Pesticidal compositions

Abstract

A formulated composition suitable for controlling or preventing pathogenic damage in a plant comprising (A) at least one solid active ingredient having a water solubility of at most 100 μg/liter at 25° C. at neutral pH, in an amount of at least 1 weight %, based on the total weight of the formulated composition, (B) at least one non-ionic surface active compound having a hydrophile-lipophile balance (HLB) of between 10 and 18, one or more customary formulation auxiliaries, and water; wherein active ingredient (A) is suspended or dispersed in the water, the weight ratio of surface active compound (B) to active ingredient (A) is in the range of from 1.5 to 15.0, provided the minimum amount of surface active compound (B) is at least 6 weight %, based on the total weight of the formulated composition. Also a method of improving pesticide residue levels in agriculture.

Claims

1. An aqueous agrochemical pesticide formulated composition in the form of a suspension concentrate or suspoemulsion comprising: (A) 1.5 to 15 weight % of abamectin; (B) 7 to 20 weight % of ethoxylated sorbitan oleate having 20 ethyleneoxy groups and a hydrophile-lipophile balance (HLB) of between 14 and 17; (C) one or more surfactants selected from the group consisting of ethoxylated tristyryl phenol and ethoxylated tristyrylphenol phosphate, wherein (C) is present in the formulated composition and is present in an amount up to 3 weight %; one or more customary formulation auxiliaries; water; and optionally (D) one or more other agrochemical pesticides different from (A); wherein (1) each of said weight % is based on the total weight of the formulated composition, (2) the weight ratio of (B) to (A) is from 1.6 to 10.0, and (3) (A) and (D) have a particle size in the range 0.1 to 0.9 μm at x.sub.50 as defined in ISO 13320-1 and (A) and (D) have a particle size in the range 0.7 to 1.5 μm at x.sub.95 as defined in ISO 13320-1.

2. The composition according to claim 1 wherein the ratio of (B) to (A) is in the range of from 1.7 to 7.0.

3. The composition according to claim 1, wherein said abamectin is present in an amount of in the range of 6 to 10 weight % and the ratio of (B) to (A) is in the range of from 1.6 to 3.0.

4. The composition according to claim 1, wherein said abamectin is present in an amount of in the range of 2 to 5 weight % and the ratio of (B) to (A) is in the range of from 4.0 to 8.0.

5. The composition according to claim 1, wherein said abamectin is present in an amount of in the range of 2 to 5, weight % and the ratio of (B) to (A) is in the range of from 4.0 to 7.0.

6. The composition according to claim 1 wherein the other agrochemical pesticide (D) is selected from the group consisting of thiamethoxam, imidacloprid, clothianidin, tefluthrin, cyflumetofen, chlorantraniliprole, cyantraniliprole, difenconazole, fipronil, azoxystrobin, and fludioxonil.

7. The composition according to claim 6 wherein the weight ratio of (D) to (A) is at least 1.5.

8. A method of improving the translaminarity of abamectin and for improving the resuspension properties of a suspension, comprising: forming the aqueous agrochemical pesticide formulated composition of claim 1.

9. A method of controlling pathogenic damage or pest damage in a plant propagation material, a plant, parts of a plant and/or plant organs that grow at a later point in time, which comprises applying on the plant, part of the plant, plant organs, plant propagation material or a surrounding area thereof the aqueous agrochemical formulated composition defined in claim 1.

10. The method according to claim 9 wherein the formulated composition is applied at a rate of 1 to 100 grams of Al per hectare.

11. A tank-mix composition suitable for directly applying on a plant, part of the plant, plant organs, plant propagation material comprising the aqueous agrochemical pesticide formulated composition of claim 1, a solvent, optionally one or more other adjuvants and optionally one or more other pesticide formulated compositions.

Description

EXAMPLES

Preparation Examples

P.1—Preparation of an Abamectin Millbase

(1) In a suitably-sized vessel, polyarylphenol alkoxylate (Soprophor BSU, 28.4 g) and polyarylphenol alkoxylate phosphate (Soprophor 3D33, 18.9 g) were added to potable water (622.5 g) and mixed. Propylene glycol (94.7 g), antifoam (Antifoam 1510, 3.8 g) were further added with mixing, followed by Abamectin (900 g). The pH of the mixture was adjusted to approximately pH 6 using sodium hydroxide (25% in water, 1.2 g). The crude suspension was first passed through a Dyno-Mill (0.6 liter mill chamber volume) to reduce particle size of the suspended particles below 50 micrometers, followed by milling in recirculation mode on Netzsch Lab Mini Zeta IIE mill until the particle size of the suspended particles was below 1.5 micrometers (X.sub.95).

P.2—Preparation of Example 2

(2) In a suitably-sized vessel, propylene glycol (31.3 g), polyarylphenol alkoxylate (Soprophor BSU, 6.2 g), polyarylphenol alkoxylate phosphate (Soprophor 3D33, 22.5 g), polyoxalkylene sorbitan ester (Tween 80, 127.7 g), preservative (Proxel GXL, 0.6 g) and antifoam (Antifoam 1510, 1.3 g) were mixed using a Cowles impeller. Potable water (442.0 g) and Abamectin millbase (P.1, 120.0 g) were added with continued mixing. Thickener (Kelzan, 1.9 g) was added with mixing for one hour to assure satisfactory dispersion. The pH of the suspension concentrate was adjusted to approximately 6 with sodium hydroxide (25% in water, 1.0 g).

P.3—Preparation of Example 13

(3) Step 1: In a suitably-sized vessel, propylene glycol (119.2 g), polyarylphenol alkoxylate phosphate (Soprophor 3D33, 40.6 g) and polyarylphenol alkoxylate (Soprophor BSU, 20.1 g) were mixed to homogeneity. Potable water (517.1 g), antifoam (Antifoam 1500, 1.0 g) and potassium hydroxide (50% in water, 1.99 g) were further added with mixing, followed by an active ingredient (D) (287.4 g). The crude suspension was milled with a Netzsch Lab Mini Zeta IIE mill until the particle size of the suspended particles is below 1.2 micrometers (X.sub.95) to yield a millbase of the active ingredient.

(4) Step 2: Thereafter, in a suitably-sized vessel, propylene glycol (485.3 g), polyoxyalkylene sorbitan ester (Tween 80, 400.0 g), polyarylphenol alkoxylate phosphate (Soprophor 3D33, 59.1 g) and polyarylphenol alkoxylate (Soprophor BSU, 75.1 g) were mixed to homogeneity. Potable water, antifoam (Antifoam 1500, 13.1 g) potassium hydroxide (50% in water, 2.6 g), preservative (Proxel GXL, 12.5 g) were added with mixing followed by Abamectin millbase (P.1, 171.7 g) and millbase prepared in step 1 (30 wt. %, 750.2 g). Thickener (Rhodopol 23, 9.5 g) and suspending agent (Attaflow FL, 100.1 g) were added and mixed to fully disperse.

P.4—Preparation of Example 15

(5) Step 1: In a suitably-sized vessel, potable water (3104.0 g), lignosulfonate (Borresperse NA, 61.2 g), propylene glycol (243.9 g), polyarylphenol alkoxylate phosphate (Soprophor 3D33, 175.5 g) and antifoam (Antifoam 1510, 30.9 g) were mixed with moderate agitation using a Cowles impeller. Active ingredient (D) (2442.3 g) was added until well-mixed. The pH of the crude suspension was adjusted with sodium hydroxide (25% in water, 8.6 g) to approximately 4.6. The suspension was milled with two passes through a Dyno-mill (0.6 liter mill chamber), resulting in particle size of 8.0 micrometers (X.sub.95) to yield a millbase of the active ingredient.

(6) Step 2: Thereafter, in a suitably-sized vessel, potable water (6700.0 g) and polyoxyalkylene sorbitan ester (Tween 80, 1996.0 g) were added with moderate agitation to homogeneity. Preservative (Proxel GXL, 8.1 g), millbase prepared in step 1 (2042.0 g) and Abamectin millbase (P.1, 819.6 g) and suspending agent (Attaflow FL, 236.0 g) were added and mixed with moderate agitation. Thickener (Rhodopol 23, 18.7 g) was slowly added with high agitation. The pH is adjusted to approximately 6.5 with sodium hydroxide (25% in water, 0.5 g) and the suspension concentrate was further mixed for one hour.

P.5—Preparation of Example E

(7) Step 1: Thereafter, in a suitably-sized vessel, suspoemulsion (P.6, 62.49 g), potable water (52.73 g), preservative (Acticide GA, 0.23 g) and antifoam (Antifoam 1500, 0.19 g) were added with moderate agitation to homogeneity. Abamectin millbase (P.1, 4.33 g) was added and mixed with moderate agitation. The pH is adjusted to approximately 5.4 with sulfuric acid (85%, 0.05 g) and allowed to mix at moderate agitation. The suspending agent (Attaflow FL, 1.67 g) was added and mixed with moderate agitation Thickener (Rhodopol 23, 0.30 g) was slowly added with high agitation and the suspension concentrate was further mixed for 30 minutes.

P.6—Preparation of Example 20

(8) Step 1: In a suitably-sized vessel, polyarylphenol alkoxylate phosphate (Soprophor 3D33, 35.13 g) and polyarylphenol alkoxylate (Soprophor BSU, 34.74 g) were mixed to homogeneity. Potable water (442.0 g), antifoam (Antifoam 1500, 2.22 g) and potassium hydroxide (50% in water, 2.16 g) were further added with mixing, followed by an active ingredient (D) (475.8 g). The crude suspension was milled with a Netzsch Lab Mini Zeta IIE mill until the particle size of the suspended particles is below 1.8 micrometers (X.sub.95) to yield a millbase of the active ingredient.

(9) Step 2: Thereafter, in a suitably-sized vessel, potable water (80.0 g), polyarylphenol alkoxylate (Soprophor BSU, 40.4 g) and propylene glycol (32.0 g) were added with high shear mixing via a Silverson mixer (3.0 rpm) to homogeneity. Rape seed oil methyl ester (Steposol ROE-W, 48.0 g) was added slowly to a Silverson mixer at a rate of 3.5 rpm. Mixing continued at this rate for 4 minutes, resulting in particle size of 0.61 micrometers (X.sub.95).

(10) Step 3: Thereafter, in a suitably-sized vessel, suspoemulsion prepared in Step 2 (62.57 g), potable water (25.75 g), preservative (Acticide GA, 0.19 g) and antifoam (Antifoam 1500, 0.17 g) were added with moderate agitation to homogeneity. Millbase prepared in Step 1 (26.30 g) and Abamectin millbase (P.1, 4.28 g) and suspending agent (Attaflow FL, 1.54 g) were added and mixed with moderate agitation. Thickener (Rhodopol 23, 0.28 g) was slowly added with high agitation. The suspension concentrate was further mixed for 30 to 40 minutes or until homogeneous.

(11) The remaining examples were prepared analogously with appropriate adjustments to active ingredients, inert concentrations and types, and particle sizes.

(12) Examples J & K are commercial emulsifiable concentrates of abamectin—Example J is the US product known as AGRIMEK and Example K is the European product called VERTIMEC

(13) TABLE-US-00001 TABLE 1 Examples of formulations (wt %) A 1 B 2 C D 3 4 Abamectin (component (A)) 8.24 8.24 8.00 8.00 4.00 4.03 4.02 4.01 a polyoxyalkylene-sorbitan ester having an HLB of 15 — 16.67 — 17.00 — — 16.91 17.00 (component (B)) a polyoxyalkylene-sorbitan ester having an HLB of 16 — — — — — — — (component (B)) alkoxylated polyarylphenol (component (C)) 1.00 0.81 1.00 1.00 0.92 0.91 0.92 0.93 alkoxylated polyarylphenol phosphate (component (C)) 1.48 1.25 1.50 1.50 1.38 1.39 1.36 1.38 antifreeze 4.95 4.95 5.02 5.00 4.59 4.58 4.58 4.57 antifoam 0.20 0.20 0.20 0.25 0.20 0.21 0.21 0.18 preservative 0.06 0.06 0.08 0.10 0.09 0.10 0.08 0.09 thickener 0.13 0.13 0.15 0.25 0.24 0.27 0.24 0.27 pH buffer 0.25 0.12 0.12 0.11 0.10 0.07 0.10 0.10 water balance balance balance balance balance balance balance balance Particle size, x50 of component A (μm) 3.0 3.0 0.7 0.7 2.07 0.57 0.57 2.07 Particle size, x95 of component A (μm) 12 12 1.5 1.5 9.87 1.35 1.35 9.87 Particle size, x50 of formulation (μm) 3.0 3.0 0.7 0.7 2.07 0.57 0.57 2.07 Ratio of (B):(A) — 2.0 — 2.1 — — 4.3 4.3

(14) TABLE-US-00002 TABLE 2 Examples of formulations (wt %) 5 6 7 Abamectin (component (A)) 4.02 4.00 8.0 a polyoxyalkylene-sorbitan ester having an — — 17.00 HLB of 15 (component (B)) a polyoxyalkylene-sorbitan ester having an 16.98 16.91 — HLB of 16 (component (B)) alkoxylated polyarylphenol (component (C)) 0.90 0.92 — alkoxylated polyarylphenol phosphate 1.39 1.38 — (component (C)) Complex organic phosphate ester, free acid — — 1.00 Block copolymer PO/EO — — 1.00 antifreeze 4.58 4.57 5.00 antifoam 0.20 0.20 0.21 preservative 0.08 0.10 0.11 thickener 0.24 0.24 0.25 pH buffer 0.08 0.08 0.11 water balance balance balance Particle size, x50 of component A (μm) 0.57 2.07 — Particle size, x95 of component A (μm) 1.35 9.87 1.5 Particle size, x50 of formulation (μm) 0.57 2.07 — Ratio of (B):(A) 4.2 4.2 2.1

(15) TABLE-US-00003 TABLE 3 Examples of formulations (wt %) 8 E 9 10 F 11 12 Abamectin (component (A)) 1.75 1.75 1.78 1.87 1.73 1.71 1.78 a polyoxyalkylene-sorbitan ester having an HLB of 15 8.24 — — — — — — (component (B)) Tall oil fatty acid having an HLB of 13 (component B) — — 20.22 — — — — Condensation product of castor oil and EO having an — — — 9.97 — — — HLB of 13 (component B) a polyoxyalkylene-sorbitan ester having an HLB of — — — — — 8.33 — 13.3 (component (B)) a polyoxyalkylene-sorbitan ester having an HLB of 16 — — — — — — 8.27 (component (B)) alkoxylated polyarylphenol (component (C)) 1.84 10.11 — — 1.87 1.87 1.85 alkoxylated polyarylphenol phosphate (component (C)) 2.00 0.06 — — 1.86 1.87 1.88 Rape seed oil methyl ester (an oil) 12.13 — — Medium chain triglycerides (an oil) — — 11.97 antifreeze 11.47 9.56 21.43 9.87 11.64 11.65 11.65 antifoam 0.23 0.15 0.13 0.17 0.26 0.29 0.26 preservative 0.26 0.19 0.26 0.24 0.25 0.28 0.32 thickeners 2.22 1.60 1.43 1.70 2.25 2.31 2.69 Base pH buffer 0.23 0.004 0.004 0.004 0.09 0.05 0.04 Acid pH buffer — 0.04 0.06 0.05 — — — water balance balance balance balance balance balance balance Particle size, x50 of component A 0.57 0.57 0.57 0.57 0.57 0.57 0.57 Particle size, x95 of component A 1.35 1.35 1.35 1.35 1.35 1.35 1.35 Particle size, x50 of formulation 0.57 0.57 0.57 0.57 0.57 0.57 0.57 Ratio of (B):(A) 4.7 — 11.4 5.3 — 4.9 4.6

(16) TABLE-US-00004 TABLE 4 Examples of formulations (wt %) 13 14 15 16 G Abamectin (component (A)) 1.71 2.12 3.02 3.43 1.71 co-active ingredient (component (D)) 4.29* 8.49* 13.85+ 6.86+ 4.29 a polyoxyalkylene-sorbitan ester having an HLB of 15 8.00 8.00 17.00 17.00 — (component (B)) alkoxylated polyarylphenol (component (C)) 1.84 2.14 0.06 0.07 1.80 alkoxylated polyarylphenol phosphate (component (C)) 1.84 2.77 1.09 0.60 1.78 lignosulfonate 0 0 0.35 0.17 — antifreeze 11.69 10.32 1.70 1.04 11.56 antifoam 0.29 0.30 0.20 0.12 0.28 preservative 0.25 0.25 0.25 0.25 0.25 thickener 0.19 0.19 0.15 0.16 0.19 pH buffer 0.08 0.11 0.30 0.31 0.08 suspension aid 2.00 1.94 1.91 2.00 2.00 water balance balance balance balance balance Particle size, x50 of Al (A) 0.5 0.5 0.5 0.5 0.5 Particle size, x95 of Al (A) 1.3 1.3 1.3 1.3 1.3 Particle size, x50 of Al (D) 0.5 0.5 2.9 2.9 0.5 Particle size, x95 of Al (D) 1.3 1.5 8.0 8.0 1.3 Particle size, x50 (formulation) 0.5 0.5 1.6 1.6 0.5 Ratio of (B):(A) 4.7 3.8 5.6 5.0 — *chlorantraniliprole; +thiamethoxam

(17) TABLE-US-00005 TABLE 5 Examples of formulations (wt %) 17 18 19 20 21 22 23 H Abamectin (component (A)) 1.71 1.75 1.75 1.75 1.75 1.75 1.75 1.75 Cyantraniliprole (component (D)) 5.98 8.75 8.75 8.75 8.75 8.75 8.75 8.75 a polyoxyalkylene-sorbitan ester having an HLB of 15 20.04 20.13 20.14 — — — 8.29 — (component (B)) Tall oil fatty acid having an HLB of 13 (component B) — — — — 20.05 20.32 — — Condensation product of castor oil and EO having an — — — 10.00 — — — — HLB of 13 (component B) a polyoxyalkylene-sorbitan ester having an HLB of — — — — — — — — 13.3 (component (B)) a polyoxyalkylene-sorbitan ester having an HLB of 16 — — — — — — — — (component (B)) alkoxylated polyarylphenol (component (C)) 0.53 0.77 0.79 0.79 0.78 0.79 2.57 11.00 alkoxylated polyarylphenol phosphate (component (C)) 0.55 0.79 0.81 0.81 0.80 0.81 2.38 0.81 Rape seed oil methyl ester (an oil) — — — — — — — 12.26 Medium chain triglycerides (an oil) — — — 10.00 — — — — antifreeze 20.96 21.00 20.97 9.34 20.82 21.02 4.98 9.57 antifoam 0.17 0.18 0.23 0.14 0.18 0.18 0.31 0.18 preservative 0.20 0.25 0.24 0.23 0.24 0.23 0.23 0.21 thickeners 1.22 1.18 1.25 1.21 1.17 1.25 1.91 1.21 Base pH buffer 0.04 0.06 0.06 0..06 0.06 0.06 0.19 0.06 Acid pH buffer 0.05 0.10 0.02 0.45 0.09 0.29 0.02 0.02 water balance balance balance balance balance balance balance balance Particle size, x50 of component A 0.57 0.57 0.57 0.57 0.57 0.57 0.57 0.57 Particle size, x95 of component A 1.35 1.35 1.35 1.35 1.35 1.35 1.35 1.35 Particle size, x50 of component D 0.48 1.06 0.48 0.48 1.06 0.48 0.48 0.48 Particle size, x95 of component D 1.80 11.80 1.80 1.80 11.80 1.80 1.80 1.80 Ratio of (B):(A) 11.7 11.5 11.5 5.7 11.5 11.6 4.7 —
Dilution Tests:

(18) Dilution tests were carried out room temperature. Using an Eppendorf pipette, 4 mL of each formulation was diluted into 96 mL of water in a 100 mL glass graduated cylinder. The water having different levels of water hardness, e.g. 50 ppm, 342 ppm and 1000 ppm corresponding to concentrations of divalent ions (namely calcium and magnesium) was used. The time intervals were chosen to simulate diluted product standing over a typical “break” for the applicator (1, 2 or 4 hours) and overnight (24 hours). The dilutions were inverted 20× and allowed to stand. After standing for the desired time, the cylinders were noted for the volume of settled sediment and after the 24 hour reading they were subsequently subjected to cycles of inversions until the bottom of each cylinder was visually free of sediment. Inversions were performed manually (see Table X & Y for the results).

(19) TABLE-US-00006 TABLE X Active ingredient (A) Water hardness Sediment (mL) Particle size for dilutions 1 4 24 % # reinversions after Example (D95/D50, in microns) (ppm)) Hour Hours Hours serum standing overnight 3 1.35/0.57 50 — — — — 2 3 1.35/0.57 342 — — — — 2 3 1.35/0.57 1000 — — — — 2 4 9.87/2.07 50 — — — 1.0 15 4 9.87/2.07 342 — — 0.5 1.5 11 4 9.87/2.07 1000 — — 0.5 1.5 13 5 1.35/0.57 50 — — — — 7 5 1.35/0.57 342 — — — — 4 5 1.35/0.57 1000 — — 0.25 — 7 6 9.87/2.07 50 — — 0.5 1.0 8 6 9.87/2.07 342 — — 0.75 1.0 6 6 9.87/2.07 1000 — trace 0.5 1.0 10 D 1.35/0.57 50 — — — — 10 D 1.35/0.57 342 — — — — 10 D 1.35/0.57 1000 — — — — 10 C 9.87/2.07 50 — — — 1.0 14 C 9.87/2.07 342 — — 0.25 1.0 12 C 9.87/2.07 1000 — — 0.5 1.0 16

(20) TABLE-US-00007 TABLE Y active ingredient (D) active ingredient Water hardness Sediment, # reinversions particle Size (D95, (A) particle size for dilutions Sediment, Sediment, overnight, after standing Example D50 in microns) (D95, in microns) (ppm) 1 hr in mL 2 hr in mL in mL overnight 12 .sub.  8.52, 1.07 1.16 50 nil nil trace 22 12 .sub.  8.52, 1.07 1.16 1000 trace trace 1.5 12 G .sub.  8.52, 1.07 1.16 50 trace trace trace 31 G .sub.  8.52, 1.07 1.16 1000 trace trace 0.5 12 12(2) 4.56, 0.69 1.16 50 nil trace trace 23 12(2) 4.56, 0.69 1.16 1000 nil 0.25 2.5 5 G(2) 4.56, 0.69 1.16 50 nil trace trace 20 G(2) 4.56, 0.69 1.16 1000 trace 0.25 3 9 12(3) 1.34, 0.17 1.16 50 nil nil trace 6 12(3) 1.34, 0.17 1.16 1000 nil nil 0.25 6 G(3) 1.34, 0.17 1.16 50 nil nil trace 8 G(3) 1.34, 0.17 1.16 1000 nil trace 0.5 8 Note: Examples 12(2), 12(3) correspond compositionally to Example 12 and Examples G(2) and (G3) correspond compositionally to Example G, but the milling of the active ingredient (D) composition varied before admixing with the composition containing active ingredient (A).

Example B1

Translaminar Test Against Two Spotted Spider Mite Tetranychus urticae on French Beans (Phaseolus vulgaris)

(21) The underside of 2 week old bean plants was infested with a mixed population of T. urticae. The border of the underside of the leaves is surrounded with a gum barrier to prevent the mites to move to the upper side of the leaves. One day after the infestation plants were treated with a track sprayer from the top with 200 L/ha of Example 2 products containing different amounts of Penetrator Plus. Plants were incubated in the greenhouse for 9 days and the evaluation was done on mortality against eggs and mobile stages (see Table A for the results of ABA efficacy).

Example B2

Control of Tetranychus Sp. Adults on Vegetables

(22) In a plot size of 14 m2, two foliar spray applications of each composition were made at a treatment rate of 9 grams/ha (second was 7 days after the first application). Each treatment was done in three replicates. Each adjuvant was added to Example 1 in a tank-mix based on 17 ml product/ha. First application was conducted 71 days after transplanting and the evaluation was done on mortality against mobile stages by taking 20 leaves from each plot at different intervals (see Table B for the results).

Example B3

Control of Colorado Potato Battle on Potatoes

(23) In a plot size of 7.5 m2, one foliar spray application of each composition were made at a treatment rate of 1 grams/ha. Each treatment was done in three replicates. Each adjuvant was added to Example 1 in a tank-mix based on 2 ml product/ha. The application was conducted 53 days after planting and the evaluation was done on mortality against larvae by counting the live larvae present per plot at different intervals and converting the data in % of control (see Table C for the results).

Example B4

Control of Liriomyza trifolii Pupae on Chrysanthemums

(24) CHRYSANTHEMUMS potted plants were infested with a very high population of adult leafminers allowing them to lay eggs. Four days after the initial infestation plants were sprayed using a CO2 compressed backpack sprayer with an application volume of 1800 L/ha. Plants were incubated in the greenhouse for 9 days after the application and the evaluation was done by counting the number of pupae per plant obtained for each treatment (see Table D for the results).

Example B5

Residue Study

(25) In a plot size of 25 ft×5 ft with 2 rows of Romaine lettuce (30″ row spacing, 8″ plant spacing so ˜70 plants/plot), a single application of a treatment listed in Table below was made as a post foliar broadcast spray at a rate of 0.038 lb. a.i. per acre. Each treatment was done in two replicates with a control in each replicate. A minimum of ˜3 lb of lettuce leaves were collected for each sample. Samples were harvested at 0, 0.25 (corresponding to 6 hrs), 3, 7, 14 and 21 days after last application (DALA). The O-DALA samples were harvested as soon as the spray dried. Samples were transported frozen and were prepared by grinding the samples with dry ice using a tabletop mill. The abamectin residue was analysed using a HPLC-Fluorescence Method (see Table E for the results).

(26) TABLE-US-00008 Treatment Application Application Type GPA 1 Control — — 2 Example J Post foliar broadcast/on the day 29.5 (comparative) of harvest of mature leaves 3 Example A Post foliar broadcast/on the day 29.9 of harvest of mature leaves 4 Example 2 Post foliar broadcast/on the day 30.5 of harvest of mature leaves 5 Example J & Dyne- Post foliar broadcast/on the day 29.7 Amic ® at 0.25% v/v of harvest of mature leaves 6 Example A & Dyne- Post foliar broadcast/on the day 30.1 Amic ® at 0.25% v/v of harvest of mature leaves 7 Example 2 & Dyne- Post foliar broadcast/on the day 29.9 Amic ® at 0.25% v/v of harvest of mature leaves

Example B6

UV Degradation Study

(27) Photostability was assessed using an Atlas SUNTEST XLS+ unit (Part number 55007820) which utilises a xenon arc-lamp and a Special UV-filter (Part number 56052371) to simulate natural sunlight in both spectrum and intensity.

(28) Treatments were diluted either in ultra-pure water (or in ultra-pure water containing 0.1% Penetrator Plus) to give dilutions that were 125 ppm wrt abamectin. 8×2 ul drops were dispensed using a Hamilton PB600 repeating dispenser fitted with a glass 100 μl Hamilton syringe onto pre-scored glass microscope slides—typically seven or eight for each treatment. These were allowed to dry prior to being covered with clean UV transparent silica slides to minimise volatile loss from the deposit. One slide for each compound was not irradiated and designated as time zero (T0). The other prepared slides were placed in the SUNTEST XLS+ on a water-cooled sample table (attached to a circulating water bath set to 15° C.) and irradiated for time periods ranging from 30 minutes up to 43 hours.

(29) To quantify the amount of compound remaining, one slide was removed for each treatment from the SUNTEST unit, broken in half across the shaft of a small spatula, sandwiched with the clean sides together and placed in a 60 ml wide necked glass screw topped jar. The silica slide was rinsed with 2×2.5 mls of 50:50 (80/20 MeCN/THF): 0.1% H3PO4 into the jar, the lid replaced and the jar sonicated for 30 minutes. All jars were left standing at room temperature in covered boxes prior to analysis by LC with MS detection without further preparation (see Table F for the results).

Example B7

(30) Two golden Delicious apple plants grown outside in a propagation container (1-2 years old) were treated with the products. The treatment areas for new and old leaves were defined and marked before product application. A horizontal band was marked on each leaf (approximately ¾ of the way down from the leaf tip) with a permanent marker pen. All treatments were applied using a hand held pipette to the marked areas on each leaf as 10×0.5 ul droplets (corresponding to 25 ug Al per leaf) with four replicate leaves per treatment, and the plants left outside. The products were AGRIMEK, Example 2, and Example 2 with 0.25% v/v Horticultural spray oil (i.e summer oil). After 1, 3 and 6 days after treatment, abamectin residues were assessed either on the leaf surface or inside the leaf tissue on all four leaves per product treatment. Surface analysis involved washing the leaf with acetone, followed by a chloroform and then LCMS, while inside the leaf tissue analysis involved freezing the leaves, homogenising in 5 ml acetone, centrifuging and 1 ml of the resulting supernatant used for LCMS analysis (see Table G & H for the results).

(31) TABLE-US-00009 TABLE A control of Tetranychus urticae Varying amounts of Penetrator Plus, based on %, v/v ABA a.i ppm 0 0.05 0.1 0.2 12.5 35 100 100 100 3 0 97 100 100 0.8 0 40 96 100 0.2 0 0 47 97

(32) TABLE-US-00010 TABLE B control of tetranychus sp. adults ABA formulation, Adjuvant, 17 ml 3DAA1, 5DAA1, 7DAA1, 3DAA2, 7DAA2, 10DAA2, 15DAA2, 9 g Al/ha product/ha % % % % % % % Example K — 75 75 61 83 79 78 74 (comparative) Example B — 62 41 41 54 62 64 49 Example 2 — 79 55 56 67 79 68 58 Example B ADIGOR 65 52 40 60 78 75 61 Example B SILWET L77 57 50 42 59 81 77 69 Example B ATLOX 58 54 41 63 77 71 67 SEMKOTE E-135 Example B ATPLUS 463 76 56 45 78 78 82 77

(33) TABLE-US-00011 TABLE C control of Colorado potato bettle ABA formulation, Adjuvant, 2 ml 1DAA1, 3DAA1, 5DAA1, 7DAA1, 9 g Al/ha product/ha % % % % 11DAA1, Example K — 100 97 74 66 35 (comparative) Example 2 — 100 100 100 100 97 Example B ADIGOR 100 100 100 100 97 Example B SILWET L77 100 100 99 100 98 Example B ATLOX SEMKOTE E-135 100 100 100 100 98 Example B ATPLUS 463 100 100 97 100 97 Example B ALKAMUL BR 100 100 100 100 97 Example B TURBOCHARGE D 100 100 100 100 97 Example B TWEEN 80 100 100 98 100 95 Example B CET SPEED* 100 100 95 100 97 *applied at 10.1 ml product/ha

(34) TABLE-US-00012 TABLE D control of Liriomyza Trifolii pupae 9DAA1, % Example J (comparative) 52 Example A 0 Example 1 21 Example B 16 Example 2 44

(35) TABLE-US-00013 TABLE E recovered abamectin (ppb) Abamectin (ppb) Ex J & Ex. A & Ex. 2 & Interval Dyne- Dyne- Dyne- (DALA) Ex. J Ex. A Ex. 2 Amic ® Amic ® Amic ® 0 301 319 407 313 402 397 0.25 192 340 347 203 195 133 3 63 192 228 99 94 110 7 16 112 143 39 72 38 14 9 52 53 12 37 22 21 6 62 48 9 40 11 Note: Residues reported above represent the average of two replicates expressed as Abamectin B1a (avermectin B1a and its 8,9-Z isomer) plus Abamectin B1b No residues (<2.00 ppb) were detected in any of the controls analyzed during this study.

(36) TABLE-US-00014 TABLE F recovered abamectin % ABAMECTIN REMAINING - TIME AFTER IRRADIATION (Hours) Treatment 0.5 1 3 6 12 24 43 Example A 88.2 49.1 40.5 30.0 6.5 1.3 Example 2 95.5 39.0 29.4 26.3 4.2 1.1 Example 7 93.7 55.2 29.7 19.6 4.2 1.7 Example J (comparative) 91.1 35.0 25.5 10.3 8.5 4.4 Example A + Penetrator Plus 49.0 42.1 38.5 29.3 13.5 6.5 0.8 Example 2 + Penetrator Plus 51.0 38.9 26.4 15.9 4.0 0.8 0.0 Example 7 + Penetrator Plus 41.9 37.7 26.0 12.9 5.6 0.6 0.0 Example J + Penetrator Plus 59.5 41.6 25.3 19.9 6.5 1.3 1.2

(37) TABLE-US-00015 TABLE G micrograms of abamectin inside the leaf tissue Time Example K Example 2 Example 2 + oil* 0 0.22 0.24 0.39 1 0.23 0.23 0.45 3 0.15 0.14 0.13 6 0.33 0.16 0.33 *oil is Horticultural spray oil, i.e. summer oil

(38) TABLE-US-00016 TABLE H micrograms of abamectin on the leaf surface Time Example K Example 2 Example 2 + oil* 0 12.87 12.54 7.74 1 8.91 12.57 4.58 3 1.19 7.65 2.65 6 0.77 4.10 2.02 *oil is Horticultural spray oil, i.e. summer oil