulsion containing N65DW:AL3313 at 85:15 wt% and 17 diluted to 30% by weight in water ("PCI 30% + KILLEX@ 12.5%"). The KILLEX@ 18 formulations were prepared and tested as described in Example 1. The control 19 used was untreated turfgrass. 14 WO 2008/049192 PCT/CA2007/001762 1 As shown in Fig. 1, KILLEX@, formulated as an O/W emulsion 2 according to an embodiment of the invention, is effective in controlling 3 dandelions over time, expressed as days after treatment (DAT). 4 5 EXAMPLE4 6 Effects of TRIMEC@ dosage and an O/W emulsion of TRIMEC@ on white 7 clovers 8 9 Example 4 demonstrates the effect of aqueous TRIMEC@ 10 formulations on white clover counts when used at the label rate (0.5 gal/acre ) 11 and at a reduced rate (0.0625 gall Acre, 87.5% reduction). 12 Further Example 4 demonstrates the effect on the efficacy of 13 TRIMEC@ at the reduced rate when used as an O1W emulsion formulation 14 according to embodiments of the invention containing 10% by vyeight of oil plus 15 emulsifier and 20% by weight of oil plus emulsifier The TRIMEC® formulations 16 were prepared and tested as described in Example 1 at Michigan State 17 University, with the O/W emulsions being applied at a rate of 62 gal /acre. The 18 results are shown in Table 5 below. 15 WO 2008/049192 PCT/CA2007/001762 1 Table 5 2 3 Clover (%cover) 24 days after treatment Clover %cover ItTurf TRIMEC@ PCI Oil-emulsifier Clo AA* Injury Sape ____ __ (24DAA*) Injury" Sample (gal/acre)
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Oil emulsifier Control (none) (none) (none) 15.7 1.0 (untreated) TRIMEC 0.5 (none) (none) 1.3 1.0 100% label rate TRIMEC 0.0625 (none) (none) 10 1.0 12.5% TRIMEC 0.0625 85 wt% 15 wt% 1.3 1.0 12.5%+ PCI N65DW A13313 10% TRIMEC 00625 85 wt% 15 wt% 1.7 1.0 12.5% + PCI N65DW A13313 4 * days after application 5 **Rating range from 0 to10, with 10 representing greatest injury 6 (phytotoxicity) 7 8 The results in Table 5 demonstrate that TRIMEC@ formulated as 9 an O/W emulsion according to embodiments of the invention has increased 10 efficacy and therefore significantly lower levels of TRIMEC@ can be used to 11 control clovers in turfgrass without increased phytotoxicity. 12 13 EXAMPLE 14 Effects of TRlMEC@Southern and an O/W emulsion of TRIMEC@Southern on 15 dollarweed and pusley 16 17 Example 5 demonstrates the effect of an aqueous 18 TRIMEC@Southern formulation on dollarweed and pusley counts when used at 19 the label rate (0.19 gal/acre) and an O/W emulsion formulation containing 10% 16 WO 2008/049192 PCT/CA2007/001762 1 by weight of oil plus emulsifier according to a embodiment of the invention 2 applied at a reduced rate (0.0625 gal/acre, 67% reduction). 3 The TRIMEC@Southem formulations were prepared and tested as 4 described in Example I at University of Florida, with the O/W emulsions being 5 applied at a rate of 62 gal /acre, The results are shown in Table 6 below. 6 7 Table 6 8 9 - Pusley and Dollarweed (%cove)- 24 days after treatment Pusley Dollarweed PCI Oil-emulsifier %cover %cover Sample Southern (28DAA*) (28DAA*) (gal/acre) Oil emulsifier Control (none) (none) (none) 100 72 (untreated) TRIMEC@ 0.19 (none) (none) 49 47 Southern 100% label rate TRIMEC@ 0.0625 85 wt% 15 wt% 39 42 Southern 33% N65DW A13313 + PCI 10% 10 * Days after application 11 The results in Table 6 demonstrate that TRIMEC®Southern 12 formulated as an O/W emulsion according to an embodiment of the invention 13 has increased efficacy and therefore significantly lower levels of 14 TRIMEC@Southern can be used to control pusley and dollarweed. 17 WO 2008/049192 PCT/CA2007/001762 1 EXAMPLE 2 Effect of KILLEX@ and O/W emulsions of KILLEX@ on turfarass - Phytotoxicit 3 Example 6 demonstrates the phytotoxic effect of KILLEX@ and 4 various O/W emulsions of KILLEX@ according to embodiments of the invention 5 on turfgrass. 6 The KILLEX@ formulations were prepared and tested as described 7 in Example 1, with the O/W emulsions comprising oil plus emulsifier at 20% by 8 weight in water. The formulations were applied at a total spray volume 107 9 gal/acre. The results are shown in Table 6 below. 10 11 Table 6 12 13 Turfgrass phytotoxicity -KILLEX@ formulations applied at 0.0885 gal/acre Oil-emulsifier Phyto Sample Oil Emulsifier toxicity (scale 0 ----------- ----- -------------- 1 0 )* * Control (none) (none) 0.25 KILLEX 12.5% (none) (none) 0.25 KILLEX 12.5%+PCI 20% 85 wt% N65DW 15 wt% A13313 0.25 KILLEX 12.5%+PCil 20% 85 wt% N65DW 15-wt% Atp-us300 0.5 KILLEX 12.5%+PCII 20% 50 wt% N65DW 50 wt% Atplus300 0.25 14 Phytoxicity scale from 0 to 10, 10 representing greatest phytotoxicity 15 The results shown in Table 6 demonstrate that the ratio of oil to 16 emulsifier and the type of emulsifier used in the oil-emulsifier mixture can affect 17 the phytotoxic effects of KILLEX@ in O/W formulations according to 18 embodiments of the invention. 18 WO 2008/049192 PCT/CA2007/001762 1 EXAMPLE7 2 Effect of TRIMEC. O/W emulsion on the control of tropical sod webworms 3 Applicant has found that TRIMEC@ O/W emulsions, according to 4 embodiments of the invention described herein, are also effective to control sod 5 webworms and fall armyworms in turfgrass. 6 Example 7 demonstrates the effect of the O/W formulations 7 according to embodiments of the invention on killing tropical sod webworm 8 larvae on St. Augustinegrass. 9 The O/W formulation was prepared having a reduced rate of 10 TRIMEC@ (0.0625 gal/acre) containing 10% by weight of oil plus emulsifier. The 11 field trial was carried out at University of Florida on St. Augustine grass. Ten 12 medium sized tropical sod webworm larvae per PVC ring were used, the larvae 13 in the rings being retained outside on turfgrass for 4 days after the application of 14 the O/W emulsion. The O/W emulsion was applied at a rate of 80 gal/acre. Live 15 larvae numbers were counted four days after application. The results are 16 shown in Table 7 below. 17 Table 7 18 19 Live Tropical Sod Webworm larvae 4 days after treatment Treatment # # live larvae - untreated # live larvae - O/ herbicide emulsior Control (4DAA) treated plot (4DAA) 1_ 4 2 2 4 -- 0 -- 3 7 2 - 4 7 _ _ _ _ _ _ _ 5 - 4 --- 5 _5 6 5 - 1 - --- 7 7 5 - 8 51 9- 6 3 - mean 5.44 2.22 % control 0 59.18 20 19 H:Vbr\Intrwovn\NRPortbl\DCC\RBR\8664178_I.docx-16/10/2015 1 The results in Table 7 demonstrate that TRIMEC@ formulated as an 2 O/W emulsion according to an embodiment of the invention is effective to control sod 3 webworms in turfgrass. 4 The reference in this specification to any prior publication (or information 5 derived from it), or to any matter which is known, is not, and should not be taken as 6 an acknowledgment or admission or any form of suggestion that that prior publication 7 (or information derived from it) or known matter forms part of the common general 8 knowledge in the field of endeavour to which this specification relates. 9 Throughout this specification and the claims which follow, unless the 10 context requires otherwise, the word "comprise", and variations such as "comprises" 11 and "comprising", will be understood to imply the inclusion of a stated integer or step 12 or group of integers or steps but not the exclusion of any other integer or step or 13 group of integers or steps. 14 20