WO2016113665A1

WO2016113665A1 - Agricultural composition

Info

Publication number: WO2016113665A1
Application number: PCT/IB2016/050116
Authority: WO
Inventors: Warren John BANKS; David Anthony WRIGHT; Trevor Anthony Jackson; Terrence John Smith; Per John WESSMAN
Original assignee: Agresearch Limited
Priority date: 2015-01-13
Filing date: 2016-01-12
Publication date: 2016-07-21
Also published as: AU2016207758B2; AU2016207758A1; AU2016207758C1

Abstract

The present invention provides granules comprising a deformable core, a binder and an exterior coating, in addition to methods of manufacturing and using such granules, for example, for controlling pests and improving plant health and production, such as treating the soil to reduce pests or to increase pasture production. 5

Description

AGRICULTURAL COMPOSITION

FIELD OF THE INVENTION

[0001] The present invention relates to granules comprising a deformable core, a binder and an exterior coating comprising a particulate material, methods of preparing such granules, and application of such granules into or on to soil.

BACKGROUND TO THE INVENTION

[0002] Biological materials, such as beneficial microorganisms including bacteria, are useful alternatives to chemical agents for the improvement and/or maintenance of soil and plant health, including the control of pests. [0003] Biological materials are sensitive to environmental exposure, particularly desiccation and UV radiation. The utility of biological materials, for example, microbes, for application into or on to soil is limited by the sensitivity of such materials to environmental conditions on the soil surface prior to entry into the soil and during storage of compositions comprising the biological material, such as granules. [0004] There remains a need for granules comprising biological material that are suitable for application on to or into the soil and that adequately protect the biological material in the granule until the biological material is released from the granule and enters the soil profile.

[0005] It is an object of the present invention to provide granules that meet one or more of these needs, or to at least provide the public with a useful choice.

SUMMARY OF THE INVENTION

In a first aspect the invention relates to granules, the granules comprising a deformable core,

a binder incorporated within and/or coated on the deformable core, and an exterior coating that at least partially coats the deformable core

comprising a particulate material, the particulate material comprising particles having a mean size of from about 0.1 μηη to about 50 μηη.

[0007] For example, in one embodiment the granules may comprise

a) a deformable core comprising

(i) a substrate, (ii) a first coating that at least partially coats the substrate, the first

coating comprising biological material, and

(iii) a second coating that at least partially coats the first coating, the

second coating comprising at least one particulate desiccant and a binder, and

b) an exterior coating that at least partially coats the deformable core, the

exterior coating comprising a particulate material, the particulate material comprising particles having a mean size of from about 0.1 μηη to about 50 m.

For example, in a further embodiment the granules may comprise a deformable core comprising

(i) zeolite,

(ii) a first coating that at least partially coats the substrate, the first

coating comprising biological material, and optionally a biodegradable polymer and/or a non-cytotoxic oil, and

(iii) a second coating that at least partially coats the first coating, the

second coating comprising at least one particulate desiccant and a polymeric compound, and

an exterior coating that at least partially coats the deformable core, the exterior coating comprising microsilica particles.

[0009] In a second aspect the invention relates to an agricultural composition comprising granules of the present invention.

[0010] In a third aspect the invention relates to a method of producing a granule, the method comprising

a) providing a deformable core comprising a binder incorporated within and/or coated on the deformable core,

b) at least partially coating the deformable core with a particulate material, and comprising particles having a mean size of from about 0.1 m to about 50 pm to form a coated granule.

[0011] For example, in one embodiment the method may comprise

a) providing a substrate,

b) coating the substrate with a first coating comprising biological material to form a first coated material,

c) coating the first coated material with a second coating comprising at least one particulate desiccant and with a binder to form the deformable core, d) coating the deformable core with microsilica to form a coated granule, and e) drying the coated granule.

[0012] For example, in a further embodiment the method may comprise

a) providing a substrate,

b) coating the substrate with a first coating comprising biological material, and optionally a biodegradable polymer and/or a non-cytotoxic oil to form a first coated material,

c) coating the first coated material with a second coating comprising at least one particulate desiccant and with a polymeric compound to form a deformable core,

d) coating the deformable core with microsilica to form a coated granule, and e) drying the coated granule.

[0013] In a fourth aspect the invention relates to the use of a particulate material comprising particles having a mean size of from about 0.1 μηη to about 50 μηη to at least partially coat deformable granules to form coated granules that are substantially resistant to deformation upon application of a pressure of up to about 0.5 kg/cm².

[0014] For example, in one embodiment, the particulate material is microsilica, such that the invention relates to the use of microsilica to at least partially coat deformable granules to form coated granules that are substantially resistant to deformation upon application of a pressure of up to about 0.5 kg/cm².

[0015] In a fifth aspect the invention relates to a method of distributing granules or a composition of the invention into or on soil, the method comprising

a) supplying granules or a composition of the invention to a distribution device, and

b) applying the granules or composition into or on to soil using the distribution device.

[0016] In a sixth aspect the invention relates to a method of treating soil to control a pest, preferably an insect pest, comprising applying granules or a composition of the invention into or on to soil.

[0017] In a seventh aspect the invention relates to a method of treating soil to maintain or increase plant growth, the method comprising applying granules or a

composition of the invention into or on to soil. [0018] In an eighth aspect the invention relates to a method of treating soil of pastoral land to maintain or increase pasture production, the method comprising applying granules or a composition of the invention into or on to soil.

[0019] In a ninth aspect the invention relates to use of granules or a composition of the invention to control pests, preferably insect pests.

[0020] In a tenth aspect the invention relates to use of granules or a composition of the invention to maintain or increase plant growth.

[0021] In an eleventh aspect the invention relates to use of granules or a composition of the invention to maintain or increase pasture production. [0022] Any one or more of the following embodiments may relate to any of the aspects described herein or any combination thereof.

Core

[0023] In one embodiment the deformable core may comprise

(i) a substrate,

(ii) a first coating that at least partially coats the substrate, the first

coating comprising biological material, and

(iii) a second coating that at least partially coats the first coating, the

second coating comprising at least one particulate desiccant and a binder. [0024] In various embodiments the first coating may coat at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% of the surface of the substrate, and suitable ranges may be selected between any of these values (for example, about 50 to about 100, about 60 to about 100, about 70 to about 100, about 80 to about 100, or about 90 to about 100%). In one embodiment the first coating coats at least about 90% of the surface of the substrate. In another embodiment the first coating fully coats the substrate.

[0025] In various embodiments the second coating may coat at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% of the first coating, and suitable ranges may be selected between any of these values (for example, about 50 to about 100, about 60 to about 100, about 70 to about 100, about 80 to about 100, or about 90 to about 100%). In one embodiment the second coating coats at least about 90% of the first coating. In another embodiment the second coating fully coats the first coating. [0026] In various embodiments the substrate is selected from the group comprising a clay, a clay mineral, a seed, a pelletised grain, a granulate or an extruded granule, or a combination of any two or more thereof. In a preferred embodiment the substrate is selected from the group comprising a clay, a clay mineral, a pelletised grain, a granulate or an extruded granule, or a combination of any two or more thereof.

[0027] In various embodiments the substrate is selected from the group comprising a clay granule, a silicate mineral, an aluminosilicate mineral, for example, zeolite,

diatomaceous earth or perlite, vermiculite, a seed, for example, a vegetable seed, a fertiliser granule, or a combination of any two or more thereof. In various embodiments the substrate may comprise a seed, for example an angiosperm, vegetable, legume, cereal or conifer seed. In various embodiments the seed comprises a spinach, carrot, onion, soybean, lucerne, plantain, brassica, maize rye grass, canola or clover seed. In various embodiments the substrate may comprise wheat, barley, bran, maize, rye, rice, sorghum, millet, oats, forage brassica, canola or triticale, or a combination of any two or more thereof. In various embodiments the substrate may comprise a granule comprising a fertiliser, for example, a granule of urea, superphosphate, monoammonium phosphate (MAP), diammonium phosphate (DAP, single superphosphate (SSP), triple superphosphate (TSP), calcium ammonium nitrate (CAN) or muriate of potash (MOP).

[0028] In one embodiment the first coating may comprise one or more biodegradable polymers. In another embodiment the first coating may comprise biological material, a biodegradable polymer and/or a non-cytotoxic oil.

[0029] In one embodiment the biodegradable polymer may comprise a polysaccharide. In one embodiment the biodegradable polymer may comprise an exopolysaccharide produced by a microorganism, for example, an exopolysaccharide produced by

Achromobacter, Acetobacter, Acinetobacter, Agrobacterium, Alcaligenes, Aspergillus,

Aureobasidium, Aureomonas, Azotobacter, Bacillus, Beijerinckia, Lactobacillus, Lentinus, Leuconostoc, Mucorales, Pantoea stewartii, Pseudomonas, Rhizobium, Schizophylum, Sclerotium, Serratia, Sinorhizobium, Sphingomonas, Streptococcus, Xanthomonas, Zooglea, or Zymomonas spp. [0030] In one embodiment the biodegradable polymer may comprise a gum such as a plant gum. In various embodiment the biodegradable polymer may be selected from the group comprising xanthan gum, agar, alginate, cassia, dammar, pectin, beta-glucan, glucomannan, mastic, chicle, psyllium, spruce gum, gellan gum, acacia gum, guar gum, locust bean gum, carrageenans, gum arabic, karaya gum, ghatti gum, tragacanth gum, konjac gum, tara gum, pullulan or a combination of any two or more thereof. [0031] In another embodiment the biodegradable polymer may comprise a synthetic polysaccharide, for example a synthetic polymer of sucrose. In one embodiment the polysaccharide may comprise Ficoll^®.

[0032] In various embodiments the first coating may comprise about 10, 15, 20, 25, 30, 25, 40, 45 or about 50% by weight of the biodegradable polymer, and useful ranges may be selected between any of these values, for example, from about 10% to about 50% by weight.

[0033] In one embodiment the first coating may comprise a non-cytotoxic oil. In various embodiments the non-cytotoxic oil may comprise a plant, animal, paraffin or mineral oil. For example, in various embodiments the non-cytotoxic oil may be selected from the group comprising canola, olive, sunflower seed, palm, coconut, corn, peanut, safflower, sesame, soybean, peanut, wheat germ, rice bran, flaxseed, palm or grapeseed oil, hydrolysed oils, or a combination of any two or more thereof. In another embodiment, the non-cytotoxic oil may comprise a marine oil, for example a fish, seal, krill or seaweed oil. In various embodiments the non-cytotoxic oil may comprise Excel^® Oil, Excel^® Organic Oil, Organic JMS Stylet-Oil or Syn Oil.

[0034] In various embodiments the first coating may comprise about 10, 15, 20, 25, 30, 25, 40, 45 or about 50% by weight of the non-cytotoxic oil, and useful ranges may be selected between any of these values, for example, from about 10% to about 50% by weight.

[0035] In various embodiments the biological material may comprise one or more microorganisms, hormones, pheromones, spores, proteins or a combination of any two or more thereof. In various embodiments the biological material may comprise bacteria, yeast, fungi, or an endophyte. In various embodiments the biological material is agriculturally and/or horticulturally useful, for example, the biological material is pesticidal and/or insecticidal, and/or supports plant growth and/or development, or any combination thereof.

[0036] In various embodiments the biological material may comprise Serratia (for example, Serratia entomophila or Serratia proteomaculans), Xanthamonas, Pseudomonas, Rhizobium, Beauveria, Penicillium, Metarhizium, Bifidobacterium, Lactobacillus,

Streptococcus (Enterococcus), Yersinia (for example, Yersinia entomophaga) Trichoderma, Pseudomonas, Bacillus, Pasteuria, Azobacter, Enterobacter, Azospirillum, Cyanobacteria, Gliocladium, Coniotherium, Verticillium, Paecilomyces, Streptomycetes, Chromobacterium, Rhanella, Burkholderia Paenibacillus, Collimonas, Sinorhizobium, Pantoea, Lecanicillum, Erwinia, Pediococus, Sclerotinia, Leuconostoc, Aeromonas, Neptunomonas, Klebsiella, Ponchonia, Brevibacillus, Acinetobacter or a combination of any two or more thereof. In one embodiment the biological material may comprise one or more bacteria and one or more fungi. In one exemplary embodiment the biological material comprises Serratia entomophila and Metarhizium anisopliae. In various embodiments the protein may comprise a metabolite produced by a microorganism, for example a toxin produced by a Yersinia, Bacillus or Metarhizium species. In a preferred embodiment the biological material may comprise Serratia entomophila, Pseudomonas chloraphis, Burkholderia terricola, Rhizobium leguminosarum biovar TA1, Serratia proteomaculans, Penicillium janczewskii, Beauveria bassiana, Metarhizium anisopliae, Bacillus subtilis, or a combination of any two or more thereof. [0037] In various embodiments the first coating may comprise about 10, 15, 20, 25, 30, 25, 40, 45, 50, 55, 60, 65, 70, 75 or about 80% by weight of a composition comprising the biological material, and useful ranges may be selected between any of these values, for example, from about 10% to about 80% by weight.

[0038] In one embodiment the first coating may further comprise one or more layers of one or more particulate desiccants as described below.

[0039] In one embodiment, the granules may further comprise an agricultural agent, that is, an agent that is beneficial for agricultural and/or horticultural purposes. In various embodiments the granule may comprise one or more fertilisers, one or more trace elements, one or more nitrification inhibitors, one or more urease inhibitors, one or more plant growth promoters, such as hormones, or one or more pesticides, for example fungicides. For example, in one embodiment the agricultural agent may comprise a NPK fertiliser. In various embodiments the agricultural agent may comprise one or more plant hormones selected from the group comprising gibberellins, auxins, cytokinins, abscisic acid, ethylene, salicylic acid, brassinosteroids, jasmonates, peptide hormones, polyamines, nitric oxide, and strigolactones, or a combination of any two or more thereof.

[0040] In various embodiments the granules may further comprise a surfactant. In various embodiments the surfactant is selected from the group comprising nonionic surfactants, anionic surfactants, cationic surfactants and/or amphoteric surfactants.

Examples of surfactants include but are not limited to Tween™ and Triton™ (Rohm and Hass Company), Fortune^®, Pulse, C. Daxoil^®, Codacide oil^®, D-C. Tate^®, Supamet Oil, Bond^®, Penetrant, Glowelt® and Freeway, Citowett®, Fortune Plus™, Fortune Plus Lite, Fruimec, Fruimec lite, alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and

dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.

[0041] In various embodiments the granules may further comprise a lubricant. In various embodiments the lubricant is selected from the group comprising a lipid such as a fat or oil, for example magnesium stearate, vegetable stearin, or stearic acid, or a mineral, for example talc or silica.

[0042] In various embodiments the particulate desiccant may be selected from the group comprising a clay, a silicate mineral, a calcium salt, or a volcanic glass. In various embodiments the particulate desiccant may be selected from the group comprising a sulphate mineral, an aluminosilicate, a phyllosilicate, a clay mineral, a silicate, or a combination of any two or more thereof. In various embodiments the particulate densifier may be selected from the group comprising bentonite, montmorillonite, gypsum, zeolite, kaolin, calcium carbonate, calcium phosphate, perlite, celite, diatomaceous earth, talc, silicon dioxide, or a combination of any two or more thereof. In a preferred embodiment the particulate desiccant comprises bentonite, gypsum, or bentonite and gypsum. In a particularly contemplated embodiment the particulate desiccant comprises bentonite and gypsum.

[0043] In one embodiment the second coating may comprise one or more

disintegrants. In various embodiments the disintegrant may comprise a starch, preferably a pre-gelatinised starch, a cross-linked polymer, or an effervescent agent. In various embodiments the disintegrant may comprise potato starch, peat, rice powder, corn starch, sodium starch glycolate, cellulose, methylcellulose, sodium alginate, polyvinylpyrrolidone, croscarmellose sodium, alginic acid, citric acid, sodium bicarbonate or tartaric acid or a combination of any two or more thereof.

[0044] In various embodiments the granules may comprise a particulate desiccant in an amount of about 0.1, 0.25, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5 or 8 fold relative to the mass of the core, and useful ranges may be selected between any of these values, for example, from about 0.25 to about 8, about 0.25 to about 5, about 0.25 to about 3, about 0.5 to about 8, about 0.5 to about 5, about 0.5 to about 3, about 1 to about 8, about 1 to about 5, about 1 to about 4, about 1 to about 3, about 2 to about 8, about 2 to about 7, about 2 to about 6, about 2 to about 5, about 2 to about 4, about 3 to about 8, about 3 to about 7, about 3 to about 6, about 3 to about 5, about 4 to about 8, about 4 to about 7, about 4 to about 6, about 5 to about 8, about 5 to about 7, or about 6 to about 8 fold. In a particularly contemplated embodiment the granule comprises particulate desiccant in an amount of from about 1 fold to about 4 fold relative to the mass of the core.

[0045] In various embodiments the second coating may comprise at least about 50, 60, 70, 75, 80, 85, 90, 95 or about 99% by weight of particulate desiccant, and useful ranges may be selected between any of these values, for example, from about 50 to about 99, about 50 to about 95, about 50 to about 90, about 50 to about 85, about 50 to about 80, about 50 to about 75, about 60 to about 99, about 60 to about 95, about 60 to about 90, about 60 to about 85, about 70 to about 99, about 70 to about 95, about 70 to about 90, about 70 to about 85, about 80 to about 99, about 80 to about 95, about 80 to about 90, about 90 to about 99, or about 90 to about 99% by weight of particulate desiccant. [0046] In various embodiments the second coating may comprise about 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12.5, 13, 14 or about 15% by weight of disintegrant, and useful ranges may be selected between any of these values, for example, from about 0.1 to about 15, about 0.1 to about 12.5, about 0.1 to about 10, about 0.1 to about 8, about 0.1 to about 6, about 0.5 to about 15, about 0.5 to about 12.5, about 0.5 to about 10, about 0.5 to about 8, about 0.5 to about 6, about 1 to about 15, about 1 to about 12.5, about 1 to about 10, about 1 to about 9, about 1 to about 8, about 1 to about 7, about 2 to about 15, about 2 to about 12.5, about 2 to about 10, about 2 to about 9, about 2 to about 8, about 2 to about 7, about 2 to about 6, about 3 to about 15, about 3 to about 12.5, about 3 to about 10, about 3 to about 9, about 3 to about 8, about 3 to about 7, about 4 to about 15, about 4 to about 12.5, about 4 to about 10, about 4 to about 9, about 4 to about 8, about 4 to about 7, about 5 to about 15, about 5 to about 12.5, about 5 to about 10, about 5 to about 9, about 5 to about 8, about 5 to about 7%, by weight of disintegrant.

[0047] In various embodiments the mass of the second coating applied to the granules may be about 0.1 : 1, 0.25 : 1, 0.5 : 1, 1 : 1, 2: 1, 3 : 1, 4: 1, 5: 1, 6: 1, 7 : 1 or 8: 1 relative to the combined mass of the substrate and first coating. Useful ranges may be selected between any of these values, for example, from about 0.1 : 1 to about 8: 1, about 0.1 : 1 to about 6: 1, about 0.1 : 1 to about 5 : 1, about 0.1 : 1 to about 4: 1, about 0.5 : 1 to about 8: 1, about 0.5 : 1 to about 7 : 1, about 0.5 : 1 to about 6: 1, about 0.5 : 1 to about 5: 1, about 0.5 : 1 to about 4: 1, about 1 : 1 to about 8: 1, about 1 : 1 to about 8: 1, about 1 : 1 to about 7: 1, about 1 : 1 to about 6: 1, about 1 : 1 to about 5: 1, about 1 : 1 to about 4: 1, about 2: 1 to about 8: 1, about 2: 1 to about 6: 1, about 2 : 1 to about 5 : 1, or about 2 : 1 to about 4: 1 relative to the mass of the substrate and first coating.

Binder

[0048] In one embodiment the binder may comprise one or more or two or more polymeric compounds. In various embodiments the binder may comprise one or more or two or more polyhydroxyl compounds.

[0049] In various embodiments the binder may be agriculturally and/or horticulturally acceptable, non-cytotoxic, food grade and/or biodegradable.

[0050] In various embodiments the polymeric compound may be a polyhydroxyl compound, a polymer or copolymer of a C1-C6 alkyl substituted with one or more groups selected from the group comprising lactams or 2-pyrollidone, a shellac resin, a disaccharide, a polyelectrolyte, a polyethylene glycol, a polyethylene oxide, a polyacrylamide, a polyester, a cellulose, a lignin, a biodegradable gum, an oligopeptide, a polypeptide or a latex.

[0051] In various embodiments the polymeric compound may be a polyhydroxyl compound, a polymer or copolymer of a C1-C6 alkyl substituted with one or more groups selected from the group comprising lactams or 2-pyrollidone, for example,

polyvinylpyrollidone, or a latex.

[0052] In one embodiment the polymeric compound may be a latex polymer, for example, EC 23009. In various embodiments the polymeric compound may be a

polyvinylpyrrolidone, shellac resin, a disaccharide, an oligosaccharide, a polysaccharide, a cellulose or a starch.

[0053] In various embodiments the polyhydroxyl compound may be selected from the group comprising a polyvinyl alcohol, a polyvinyl alcohol co-polymer, a polysaccharide, or an oligosaccharide. In one embodiment the polyhydroxyl compound may be a polyvinyl alcohol-polyethylene glycol co-polymer (e.g. Kollicoat® Protect). In a particularly preferred embodiment the polyhydroxyl compound is a polyvinyl alcohol.

[0054] In various embodiments the polyhydroxyl compound may be selected from the group comprising a polyvinyl alcohol, a polyethylene oxide, methyl cellulose, a polyvinyl alcohol-polyethylene glycol co-polymer (e.g. Kollicoat^® Protect) or gum arabic. In a particularly preferred embodiment the polyhydroxyl compound is a polyvinyl alcohol.

[0055] In various embodiments the polysaccharide may be selected from the group comprising a starch, a dextrin, chitosan, a gum or a synthetic polysaccharide. In various embodiments the starch may be potato starch or maize starch. In one embodiment the starch is a pre-gelatinised starch. In one embodiment the dextrin may be maltodextrin. In various embodiments the gum may be xanthan gum or gum arabic. In one embodiment the synthetic polysaccharide may be Ficoll^®. [0056] In one embodiment the polyhydroxyl compound may be a polymer or copolymer of

(1) a C2-C6 hydroxyalkyl, or

(2) a C2-C10 hydroxyalkyl, optionally substituted with acyl and/or optionally

comprising an ether moiety, for example, methacrylic acid-ethyl acrylate copolymer (Kollicoat® MAE100).

[0057] In various embodiments the polyelectrolyte may be polyacrylic acid or xanthan gum.

[0058] In one embodiment the polymer or copolymer of a C1-C6 alkyl may be substituted with one or more γ-lactam groups. In one embodiment the polymer or copolymer of a C1-C6 alkyl substituted with one or more groups selected from the group comprising lactams or 2-pyrollidone is polyvinylpyrollidone.

[0059] In one embodiment the polyester is an aliphatic polyester. In one embodiment the polyester is polylactic acid. In various embodiments the cellulose may be selected from the group comprising methyl cellulose, carboxymethylcellulose, hydroxypropyl

methylcellulose and hydroxyethyl cellulose. In various embodiments the biodegradable gum may be an exopolysaccharide produced by a microorganism or a plant gum as described above. In various embodiments the biodegradable gum may be xanthan gum or gum arabic. In various embodiments the polypeptide is gluten or gelatin. In one embodiment the latex is EC 23009. [0060] In various embodiments the polymeric compound may be a compound selected from the group comprising copolymers of vinyl pyrrolidone, and vinyl acetate, poly (methyl vinyl ether), maleic anhydride copolymers, free acids of the copolymer of methyl vinyl ether and maleic anhydride, vinyl pyrrol idone/styrene copolymers, vinyl acetate/butyl acrylate copolymers, vinyl acetate homopolymers, acrylic copolymers, styrene/acrylic ester copolymers, vinyl acetate/ethylene copolymers and polyvinyl acetate, or a combination of any two or more thereof.

[0061] In various embodiments the polyhydroxyl compound may comprise at least 2, 3, 4, 5, 10, 20, 50, 100, 200, 300, 400, 500, 750, 800, 1,000, 1,200, about 1,500, about 2,000, about 3,000, about 4,000 or at least about 5,000 hydroxyl groups, and useful ranges may be selected between any of these values, for example, from about 2 to about 5,000, about 2 to about 3,000, about 2 to about 1,500, about 2 to about 1,000, about 2 to about 800, about 2 to about 500, about 2 to about 300, about 2 to about 50, about 10 to about 5,000, about 10 to about 3,000, about 10 to about 1,500, about 10 to about 1,000, about 10 to about 500, about 10 to about 300, about 10 to about 100, about 10 to about 50, about 50 to about 5,000, about 50 to about 4,000, about 50 to about 3,000, about 50 to about 1,500, about 50 to about 1,000, about 50 to about 800, about 50 to about 500, about 50 to about 200, about 100 to about 5,000, about 100 to about 3,000, about 100 to about 1,500, about 100 to about 1,000, about 100 to about 800, about 100 to about 500, about 300 to about 5,000, about 300 to about 3,000, about 300 to about 1,500, about 300 to about 1,000, about 300 to about 800, about 300 to about 500, about 500 to about 5,000, about 500 to about 4,000, about 500 to about 3,000, about 500 to about 1,500, about 500 to about 1,000, about 800 to about 5,000, about 800 to about 4,000, about 800 to about 3,000, about 800 to about 1,500, about 800 to about 1,000, about 1,000 to about 5,000, about 1,000 to about 4,000, about 1,000 to about 3,000, about 1,000 to about 2,000, about 1,500 to about 5,000, about 1,500 to about 4,000, or from about 1,500 to about 3,000 hydroxyl groups.

[0062] In various embodiments the polymeric compound may comprise a polymer of a monomer comprising at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 hydroxyl groups, and useful ranges may be selected between any of these values, for example, from about 1 to about 10, about 1 to about 8, about 1 to about 6, about 1 to about 5, about 1 to about 4, about 1 to about 3, about 2 to about 10, about 2 to about 8, about 2 to about 6, about 2 to about 4, about 3 to about 10, about 3 to about 8, about 3 to about 6, about 3 to about 5, about 4 to about 10, about 4 to about 8, about 4 to about 7, about 4 to about 6, about 5 to about 10, about 5 to about 9, about 5 to about 8, about 5 to about 7, about 6 to about 10, about 6 to about 9, about 6 to about 8, about 7 to about 10, about 7 to about 9, or about 8 to about 10 hydroxyl groups.

[0063] In various embodiments the polymeric compound may have an average molecular weight of about 1, 2, 5, 10, 20, 22.5, 24.5, 25, 30, 40, 50, 75, 80, 90, 100, 118, 120, 125, 126, 130, 140, 150, 200, 250, 300 or about 350 kDa, and useful ranges may be selected between any of these values, for example, from about 1 to about 350, 5 to about 350, about 5 to about 250, about 5 to about 200, about 5 to about 150, about 5 to about 125, about 5 to about 100, about 5 to about 75, about 5 to about 50, about 10 to about 350, about 10 to about 250, about 10 to about 200, about 10 to about 150, about 10 to about 100, about 10 to about 75, about 10 to about 50, about 25 to about 350, about 25 to about 250, about 25 to about 200, about 25 to about 150, about 25 to about 125, about 25 to about 100, about 25 to about 75, about 25 to about 150, about 25 to about 125, about 25 to about 100, about 25 to about 75, about 50 to about 350, about 50 to about 250, about 50 to about 200, about 50 to about 150, about 50 to about 150, about 50 to about 100, about 75 to about 350, about 75 to about 250, about 75 to about 200, about 75 to about 150, about 75 to about 100, about 100 to about 350, about 100 to about 250, about 100 to about 200, about 100 to about 150, or from about 100 to about 150 kDa.

[0064] In various embodiments the polyhydroxyl compound may have a degree of hydrolysis of at least about 80, 82.5, 85, 87.5, 90, 92.5, 95 or 98 mol%, and useful ranges may be selected between any of these values, for example, from about 80 to about 100, about 80 to about 98, about 80 to about 95, about 80 to about 90, about 85 to about 100, about 85 to about 98, about 85 to about 95, about 85 to about 90, about 90 to about 100, about 90 to about 98, or from about 90 to about 95 mol%.

[0065] In one embodiment the binder may further comprise a plasticiser, for example, an acetylated monoglyceride or alkyl citrate, a polyethylene glycol or monopropylene glycol. [0066] In various embodiments, the binder, second binder and/or second coating may comprise a dye, for example, Rhodamine B500, Methyl Violet, Blue 2313, Eosine Y, Sunset Yellow, Magenta, Blue 23123, Pigment Green 7, Tartrazine, Malachite Green, Auramine 0, Oil Yellow 21756, Green 19102 and Methylene Blue 2B, or titanium dioxide-coated micas (lustres) such as 100 Silver Pearl, 120 Lustre Pearl, 235 Green Pearl, 300 Gold Pearl, 500 Bronze Pearl and 504 Red Pearl.

[0067] In various embodiments the granules may comprise about 0.01, 0.025, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9 or 1% of the binder relative to the mass of the core of the granule, and useful ranges may be selected between any of these values, for example, from about 0.01 to about 0.1, 0.05 to about 1, 0.05 to about 0.4, about 0.05 to about 0.35, about 0.05 to about 0.3, about 0.05 to about 0.25, about 0.05 to about 0.2, about 0.15 to about 1, about 0.1 to about 0.4, about 0.1 to about 0.35, about 0.1 to about 0.3, about 0.1 to about 0.25, about 0.1 to about 0.2, about 0.15 to about 1, about 0.15 to about 0.4, about 0.15 to about 0.35, about 0.15 to about 0.3, about 0.15 to about 0.25, about 0.15 to about 0.2, about 0.2 to about 1, about 0.1 to about 0.4, about 0.1 to about 0.35, about 0.1 to about 0.3, about 0.1 to about 0.25, about 0.1 to about 0.2, about 0.2 to about 1, about 0.2 to about 0.4, about 0.2 to about 0.35, about 0.2 to about 0.3, about 0.25 to about 1, about 0.25 to about 0.4, about 0.25 to about 0.35, about 0.25 to about 0.3, about 0.3 to about 1, about 0.3 to about 0.4, or about 0.4 to about 1% binder relative to the mass of the deformable core of the granules. [0068] In one embodiment the granules may comprise at least one layer of the second coating. In one embodiment the granules may comprise two or more layers of the second coating comprising alternating layers of the binder and the second coating.

[0069] In one embodiment the granules may comprise a second binder. In various embodiments the granules may comprise about 0.01, 0.025, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9 or 1% of the second binder relative to the mass of the core of the granule, and useful ranges may be selected between any of these values, for example, from about 0.01 to about 0.1, 0.05 to about 1, 0.05 to about 0.4, about 0.05 to about 0.35, about 0.05 to about 0.3, about 0.05 to about 0.25, about 0.05 to about 0.2, about 0.15 to about 1, about 0.1 to about 0.4, about 0.1 to about 0.35, about 0.1 to about 0.3, about 0.1 to about 0.25, about 0.1 to about 0.2, about 0.15 to about 1, about 0.15 to about 0.4, about 0.15 to about 0.35, about 0.15 to about 0.3, about 0.15 to about 0.25, about 0.15 to about 0.2, about 0.2 to about 1, about 0.1 to about 0.4, about 0.1 to about 0.35, about 0.1 to about 0.3, about 0.1 to about 0.25, about 0.1 to about 0.2, about 0.2 to about 1, about 0.2 to about 0.4, about 0.2 to about 0.35, about 0.2 to about 0.3, about 0.25 to about 1, about 0.25 to about 0.4, about 0.25 to about 0.35, about 0.25 to about 0.3, about 0.3 to about 1, about 0.3 to about 0.4, or about 0.4 to about 1% of the second binder relative to the mass of the deformable core of the granules.

Particulate material [0070] In various embodiments the particulate material may be selected from the group comprising a phyllosilicate, for example, attapulgite, an aluminosilicate, for example zeolite, a clay mineral, for example kaolin or kaolin/TiCh, a sulphate mineral, for example, gypsum, a silicate, for example talc, silica, microsilica, or a combination of any two or more thereof. In one embodiment the particulate material is selected from the group comprising hydrophilic fumed silica, amorphous silica, microsilica and kaolin/TiCh. In a preferred embodiment the particulate material is selected from the group comprising hydrophilic fumed silica, amorphous silica and microsilica. In a particularly contemplated embodiment the particulate material is microsilica.

[0071] In various embodiments the particulate material may comprise particles having a mean size of about 0.1, 0.5, 1, 2.5, 5, 7.5, 10, 12.5, 15, 17.5, 20, 22.5, 25, 27.5 30, 32.5, 35, 37.5, 40, 42.5, 45, 47.5 or about 50 μηη, and useful ranges may be selected between any of these values, for example, from about 0.1 to about 50 μηη, about 0.1 to about 40, about 0.1 to about 30, about 0.1 to about 20, about 0.1 to about 10, about 0.5 to about 50, about 0.5 to about 40, about 0.5 to about 30, about 0.5 to about 20, about 0.5 to about 100, about 1 to about 50, about 1 to about 40, about 1 to about 30, about 1 to about 20, about 1 to about 10, about 5 to about 50, about 5 to about 40, about 5 to about 30, about 5 to about 20, about 5 to about 10, about 10 to about 50, about 10 to about 40, about 10 to about 30, about 10 to about 20, about 20 to about 50, about 20 to about 40, about 20 to about 30, about 30 to about 50, about 30 to about 40, or about 40 to about 50 μΓη .

[0072] In various embodiments the particulate material may comprise particles having a D90% of about 0.1, 0.5, 1, 5, 7.5, 10, 12.5, 15, 17.5, 20, 22.5, 25, 27.5 30, 32.5, 35, 37.5, 40, 42.5, 45, 47.5 or about 50 μηη, and useful ranges may be selected between any of these values, for example, from about 0.1 to about 50 μιτι, about 2 to about 50, about 2 to about 20, about 2 to about 15, about 2 to about 10, about 5 to about 50, about 5 to about 20, about 5 to about 15 or about 5 to about 10 μηη.

[0073] In various embodiments the particulate material may comprise particles having a D50% of about 0.1, 0.5, 1, 5, 7.5, 10, 12.5, 15, 17.5, 20, 22.5, 25, 27.5 30, 32.5, 35, 37.5, 40, 42.5, 45, 47.5 or about 50 μηη, and useful ranges may be selected between any of these values, for example, from about 0.1 to about 50 μιτι, about 0.1 to about 20, about 0.1 to about 5 about 0.1 to about 2, about 0.5 to about 50 μιτι, about 0.5 to about 20, about 0.5 to about 5 about 0.5 to about 2, about 1 to about 50 μιτι, about 1 to about 20, about 0 to about 5 or about 0.1 to about 2.

[0074] In various embodiments the granules may comprise about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5 or 8% of the particulate material relative to the mass of the granules, and useful ranges may be selected between any of these values. For example, the granules comprise about 0.5 to about 8, about 0.5 to about 7, about 0.5 to about 6, about 0.5 to about 5, about 0.5 to about 4, about 0.5 to about 3, about 1 to about 8, about 1 to about 8% by weight. In a particularly contemplated embodiment the granules comprise from about 2 to about 5% particulate material.

[0075] In various embodiments, the particulate material may coat at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% of the granule surface, and suitable ranges may be selected between any of these values. For example, the particulate material coats at least about 10 to about 95, about 10 to about 90, about 10 to about 80, about 20 to about 95, about 20 to about 90, about 20 to about 80, about 30 to about 95, about 30 to about 90, about 30 to about 80, about 40 to about 95, about 40 to about 90, about 40 to about 80, about 50 to about 95, about 50 to about 90, about 50 to about 80, about 60 to about 95, about 60 to about 90, about 70 to about 95, about 70 to about 90, about 70 to about 80, about 80 to about 95, about 80 to about 90, about 50 to about 100, about 60 to about 100, about 70 to about 100, about 80 to about 100, or about 90 to about 100% of the granule surface.

[0076] In one particularly contemplated embodiment the particulate material coats at least about 90% of the granule surface. In another embodiment the particulate material fully coats the granule surface.

Granule properties

[0077] In various embodiments the granules may comprise up to about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or about 25% by weight moisture and useful ranges may be selected between any of these values. For example, the granules comprise from about 5 to about 25, 5 to about 20, about 5 to about 17, about 5 to about 16, about 5 to about 15, about 5 to about 14, about 5 to about 13, about 5 to about 12, about 5 to about 11, about 5 to about 10, 8 to about 25, about 8 to about 20, about 8 to about 17, about 8 to about 16, about 8 to about 15, about 8 to about 14, about 8 to about 13, about 8 to about 12, about 8 to about 11, about 8 to about 10, 10 to about 25, about 10 to about 20, about 10 to about 17, about 10 to about 16, about 10 to about 15, about 10 to about 14, about 10 to about 13, about 10 to about 12, about 10 to about 11, 11 to about 25, about 11 to about 20, about 11 to about 19, about 11 to about 18, about 11 to about 17, about 11 to about 16, about 11 to about 15, 12 to about 25, about 12 to about 20, about 12 to about 17, about 12 to about 16, about 12 to about 12, about 12 to about 14, about 12 to about 13% moisture. In a particularly contemplated embodiment the granules comprise up to about 14% by weight moisture.

[0078] In various embodiments the granules have a water activity of about 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 0.98, or about 0.99, and useful ranges may be selected between any of these values. For example, the water activity of the granules is about 0.5 to about 0.99, 0.5 to about 0.98, 0.5 to about 0.95, 0.5 to about 0.9, 0.5 to about 0.85, 0.5 to about 0.8, 0.5 to about 0.75, 0.5 to about 0.7, 0.6 to about 0.99, 0.6 to about 0.98, 0.6 to about 0.95, 0.6 to about 0.9, 0.6 to about 0.85, 0.6 to about 0.8, 0.6 to about 0.75, 0.6 to about 0.7, 0.65 to about 0.99, 0.65 to about 0.98, 0.65 to about 0.95, 0.65 to about 0.9, 0.65 to about 0.85, 0.65 to about 0.8, 0.65 to about 0.75, 0.7 to about 0.99, 0.7 to about 0.98, 0.7 to about 0.95, 0.7 to about 0.9, 0.7 to about 0.85, 0.7 to about 0.8, 0.75 to about 0.99, 0.75 to about 0.98, 0.75 to about 0.95, 0.75 to about 0.9, 0.75 to about 0.85, 0.75 to about 0.8, 0.8 to about 0.99, 0.8 to about 0.98, 0.8 to about 0.95, 0.8 to about 0.9, 0.85 to about 0.99, 0.85 to about 0.98, or about 0.85 to about 0.95.

[0079] In various embodiments the granules may comprise at least about 1 x 10⁵, 2.5 x 10⁵, 5 x 10⁵, 7.5 x 10⁵, 1 x 10⁶, 2 x 10⁶, 2.5 x 10⁶, 5 x 10⁶, 7.5 x 10⁵, 1 x 10⁷, 2 x 10⁷, 2.5 x 10⁷, 5 x 10⁷, 7.5 x 10⁷, 1 x 10^s, 2 x 10⁸, 2.5 x 10⁸, 5 x 10⁸, 7.5 x 10⁸, 1 x 10⁹, 2 x 10⁹, 2.5 x 10⁹, 5 x 10⁹, 7.5 x 10⁹ or about 1 x 10¹⁰ cfu (colony forming units) of the biological material per gram of granules after 1, 2, 3, 4, 5, 6, 7 days, or 2, 3, 4, 5, 6, 7, 8, 9, 10 weeks storage, or 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 18, 24 months storage at ambient temperature, and useful ranges may be selected between any of these values, for example, from about 1 x 10⁵ to about 1 x 10¹⁰, about 1 x 10⁵ to about 7.5 x 10⁹, about 1 x 10⁵ to about 5 x 10⁹, about 1 x 10⁵ to about 1 x 10⁹, about 1 x 10⁵ to about 5 x 10⁸, about 1 x 10⁵ to about 1 x 10⁸, about 1 x 10⁵ to about 5 x 10⁷, about 1 x 10⁵ to about 1 x 10⁷, about 1 x 10⁵ to about 5 x 10⁶, about 1 x 10⁵ to about 1 x 10⁵, about 5 x 10⁵ to about 1 x 10¹⁰, about 5 x 10⁵ to about 1 x 10⁹, about 5 x 10⁵ to about 1 x 10⁸, about 5 x 10⁵ to about 1 x 10⁷, about 1 x 10⁶ to about 1 x 10¹⁰, about 1 x 10⁶ to about 1 x 10⁹, about 1 x 10⁶ to about 1 x 10⁸, about 1 x 10⁶ to about 1 x 10⁷, about 1 x 10⁷ to about 1 x 10¹⁰, about 1 x 10⁷ to about

1 x 10⁹, about 1 x 10⁷ to about 1 x 10⁸, about 1 x 10⁸ to about 1 x 10¹⁰, or about 1 x 10⁸ to about 1 x 10⁹ cfu. [0080] In various embodiments the biological material may retain at least about 0.1, 0.2, 0.5, 0.75, 2, 5, 10, 15, 20, 25, 30, 35, 40, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, 99 or 100% viability after 1, 2, 3, 4, 5, 6, 7 days, or 2, 3, 4, 5, 6, 7, 8, 9, 10 weeks, or 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 18, 24 months storage of the granules at ambient temperature, and useful ranges may be selected between any of these values for example, about 0.1 to about 99, about 0.1 to about 98, about 0.1 to about 95, about 0.1 to about 90, about 2 to about 99, about 2 to about 98, about 2 to about 95, about 2 to about 90, about

2 to about 85, about 2 to about 80, about 2 to about 70, about 2 to about 60, about 2 to about 50, about 5 to about 99, about 5 to about 98, about 5 to about 95, about 5 to about 90, about 5 to about 85, about 5 to about 80, about 5 to about 70, about 5 to about 60, about 10 to about 99, about 10 to about 98, about 10 to about 95, about 10 to about 90, about 10 to about 85, about 10 to about 80, about 10 to about 70, about 20 to about 99, about 20 to about 98, about 20 to about 95, about 20 to about 90, about 20 to about 85, about 20 to about 80, about 20 to about 70, about 20 to about 60, about 30 to about 99, about 30 to about 98, about 30 to about 95, about 30 to about 90, about 30 to about 85, about 30 to about 80, about 40 to about 99, about 40 to about 98, about 40 to about 95, about 40 to about 90, about 40 to about 80, about 40 to about 70, about 40 to about 60, about 50 to about 99, about 50 to about 98, about 50 to about 95, about 50 to about 90, about 50 to about 85, about 50 to about 80, about 50 to about 70, about 50 to about 60, about 60 to about 99, about 60 to about 98, about 60 to about 95, about 60 to about 90, about 60 to about 85, about 60 to about 80, about 60 to about 70, about 70 to about 99, about 70 to about 98, about 70 to about 95, about 70 to about 90, about 70 to about 80, about 80 to about 99, about 80 to about 98, about 80 to about 95, about 80 to about 90, about 85 to about 99, about 85 to about 98, about 85 to about 95, about 85 to about 90, about 90 to about 99, about 90 to about 98, about 90 to about 95, about 95 to about 99, or from about 95 to about 98%.

[0081] In another embodiment the colony forming units (cfu) of the biological material per gram of granules after at least about 1, 2, 3, 4, 5, 6, 7 days, or 2, 3, 4, 5, 6, 7, 8, 9, 10 weeks, or 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 18, 24 months storage at ambient temperature is at least about 2, 5, 10, 15, 20, 25, 30, 35, 40, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or at least about 1000% of the cfu of biological material per gram of freshly prepared granules, and useful ranges may be selected between any of these values, for example from about 2 to about 1000, about 2 to about 500, about 2 to about 100, about 2 to about 50, about 2 to about 25, about 5 to about 200, about 5 to about 100, about 5 to about 50, about 5 to about 25, about 10 to about 1000, about 10 to about 500, about 10 to about 200, about 10 to about 180, about 10 to about 160, about 10 to about 150, about 10 to about 140, about 10 to about 120, about 10 to about 100, about 10 to about 80, about 10 to about 60, about 10 to about 50, about 10 to about 40, about 25 to about 1000, about 25 to about 500, about 25 to about 200, about 25 to about 180, about 25 to about 150, about 25 to about 140, about 25 to about 120, about 25 to about 100, about 25 to about 80, about 25 to about 60, about 25 to about 50, about 40 to about 200, about 40 to about 180, about 40 to about 160, about 40 to about 150, about 40 to about 140, about 40 to about 120, about 40 to about 100, about 40 to about 80, about 40 to about 60, about 50 to about 1000, about 50 to about 500, about 40 to about 50, about 50 to about 200, about 50 to about 180, about 50 to about 160, about 50 to about 150, about 50 to about 140, about 50 to about 120, about 50 to about 100, about 50 to about 80, about 50 to about 60, about 75 to about 200, about 75 to about 180, about 75 to about 160, about 75 to about 150, about 75 to about 140, about 75 to about 120, about 75 to about 100, about 90 to about 200, about 90 to about 180, about 90 to about 160, about 90 to about 150, about 90 to about 140, about 90 to about 120, about 90 to about 100, about 100 to about 1000, about 100 to about 500, about 100 to about 200, about 100 to about 180, about 100 to about 160, about 100 to about 150, about 100 to about 140, about 100 to about 120, about 120 to about 200, about 120 to about 180, about 120 to about 160, about 120 to about 150, about 120 to about 140, about 140 to about 200, about 140 to about 180, about 140 to about 150, about 150 to about 1000, about 150 to about 500, about 150 to about 200, about 150 to about 180, about 150 to about 160, about 160 to about 200, about 160 to about 180, about 180 to about 200%, about 200 to about 1000, or about 200 to about 500. [0082] In various embodiments the number of colony forming units (cfu) of biological material in the granules increases by at least about 1.2, 1.25, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or at least about 10 fold after at least about 1, 2, 3, 4, 5, 6, 7 days, or 2, 3, 4, 5, 6, 7, 8, 9, 10 weeks, or 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 18, 24 months storage at ambient temperature, and useful ranges may be selected between any of these values, for example from about 1.2 to about 10 fold, about 2 to about 10 fold, about 3 to about 10 fold, or about 5 to about 10 fold.

[0083] In various embodiments the number of colony forming units (cfu) of the biological material is reduced by less than about 1 log, 2 log or 3 log after about 1, 2, 3, 4, 5, 6, 7 days, or 2, 3, 4, 5, 6, 7, 8, 9, 10 weeks, or 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 18, 24 months storage at ambient temperature, and useful ranges may be selected between any of these values, for example from about 1 log to about 3 log or from about 1 log to about 2 log.

[0084] In one embodiment the viability of the biological material in the granules 0.1, 0.5, 1, 2, 3, 4, 5, 6, or 7 days after application to the soil is at least about 2, 5, 10, 15, 20, 25, 30, 35, 40, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, 99 or 100% of the viability of the biological material in freshly prepared granules, and useful ranges may be selected between any of these values for example, about 2 to about 99, about 2 to about 98, about 2 to about 95, about 2 to about 90, about 2 to about 85, about 2 to about 80, about 2 to about 70, about 2 to about 60, about 2 to about 50, about 5 to about 99, about 5 to about 98, about 5 to about 95, about 5 to about 90, about 5 to about 85, about 5 to about 80, about 5 to about 70, about 5 to about 60, about 10 to about 99, about 10 to about 98, about 10 to about 95, about 10 to about 90, about 10 to about 85, about 10 to about 80, about 10 to about 70, about 20 to about 99, about 20 to about 98, about 20 to about 95, about 20 to about 90, about 20 to about 85, about 20 to about 80, about 20 to about 70, about 20 to about 60, about 30 to about 99, about 30 to about 98, about 30 to about 95, about 30 to about 90, about 30 to about 85, about 30 to about 80, about 40 to about 99, about 40 to about 98, about 40 to about 95, about 40 to about 90, about 40 to about 80, about 40 to about 70, about 40 to about 60, about 50 to about 99, about 50 to about 98, about 50 to about 95, about 50 to about 90, about 50 to about 85, about 50 to about 80, about 50 to about 70, about 50 to about 60, about 60 to about 99, about 60 to about 98, about 60 to about 95, about 60 to about 90, about 60 to about 85, about 60 to about 80, about 60 to about 70, about 70 to about 99, about 70 to about 98, about 70 to about 95, about 70 to about 90, about 70 to about 80, about 80 to about 99, about 80 to about 98, about 80 to about 95, about 80 to about 90, about 85 to about 99, about 85 to about 98, about 85 to about 95, about 85 to about 90, about 90 to about 99, about 90 to about 98, about 90 to about 95, about 95 to about 99, or from about 95 to about 98%. [0085] In one embodiment the granules may increase in size by at least about 2, 5, 10, 15, 20, 25, 30, 35, 40, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, 99 or 100% after 1, 2, 3, 4, 5, 6, 7 days, or 2, 3, 4, 5, 6, 7, 8, 9, 10 weeks post-application to the soil, and useful ranges may be selected between any of these values for example, about 2 to about 99, about 2 to about 98, about 2 to about 95, about 2 to about 90, about 2 to about 85, about 2 to about 80, about 2 to about 70, about 2 to about 60, about 2 to about 50, about 5 to about 99, about 5 to about 98, about 5 to about 95, about 5 to about 90, about 5 to about 85, about 5 to about 80, about 5 to about 70, about 5 to about 60, about 10 to about 99, about 10 to about 98, about 10 to about 95, about 10 to about 90, about 10 to about 85, about 10 to about 80, about 10 to about 70, about 20 to about 99, about 20 to about 98, about 20 to about 95, about 20 to about 90, about 20 to about 85, about 20 to about 80, about 20 to about 70, about 20 to about 60, about 30 to about 99, about 30 to about 98, about 30 to about 95, about 30 to about 90, about 30 to about 85, about 30 to about 80, about 40 to about 99, about 40 to about 98, about 40 to about 95, about 40 to about 90, about 40 to about 80, about 40 to about 70, about 40 to about 60, about 50 to about 99, about 50 to about 98, about 50 to about 95, about 50 to about 90, about 50 to about 85, about 50 to about 80, about 50 to about 70, about 50 to about 60, about 60 to about 99, about 60 to about 98, about 60 to about 95, about 60 to about 90, about 60 to about 85, about 60 to about 80, about 60 to about 70, about 70 to about 99, about 70 to about 98, about 70 to about 95, about 70 to about 90, about 70 to about 80, about 80 to about 99, about 80 to about 98, about 80 to about 95, about 80 to about 90, about 85 to about 99, about 85 to about 98, about 85 to about 95, about 85 to about 90, about 90 to about 99, about 90 to about 98, about 90 to about 95, about 95 to about 99, or from about 95 to about 98%. [0086] In one embodiment the moisture content of the granules may increase by at least about 2, 5, 10, 15, 20, 25, 30, 35, 40, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, 99 or 100% after 1, 2, 3, 4, 5, 6, 7 days, or 2, 3, 4, 5, 6, 7, 8, 9, 10 weeks post-application to the soil, and useful ranges may be selected between any of these values for example, about 2 to about 99, about 2 to about 50, about 5 to about 99, about 5 to about 60, about 10 to about 99, about 10 to about 70, about 20 to about 99, about 20 to about 60, about 30 to about 99, about 30 to about 80, about 40 to about 99, about 40 to about 60, about 50 to about 99, about 50 to about 60, about 60 to about 99, about 60 to about 70, about 70 to about 99, about 70 to about 80, about 80 to about 99, about 80 to about 90, about 85 to about 99, or from about 95 to about 98%. [0087] In one embodiment 10 g granules placed on paper towels wetted with 100 ml_ water absorbs at least about 1, 1.5, 2, 2.5, 2.75, 3, 3.25, 3.5, 3.75, 4, 4.25, 4.5, 4.75, 5, 5.5, 6, 6.5 or at least about 7 g water, and useful ranges may be selected between any of these values for example, from about 1 to about 7 g, about 1 to about 6 g, about 1 to about 5 g, about 2 to about 5 g, about 2 to about 4 g, about 2 to about 3.5 g, about 2.5 to about 5 g, about 2.5 to about 4.5 g, or about 2.5 to about 4 g.

[0088] In various embodiments the granules may be substantially resistant to deformation upon application of a pressure of up to about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5 kg/cm², and useful ranges may be selected between any of these values, for example from about 0.5 to about 5, about 0.5 to about 4.5, about 0.5 to about 4, about 0.5 to about 3.5, about 0.5 to about 3, about 1 to about 5, about 1 to about 4.5, about 1 to about 4, about 1 to about 3.5, about 1 to about 3, about 1.5 to about 5, about 1.5 to about 4.5, about 1.5 to about 4, about 1.5 to about 3.5, about 1.5 to about 3, about 2 to about 5, about 2 to about 4.5, about 2 to about 4, about 2 to about 3.5, about 2 to about 3, about 2.5 to about 5, about 2.5 to about 4.5, about 2.5 to about 4, about 2.5 to about 3.5, about 2.5 to about 3, about 3 to about 5, about 3 to about 4.5, about 3 to about 4 kg, about 3.5 to about 5, about 3.5 to about 4, or about 4 to about 5 kg/cm². [0089] In various embodiments, the granules may have a hardness of at least about 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 7.5, 8, 9, 10, 15, 20, 30, 40 or about 50 N, and useful ranges may be selected between any of these values, for example, from about 1 to about 50, 2 to about 50, about 2 to about 30, about 2 to about 20, about 2 to about 10, about 2 to about 9, about 2 to about 5, about 3 to about 50, about 3 to about 30, about 3 to about 20, about 3 to about 10, about 3 to about 9, about 3 to about 5, about 4 to about 50, about 4 to about 30, about 4 to about 20, about 4 to about 10, about 4 to about 9, or about 4 to about 5 N.

[0090] In various embodiments the granules may have a mean size of about 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7.5 or about 10 mm, and useful ranges may be selected between any of these values, for example, from about 0.5 to about 10, about 0.5 to about 7.5, about 0.5 to about 6, about 0.5 to about 5, 1 to about 10, about 1 to about 7.5, about 1 to about 6, about 1 to about 5, about 2 to about 10, about 2 to about 7.5, about 2 to about 6, about 2 to about 5, about 2 to about 4, about 2.5 to about 10, about 2.5 to about 7.5, about 2.5 to about 6, about 2.5 to about 5, or about 2.5 to about 4 mm. [0091] In one embodiment the agricultural composition may comprise one or more agricultural agents. In a particularly contemplated embodiment the agricultural agent is urea. Method of manufacture

[0092] In various embodiments a substrate may be coated with a first coating comprising biological material to form a first coated material.

[0093] In various embodiments the substrate may be coated with a first coating comprising biological material, and optionally a biodegradable polymer and/or a non- cytotoxic oil, followed by one or more coatings comprising one or more particulate desiccants.

[0094] In various embodiments the first coated material may be coated with a second coating comprising at least one particulate desiccant and with a binder to form a deformable core. In one embodiment the first-coated material may be coated with alternating layers of the second coating and the binder. In one embodiment the first-coated material may be coated with two or more layers of the second coating.

[0095] In one embodiment the deformable core is formed by

a) providing a substrate,

b) coating the substrate with a first coating comprising biological material to form a first coated material, and

c) coating the first coated material with a second coating comprising at least one

particulate desiccant and with a binder to form the deformable core.

[0096] In one embodiment the first coated material may be coated with the second coating and with a first binder and then coated with a second binder. In one embodiment the second binder may be less soluble in water than the first binder.

[0097] In various embodiments the first binder may be soluble in water to form a 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5% solution at a temperature of less than about 25, 30, 35, 40, 45, 50, 55, 60, 65 or about 70°C, and useful ranges may be selected between any of these values, for example, from about 25 to about 70, about 25 to about 65, about 25 to about 60, about 25 to about 55, about 25 to about 50, about 25 to about 45, about 30 to about 70, about 30 to about 65, about 30 to about 60, about 30 to about 55, about 30 to about 50, about 35 to about 70, about 35 to about 65, about 35 to about 60, about 35 to about 55, about 35 to about 50, about 35 to about 45, about 40 to about 70, about 40 to about 65, about 40 to about 60, about 40 to about 55, about 40 to about 50, about 45 to about 70, about 45 to about 65, about 45 to about 60, about 45 to about 55, about 45 to about 50, or from about 50 to about 70°C. [0098] In one embodiment the first binder completely dissolves in water in less than 2 hours. For example, the first binder completely dissolves in water in less than 2 hours at a temperature of 55 °C to form a 2% solution.

[0099] In various embodiments the second binder may be soluble in water to form a 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5% solution at a temperature of greater than about 50, 55, 60, 65, 70, 75, 80, 85, 90 or about 95°C, and useful ranges may be selected between any of these values, for example, from about 50 to about 95, about 50 to about 90, about 50 to about 85, about 50 to about 80, about 50 to about 75, about 50 to about 70, about 55 to about 95, about 55 to about 90, about 55 to about 85, about 55 to about 80, about 55 to about 75, about 55 to about 70, about 60 to about 95, about 60 to about 90, about 60 to about 85, about 60 to about 80, about 60 to about 75, about 60 to about 70, about 65 to about 95, about 65 to about 90, about 65 to about 85, about 65 to about 80, about 65 to about 75, or about 65 to about 70°C.

[OOIOO] In one embodiment the second binder completely dissolves in water in less than 2 hours. For example, the second binder completely dissolves in water in less than 2 hours at a temperature of 70 °C to form a 2% solution.

[OOIOI] In various embodiments the first binder or second binder may have a pH of about 4, 4.5, 5, 5.5, 6, 6.5, 7 or about pH 8, and useful ranges may be selected between any of these values, for example, from about pH 4 to about pH 8, about pH 4 to about pH 7, about pH 4 to about pH 6, about pH 4 to about pH 5, about pH 5 to about pH 8, about pH 5 to about pH 7, about pH 5 to about pH 6, about pH 6 to about pH 8, about pH 6 to about pH 7, or about pH 7 to about pH 8.

[00102] In various embodiments the first binder or second binder may have a viscosity of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, 20, 22, 25, 27, 30, 35, 40, 45, 50, 55, 60, 70, 75, 80, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 225, 250, 275 or 300 cP, and useful ranges may be selected between any of these values, for example, about 1 to about 300, about 1 to about 250, about 1 to about 200, about 1 to about 150, about 1 to about 100, about 1 to about 70, about 1 to about 50, 1 to about 30, about 1 to about 25, about 1 to about 20, about 1 to about 15, about 1 to about 10, about 1 to about 6, about 1 to about 5, about 1 to about 4, about 1 to about 3, 2 to about 300, about 2 to about 200, about 2 to about 100, about 2 to about 70, about 1 to about 50, 2 to about 30, about 2 to about 25, about 2 to about 20, about 2 to about 15, about 2 to about 10, about 2 to about 6, about 2 to about 5, about 2 to about 4, about 2 to about 3, 3 to about 300, about 3 to about 200, about 1 to about 100, about 3 to about 70, about 3 to about 50, about 3 to about 30, about 3 to about 10, about 3 to about 6, about 3 to about 5, about 3 to about 4, about 4 to about 300, about 4 to about 200, about 4 to about 100, about 4 to about 50, about 4 to about 20, about 4 to about 10, about 10 to about 300, about 10 to about 200, about 10 to about 100, about 10 to about 50, about 10 to about 20, about 11 to about 300, about 11 to about 200, about 11 to about 100, about 11 to about 70, about 11 to about 50, about 50 to about 300, about 50 to about 200, about 50 to about 100, about 70 to about 300, about 70 to about 200, or about 70 to about 100.

[00103] In various embodiments the first binder or second binder may comprise about 0.5, 1, 1.5, 2, 2.5, 3, 4 5, 6, 7, 7.5, 8, 9, 10, 15, 20, 25, 30, 35 or about 40% w/v of the polymeric compound, and useful ranges may be selected between any of these values, for example, about 0.5 to about 40, about 0.5 to about 30, about 0.5 to about 20, about 0.5 to about 10, about 0.5 to about 5, about 1 to about 40, about 1 to about 30, about 1 to about 20, about 1 to about 15, about 1 to about 10, about 1 to about 5, about 1 to about 3, about 1.5 to about 40, about 1.5 to about 30, about 1.5 to about 20, about 1.5 to about 10, about 1.5 to about 5, about 2 to about 40, about 2 to about 30, about 2 to about 20, about 2 to about 10, about 2 to about 5, about 2.5 to about 40, about 2.5 to about 30, about 2.5 to about 20, about 2.5 to about 10, about 5 to about 40, about 5 to about 30, about 5 to about 20, about 5 to about 10, about 7.5 to about 40, about 7.5 to about 30, about 7.5 to about 20, about 10 to about 40, about 10 to about 30, about 10 to about 20% w/v of the polymeric compound. [00104] In various embodiments about 0.1, 0.2, 0.25, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or about 5 L binder may be applied per 10 kg of coated granules, and useful ranges may be selected between any of these values, for example, about 0.25 to about 5, about 0.25 to about 4, about 0.25 to about 3, about 0.25 to about 2.5, about 0.25 to about 2, about 0.5 to about 5, about 0.5 to about 4.5, about 0.5 to about 4, about 0.5 to about 3.5, about 0.5 to about 3, about 0.5 to about 2.5, about 0.5 to about 2, about 1 to about 5, about 1 to about 4, about 1 to about 3, about 1 to about 2.5, or about 1 to about 2 L.

[00105] In one embodiment the method may additionally comprise drying the granule.

[00106] In various embodiments the coated granules may be dried in a fluid bed dryer. In one embodiment the coated granules may be dried until the granules have a moisture content of about 10, 11, 12, 12.5, 13, 13.5, 14, 14.5, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24% moisture, and useful ranges may be selected between any of these values, for example, from about 10 to about 24, 10 to about 20, about 10 to about 19, about 10 to about 18, about 10 to about 17, about 10 to about 16, about 10 to about 15, about 10 to about 14, about 10 to about 13.5, about 10 to about 12.5, from about 11 to about 20, about 11 to about 19, about 11 to about 18, about 11 to about 17, about 11 to about 16, about 11 to about 15, about 11 to about 14, about 11 to about 13.5, about 11 to about 12.5, about 12 to about 24, about 12 to about 20, about 12 to about 19, about 12 to about 18, about 12 to about 17, about 12 to about 16, about 12 to about 15, about 12 to about 14, about 12 to about 13.5, about 12 to about 12.5, about 12.5 to about 20, about 12.5 to about 17.5, about 12.5 to about 15, about 12.5 to about 14.5, about 12.5 to about 14, or about 12.5 to about 13.5 moisture. In a particularly contemplated embodiment the coated granules are dried until the granules comprise from about 11 to about 19% moisture.

Application

[00107] In one embodiment the distribution device may be a seed drill. For example, in various embodiments the distribution device may be a gravity drill or an air-speeder drill. In another embodiment the distribution device may be a truck. In a further embodiment the distribution device may be a ground spreader.

[00108] In various embodiments the granules or composition may be concurrently applied using the distribution device with a second granule or composition, for example, urea.

[00109] In various embodiments the granules or composition may be applied into the soil to a depth of about 10, 15, 20, 25, 30, 35, 40, 45 or about 50 mm under the surface of the soil, and useful ranges may be selected between any of these values, for example from about 10 to about 50, about 10 to about 45, about 10 to about 40, about 10 to about 35, about 10 to about 30, about 10 to about 25, about 10 to about 20, about 15 to about 50, about 15 to about 45, about 15 to about 40, about 15 to about 35, about 15 to about 30, about 15 to about 25, about 20 to about 50, about 20 to about 45, about 20 to about 40, about 20 to about 35, about 20 to about 30, about 25 to about 50, about 25 to about 45, about 25 to about 40, about 25 to about 35, about 25 to about 50, about 25 to about 45, about 25 to about 40, or from about 25 to about 35 mm.

[OOllO] In various embodiments the granules or composition may be applied to substantially cover a locus, for example a crop field or pasture.

[OOlll] In various embodiments the granules or composition may be applied to the soil at a rate of at least about 5, 10, 20, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or about 200 kg per hectare, and useful ranges may be selected between any of these values, for example, from about 10 to about 200, about 10 to about 150, about 10 to about 120, about 10 to about 100, about 10 to about 50, about 30 to about 200, about 30 to about 150, about 30 to about 100, about 30 to about 75, about 40 to about 200, about 40 to about 180, about 40 to about 150, about 40 to about 100, about 40 to about 80, about 40 to about 75, about 50 to about 200, about 50 to about 180, about 50 to about 160, about 50 to about 150, about 50 to about 120, about 50 to about 100, about 50 to about 75, about 60 to about 200, about 60 to about 180, about 60 to about 150, about 60 to about 120, about 60 to about 100, about 60 to about 80, about 75 to about 200, about 75 to about 180, about 75 to about 160, about 75 to about 150, about 75 to about 120, about 75 to about 100, about 90 to about 200, about 90 to about 180, about 90 to about 160, about 90 to about 150, about 90 to about 120, about 100 to about 200, about 100 to about 180, about 100 to about 160, about 100 to about 150, about 100 to about 120, about 120 to about 200, about 120 to about 180, about 120 to about 160, about 120 to about 150, or about 150 to about 200 kg.

[00112] In various embodiments the granules or composition may be applied to the soil at a rate of at least about 1 x 10⁹, 1 x 10¹⁰, 5 x 10¹⁰, 1 x 10¹¹, 5 x 10¹¹, 1 x 10¹², 2.5 x 10¹², 5 x 10¹², 7.5 x 10¹², 1 x 10¹³, 2.5 x 10¹³, 5 x 10¹³, 7.5 x 10¹³, 1 x 10¹⁴, 2.5 x 10¹⁴, 5 x 10¹⁴, 7.5 x 10¹⁴, or about 1 x 10¹⁵ cfu of biological material per hectare and useful ranges may be selected between any of these values, for example, from about 1 x 10⁹ to about 1 x 10¹⁵, about 1 x 10⁹ to about 1 x 10¹⁴, about 1 x 10⁹ to about 1 x 10¹³, about 1 x 10⁹ to about 1 x 10¹², 1 x 10¹⁰ to about 1 x 10¹⁵, about 1 x 10¹⁰ to about 5 x 10¹⁴, about 1 x 10¹⁰ to about 1 x 10¹⁴, about 1 x 10¹⁰ to about 5 x 10¹³, about 1 x 10¹⁰ to about 1 x 10¹³, about 1 x 10¹⁰ to about 5 x 10¹², about 1 x 10¹⁰ to about 1 x 10¹², about 1 x 10¹¹ to about 1 x 10¹⁵, about 1 x 10¹¹ to about 5 x 10¹⁴, about 1 x 10¹¹ to about 1 x 10¹⁴, about 1 x 10¹¹ to about 5 x 10¹³, about 1 x 10¹¹ to about 1 x 10¹³, about 1 x 10¹¹ to about 5 x 10¹², about 1 x 10¹¹ to about 1 x 10¹², about 1 x 10¹² to about 1 x 10¹⁵, about 1 x 10¹² to about 5 x 10¹⁴, about 1 x 10¹² to about 1 x 10¹⁴, about 1 x 10¹² to about 5 x 10¹³, about 1 x 10¹² to about 1 x 10¹³, about 5 x

10¹² to about 1 x 10¹⁵, about 5 x 10¹² to about 5 x 10¹⁴, about 5 x 10¹² to about 1 x 10¹⁴, about 5 x 10¹² to about 7.5 x 10¹³, about 5 x 10¹² to about 5 x 10¹³, about 5 x 10¹² to about

2.5 x 10¹³, about 5 x 10¹² to about 1 x 10¹³, about 1 x 10¹³ to about 1 x 10¹⁵, about 1 x

10¹³ to about 5 x 10¹⁴, about 1 x 10¹³ to about 1 x 10¹⁴, about 1 x 10¹³ to about 7.5 x 10¹³, about 1 x 10¹³ to about 5 x 10¹³, about 2.5 x 10¹³ to about 1 x 10¹⁵, about 2.5 x 10¹³ to about 7.5 x 10¹⁴, about 2.5 x 10¹³ to about 5 x 10¹⁴, about 2.5 x 10¹³ to about 2.5 x 10¹⁴, about 2.5 x 10¹³ to about 1 x 10¹⁴, about 2.5 x 10¹³ to about 5 x 10¹⁴, about 5 x 10¹³ to about 1 x 10¹⁵, about 5 x 10¹³ to about 7.5 x 10¹⁴, about 7.5 x 10¹³ to about 5 x 10¹⁴, about 5 x 10¹³ to about 2.5 x 10¹⁴, about 5 x 10¹³ to about 1 x 10¹⁴, about 7.5 x 10¹³ to about 1 x 10¹⁵, about 7.5 x 10¹³ to about 1 x 10¹⁴, or about 1 x 10¹³ to about 1 x 10¹⁵ cfu per hectare.

[00113] In one embodiment the granules or composition may be applied when the soil is wet, or after irrigation or rainfall. [00114] In one embodiment application of the granules or composition may kill plant pests, such as grass grubs.

[00115] In one embodiment application of the granules or composition may reduce the grass grub population in the soil by at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100% in the 12 months following application, and useful ranges may be selected between any of these values, for example, from about 10 to about 100, about 10 to about 90, about 10 to about 75, about 10 to about 60, about 10 to about 50, about 10 to about 40, about 20 to about 100, about 20 to about 90, 20 to about 75, 20 to about 60, 20 to about 50, 20 to about 40, 40 to about 100, 40 to about 90, 40 to about 75,40 to about 60, 40 to about 50, 50 to about 100, 50 to about 90, 50 to about 75, 50 to about 60, 60 to about 100, 60 to about 90, 60 to about 75, 75 to about 100, 75 to about 90, or from about 75 to about 80%. In one particularly contemplated embodiment application of the granules or composition reduces the grass grub population in the soil by at least about 50% in the 12 months following application to soil. [00116] In one embodiment application of the granules or composition may increase plant growth, such as pasture growth, or increases plant yield, such as pasture yield.

[00117] In various embodiments, application of the granules or composition may increase pasture dry matter production by at least about 2, 2.5, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100%, and useful ranges may be selected between any of these values, for example, from about 2 to about 100, about 2.5 to about 100, about 5 to about 100, about 10 to about 100, about 10 to about 90, about 10 to about 75, about 10 to about 60, about 10 to about 50, about 10 to about 40, about 20 to about 100, about 20 to about 90, 20 to about 75, 20 to about 60, 20 to about 50, 20 to about 40, 40 to about 100, 40 to about 90, 40 to about 75,40 to about 60, 40 to about 50, 50 to about 100, 50 to about 90, 50 to about 75, 50 to about 60, 60 to about 100, 60 to about 90, 60 to about 75, 75 to about 100, 75 to about 90, or from about 75 to about 80%.

[00118] It is intended that reference to a range of numbers disclosed herein (for example, 1 to 10) also incorporates reference to all rational numbers within that range (for example, 1, 1.1, 2, 3, 3.9, 4, 5, 6, 6.5, 7, 8, 9 and 10) and also any range of rational numbers within that range (for example, 2 to 8, 1.5 to 5.5 and 3.1 to 4.7).

[00119] This invention may also be said broadly to consist in the parts, elements and features referred to or indicated in the specification of the application, individually or collectively, and any or all combinations of any two or more of said parts, elements or features, and where specific integers are mentioned herein which have known equivalents in the art to which this invention relates, such known equivalents are deemed to be incorporated herein as if individually set forth.

[00120] In this specification, where reference has been made to external sources of information, including patent specifications and other documents, this is generally for the purpose of providing a context for discussing the features of the present invention. Unless stated otherwise, reference to such sources of information is not to be construed, in any jurisdiction, as an admission that such sources of information are prior art or form part of the common general knowledge in the art.

[00121] The term "comprising" as used in this specification means "consisting at least in part of". When interpreting statements in this specification which include that term, the features, prefaced by that term in each statement, all need to be present but other features can also be present. Related terms such as "comprise" and "comprised" are to be interpreted in the same manner.

BRIEF DESCRIPTION OF THE DRAWINGS [00122] The invention will now be described by way of example only and with reference to the drawings in which :

[00123] Figure 1 is a flowchart summarising methods of manufacturing granules of the invention.

DETAILED DESCRIPTION OF THE INVENTION [00124] The present invention relates to granules or an agricultural composition comprising granules, methods of preparing such granules, and application of such granules into or on soil. The granules comprise a deformable core, a binder and an exterior coating comprising a particulate material.

[00125] The present invention provides for the application of granules into or on the soil using a distribution device such as a seed drill without substantial compression of the granules. The examples below show that the granules of the invention are readily applied using a seed drill, are substantially resistant to compression when subject to high mechanical forces and are free flowing.

[00126] The present invention also provides for the delivery of beneficial biological material to the soil in granules that protect the biological material during storage of th granules and after application to the soil before the biological material enters the soil profile. The granules of the invention are suitable for delivery of a wide range of biological materials that improve soil quality and control pests and disease in plants.

1. Granules

[00127] As used herein the term "granule" includes granules, prills, pellets, small particles and grains. Granules have a mean particle size of, for example, at least about 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7.5 or about 10 mm, and useful ranges may be selected between any of these values, for example, from about 0.5 to about 10 mm.

[00128] The term "deformable" as used in this specification means "susceptible to adhesion and smearing under pressure". For example, granules of the invention or a core described herein are deformable if the granules or core smear, or adhere together or to hard surfaces, such as the surfaces of machinery, when subjected to a pressure of more than about 0.5 kg/cm² to about 4 kg/cm².

[00129] The granules of the invention comprise

a) a deformable core,

b) a binder incorporated within and/or coated on the deformable core, and c) an exterior coating that at least partially coats the deformable core

[00130] In one embodiment the binder may comprise a polymeric compound, preferably a polyhydroxyl compound as described above.

[00131] In various embodiments the polymeric compound may be selected from the group comprising a polyvinyl alcohol, a polyethylene oxide (for example, POLYOX™ N IO, POLYOX™ N750), methyl cellulose (for example, METHOCEL™ A4M) or gum arabic. In a particularly preferred embodiment the polyhydroxyl compound is a polyvinyl alcohol, for example, Poval^® PVA 105, Sigma-80 PVA, Poval^® PVA 405, Poval^® PVA 205, Poval^® PVA 205MB or BF17W, BF17 or PB17 polyvinyl alcohol.

[00132] In another embodiment the polymeric compound may comprise a latex polymer, for example, EC 23009, a shellac resin, or a polyvinylpyrrolidone.

[00133] In various embodiments the granules may comprise additional agents, for example, a dye, a plasticiser or an agricultural agent as described above. These additional agents may be incorporated into the first or second coatings.

[00134] In one embodiment the granules comprise a first binder and a second binder. The granules may comprise alternating layers of the first binder and the second coating, and a final layer of the second binder. The second binder may bind the particulate material to the granule to form the exterior coating.

[00135] It is desirable for the binder and/or second binder for use in the invention to have one or more of the following properties. [00136] Preferably, a solution comprising the binder atomises finely to enable uniform application when sprayed on to the surface of the granules. Preferably, the binder solution has a low viscosity.

[00137] Preferably the binder initially forms an adherent surface that at least partially coats the surface of the granules when first applied to the granule. The adherent surface enables adherence of the second coating and/or the particulate material to the granules.

[00138] Preferably, the binder solution dries within about 15 seconds following application to the deformable core of the granules.

[00139] When two binders are used, the first binder may comprise a first polymeric compound that rapidly dissolves when contacted by moisture in the soil to enable rapid release of the biological material and/or other agricultural agents in the granules.

Preferably, the second binder comprises a second polymeric compound that resists dissolution during storage of the granules, for example, if condensation forms in the bags in which the granules are stored. The second binder helps to protect the biological material in the granule from environmental conditions, such as UV radiation and desiccation when the granules are applied on to the soil. The second binder dissolves once the granules are applied into or on soil. The rate of dissolution of the second binder of the granules varies depending on the moisture content of the soil. For example, the exterior coating of the granules will dissolve more rapidly in a wet soil.

[00140] In various embodiments the second binder of the granules dissolves within about 1, 1.5, 2, 2.5 3, 3.5, 4, 4.5 or 5 hours of application to wet soil, and useful ranges may be selected from between any of these values, for example from about 1 to about 5, about 1 to about 4, about 1 to about 3, about 2 to about 5, about 2 to about 4, about 3 to about 4, or about 3 to about 5 hours.

[00141] In various embodiments the second binder of the granules dissolves within about 12, 24, 36, 48, 60, or about 72 hours of application to dry soil, and useful ranges may be selected from between any of these values, for example from about 12 to about 72, about 12 to about 60, about 12 to about 48, about 12 to about 36, about 12 to about 24, about 24 to about 72, or about 24 to about 48 hours. [00142] In a particularly preferred embodiment, the first binder may comprise a first polymeric compound that is soluble in water at a temperature of less than about 50°C to form a 2% solution of the first polymeric compound, and the second binder may comprise a second polymeric compound that is soluble in water at a temperature of at least about 70°C to form a 2% solution of the second polymeric compound. The second polymeric compound may have a higher degree of hydrolysis and/or a higher molecular weight than the first binder.

[00143] Polymeric compounds for use in the invention must be compatible with, and non-toxic to, the biological material contained in the granule. Preferably, the polymeric compounds are agriculturally acceptable, non-toxic, biodegradable and/or food grade.

[00144] Preferably, the binder resists fungal or mould formation on the surface of the granules.

[00145] Preferably, the polymeric compound is a film-forming compound. Preferably, the polymeric compound forms a film on the granule that is uniform.

[00146] Preferably, a film formed on the surface of the granules by the polymeric compound is non-adhesive, so that adjacent granules do not adhere to each other. This property of the binder may be assessed by determining the "cling" tendency of films comprising the binder. A binder solution is prepared and applied to two glass sheets at the maximum temperature the granules will be exposed to during manufacture, for example, 35°C. Each of the films is peeled away from the glass and then slid across each other. The absence of any bonding between the films indicates that the binder is suitable for use in the invention.

[00147] The exterior coating of the granules may comprise particulate material that is embedded or compressed on to the surface of the deformable core to at least partially coat the surface of the deformable core of the granules. The void spaces on the surface of the granules are filled by the particulate material and the surface of the granules is smoothed to form a surface with a low coefficient of friction. Without wishing to be bound by any theory, the particulate material likely forms small fractures on the surface of the granules that allow ingress of moisture when the granules are applied to soil to facilitate break up of the granule and delivery of the biological material. Suitable particulate materials for use in the exterior coating are described above.

[00148] In relation to the particle size distribution of the particulate material, this can be defined by reference to the percentage of particles below a particular particle size. For example, a D90 defines the upper limit of the diameter of 90% of the particles, whereas a D50 defines the upper limit of the diameter of 50% of the particles. A D90% of 10 μηη means that 90% of the particles have a diameter of less than 10 μηη. A D50% of 2 μηη means that 10% of the particles have a diameter of less than 2 μηη.

[00149] In one embodiment the granules may comprise

a) a deformable core comprising

(i) a substrate,

(ii) a first coating that at least partially coats the substrate, the first

coating comprising biological material, and

a second coating that at least partially coats the first coating, th second coating comprising at least one particulate desiccant and a binder, and

b) an exterior coating that at least partially coats the deformable core, the

exterior coating comprising a particulate material, the particulate material comprising particles having a mean size of from about 0.1 μηη to about 50 μηη.

[00150] The substrate is an inert, absorbent material that forms the inner core of the granule. In one embodiment the substrate may be an edible and/or biodegradable solid or semi-solid. Suitable substrates for use in the invention are described above.

[00151] The substrate is porous and absorbs a substantial amount of the first coating applied to the granule as described above. For example, in one embodiment the substrate may be zeolite that absorbs at least about 20% of the first coating material. In another embodiment the substrate may be a seed that absorbs at least about 4% of the first coating, or from about 4% to about 15% of the first coating.

[00152] The granules of the invention are suitable for delivery of a wide range of biological materials to soil. In particular, the granules of the invention are suitable for delivery of microorganisms that are sensitive to the environment, for example,

microorganisms that are sensitive to desiccation or ultraviolet radiation. The granules of the invention preserve the viability of the biological material in the first coating during storage at ambient temperature, for example, storage for at least about 5 weeks. It will be appreciated that ambient temperature is a temperature of about 20°C. The granules of the invention rapidly degrade and release the biological material in the first coating of the granule after application of the granules to soil.

[00153] In one embodiment the first coating may comprise one or more biodegradable polymers and one or more non-cytotoxic oils. The biodegradable polymer and non-cytotoxic oil may be combined to form a gel stock. The biological material is added to the gel stock before application to the granule to form the first coating of the granule. Water and the biodegradable polymer together form a gel that provides a suitable environment to support the viability of the biological material. The polymer particles in the gel are coated with the non-cytotoxic oil, which ensures that the particles disperse evenly in water volume before swelling.

[00154] Suitable biological materials for use in the invention are described above. The biological material may comprise a combination of any two or more biological materials, for example, a microorganism and a protein, or two microorganisms. In one embodiment the biological material may comprise a combination of a bacterium and a fungus.

[00155] In a particularly contemplated embodiment the biological material is Serratia entomophila.

[00156] In one embodiment the biodegradable polymer may be a polysaccharide.

Preferably, the biodegradable polymer is of neutral or negative charge. In one embodiment the biopolymer may be an exopolysaccharide produced by a microorganism, or a gum. In an alternative embodiment the biodegradable polymer may be a synthetic polysaccharide, for example a synthetic polymer of sucrose.

[00157] In one embodiment the first coating may comprise a non-cytotoxic oil that is compatible with, and non-toxic to, the biological material, particularly microorganisms in the granule. In a preferred embodiment the non-cytotoxic oil is a plant or animal oil. In various embodiments, the non-cytotoxic oil is a marine oil, for example a fish or seaweed oil, or a paraffin oil or a mineral oil.

[00158] The second coating of the granules comprises at least one particulate desiccant and preferably a disintegrant as discussed above. [00159] The particulate desiccant increases the density of the granules to enable effective distribution, contributes to the hardness of the granules, protects the biological material from environmental conditions such as desiccation and UV radiation, adsorbs and retains moisture, and regulates the rate of release of biological material from the granules.

[00160] The inclusion of a disintegrant in the second coating increases swelling and breakdown of the granules to regulate the release of the biological material from the granule.

[00161] In one embodiment the granules may comprise an agricultural agent, for example, one or more fertilizers, one or more trace elements, one or more nitrification inhibitors, one or more urease inhibitors, pesticides, for example fungicides, or other agents. In various embodiments the agricultural agent may be included in the first coating, the second coating, or in the binder.

[00162] In one embodiment the granules may further comprise a dye. For example, the dye may be included in the second coating. In one embodiment the dye may be included in the binder or second binder.

[00163] The granules of the invention may be combined with an agricultural agent to form an agricultural composition for application to soil. Alternatively, the granules may be applied to the soil in a distribution device concurrently with another agricultural agent. For example, the granules may be combined with, or applied concurrently with, urea.

[00164] Frequently, when granules are combined with urea, moisture migrates from the interior to the surface of the granules causing degradation of the granules and surface wetting of the urea. Wetted urea granules adhere together and smear preventing application of the urea and granules using distribution equipment. The exterior coating formed by the particulate material on the surface of the granules of the invention provides a barrier to prevent the egress of moisture from the granules, enabling the granules to be combined or co-administered with urea.

[00165] An exemplary granule of the invention comprises a deformable core comprising

(i) zeolite,

(ii) a first coating that at least partially coats the substrate, the first

coating comprising xanthan gum, canola oil and biological material, and

(iii) a second coating that at least partially coats the first coating, the

second coating comprising potato starch, bentonite and gypsum and polyvinyl alcohol, and

Properties of the granules

[00166] The granules of the invention are free-flowing, non-adherent, non-bridging and substantially resistant to deformation.

[00167] It is desirable that the exterior coating of the granule provide maximum slip or minimum adhesion between the granules and hard surfaces, such as those of a distribution device. It is also desirable that the exterior coating resist the deformation forces produced in a distribution device when operating. Further, it is desirable that the granules are substantially resistant to softening when exposed to condensation and dampness, for example during storage of the granules.

[00168] In various embodiments the granules may be substantially resistant to deformation upon application of a pressure of up to about 0.5 kg/cm² to about 4 kg/cm².

[00169] In various embodiments that granules may have a mean size of from about 0.5 to about 10 mm, preferably from about 2 to about 4 mm.

[00170] It is desirable that the exterior coating of the granules forms a hard shell. The hard shell resists deformation of the granule when subject to compression in distribution devices such as a seed drill. The hard shell also protects the granule from moisture to prevent smearing or premature breakdown of the granule before application. Preferably, the granules have a hardness of from about 0.1 N to about 10 N.

[00171] It is desirable that the granules are substantially round in shape with few angular surfaces. [00172] The granules of the invention exhibit favourable flowability characteristics. Flowability refers to the ease with which the granules will flow under a specified set of conditions.

[00173] The flow properties and flowability of the granules may be determined using standard powder and/or particle flow tests known in the art. [00174] For example, the flowability of the granules may be measured by pouring granules through a cone or at a tilted angle onto a flat surface to form a cone of granules. The flat surface may have a fixed base size. The maximum angle that the plane of powder makes with the horizontal surface (the angle of repose) is measured. The angle of repose may be a static or kinetic angle of repose. In various embodiments the angle of repose of the granules is about 12, 14, 15, 16, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55 or about 60 degrees (for example, about 12 to about 60 degrees). In a particularly preferred embodiment the angle of repose of the granules is about 19 degrees.

[00175] Application of biological material to the soil using the granules of the invention provides prolonged benefits that are not achieved using other methods, such as sprays. Without wishing to be bound by any theory, it is believed that the improved granule of the invention enhances the availability of the biological material to target pests, for example, grass grubs, enabling the biological material to subsist for longer periods in the soil. 2. Manufacture of granules

[00176] Processes for the preparation of coated granules for use in agricultural applications are known, and will be apparent to a person skilled in the art on reading the present specification. [00177] In one aspect the invention relates to a method of producing a granule, comprising the steps of

a) providing a deformable core comprising a binder incorporated within or

coated on the deformable core, and

b) at least partially coating the deformable core with a particulate material

comprising particles having a mean size of from about 0.1 μηη to about 50 to form a coated granule.

[00178] Referring to the process diagram shown in Figure 1, the granules may be prepared as follows.

[00179] A substrate 1 is provided, and coated with a first coating 2a comprising biological material to form a first-coated material 2. Preferably, the first coating comprises an aqueous concentrate comprising the biological material. The first coating may be applied to the substrate using a blender, seed coater or other suitable mixing device.

[00180] In one exemplary embodiment the first coating is prepared by combining a biodegradable polymer and a non-cytotoxic oil with water to form a gel stock 2b, mixing the gel stock with the biological material to form the first coating 2a, and applying the first coating 2a to the substrate to form the first coated material 2. When the biological material is a microorganism, the biological material may be provided in a broth.

[00181] In one embodiment the first coating further comprises applying one or more layers comprising one or more particulate desiccants 2c. For example, following

applications of the first coating 2a, the core is dusted with a first layer comprising two particulate desiccants and a second layer comprising one particulate desiccant. In an exemplary embodiment the first layer comprising bentonite and talc and the second layer comprises talc.

[00182] The first coated material 2 is coated with a second coating 3a comprising at least one particulate desiccant to form a deformable core 3.

[00183] The second coating may be applied by combining the first coated material 2 and the second coating 3a in a coating device and circulating the coating device to form the deformable core 3. Suitable coating devices for use in applying the second coating to the first coated material include a seed coater or a pan granulator. [00184] The second coating preferably comprises at least two particulate desiccants. Most preferably, the second coating comprises bentonite and gypsum.

[00185] The second coating 3a optionally comprises a disintegrant 3b. In one exemplary embodiment the second coating is prepared by combining the one or more particulate desiccants, with a disintegrant, for example potato starch, using a blender until the second coating is visibly uniform.

[00186] Preferably, a binder 3c is applied to the first coated material 2 concurrently with the second coating 3a to facilitate adherence of the second coating to the first coated material. Preferably, binder 3c and second coating 3a are added alternately to the first coated material 2 in a seed coater to form the deformable core 3. Binder 3c is sprayed into the coating device to ensure uniform coating of the granules as layers of the second coating 3a are built up on the first coated material.

[00187] When the first coated material 2 is stored for more than 24 hours before application of the second coating 3a, the surface of the first coated material may require re- moistening before the second coating is applied. For example, the first coated material 2 is coated with binder 3c in a coating device immediately before the second coating 3a is applied.

[00188] In one embodiment a ratio of up to 1 : 2.5, preferably a 1 : 1 ratio, w/w of the first coated material 2 to second coating 3a is used. In one embodiment such ratios may be chosen for applications of the granules into soil. In another embodiment a ratio of more than 1 : 2.5, preferably a 1 :4 ratio w/w of the first coated material 2 to second coating 3a is used. In one embodiment such ratios may be chosen for applications of the granules on to soil.

[00189] In a particularly preferred embodiment, a first binder 3c and second coating 3a are applied alternately to the first coated material 2, followed by a final layer of a second binder 3d. The second binder 3d may be used to bind the particulate material 4a.

[00190] The deformable core 3 is coated with particulate material 4a to form a coated granule 4 using a coating device as described above. Preferably, the deformable core 3 is circulated in the coating device until substantially all of the surface of the deformable core is coated with the particulate material 4a.

[00191] The coated granules 4 are dried to form the granules of the invention 5. The coated granules may be dried using devices well known in the art, for example a fluidised bed dryer. Alternatively, the coated granules may be spread out on trays to dry at ambient temperature.

[00192] In one embodiment the coated granules are dried until the granules have a moisture content of from about 11% to about 19%. The moisture content of the granules may be measured using a Berthold moisture meter.

3. Use of the granules

[00193] The granules of the present invention are suitable for application using distribution devices used for subsurface application that subject the granules to high mechanical forces. For example, the granules are suitable for application using a seed drill, for example, a gravity seed drill, a mechanical drill, or a pneumatic drill.

[00194] The granules of the present invention are also suitable for application on to the surface of soil or pasture, for example by aerial application, or using a ground spreader.

[00195] During the drying stage of the manufacture of agricultural granules, the temperature of the granules is increased, liberating moisture. When the dried granules are packaged into bags, the liberated moisture is released into the bags. Many types of bags used to store agricultural compositions are breathable, allowing water vapour to escape. However, once condensation has formed on the inside surfaces of the bags, it cannot be removed. The granules in contact with the condensation on the inside surfaces of the bag will soften and begin to smear. When the granules are applied to soil using a seed drill for example, softened granules are retained in the rotary dosing valve of the drill after each revolution, resulting in blocking of the drill and inaccurate dosing.

[00196] The granules of the invention resist softening when exposed to condensation during storage. The granules of the invention retain their hardness and flowability during storage so that they can be readily applied using distribution devices that subject the granules to high compression forces.

[00197] Advantages of the granules of the present invention include

• preservation of, or an increase in, the viability of the biological material in the

granules,

free flow of the granules, even in moist conditions,

resistance to adhesion, deformation and smearing when applied using a distribution device, for example, a seed drill,

resistance to softening in the presence of condensation or moisture, and

suitability for co-application with moist agricultural compositions, such as urea, without softening. [00198] The invention consists in the foregoing and also envisages constructions of which the following gives examples only and in no way limit the scope thereof.

EXAMPLE 1 [00199] This example describes the preparation of granules comprising Serratia entomophila. The performance of granules coated with various particulate materials was tested .

1. Preparation of the deformable core.

First coating Gel stock preparation

[00200] 10 kg xanthan gum and 10 kg canola oil were combined in a 40 L bucket, and stirred with an electric hand stirrer carefully at first until all powder was wetted, then vigorously until product was smooth and flowable.

Preparation of first coating

[00201] To coat 150 kg zeolite, 20.6 kg cold water and 15 ml. thiosulphate were combined and 27.6 kg Serratia entomophila broth added. 4.2 kg of the gel stock was added quickly with rapid stirring, until well blended. The mix was rested for 10 minutes and re- stirred to ensure uniform blending.

Application of first coating

[00202] 150 kg of zeolite was coated with the first coating in a blender for

approximately 20 minutes until the product looked uniform. The product was covered throughout blending to reduce moisture loss.

Second coating

Preparation of dry blend

[00203] Potato starch, followed by bentonite and gypsum were combined in a blender until the product was visually uniform.

Preparation of binder

[00204] 20 kg of dechlorinated, cold water was combined with 10 ml. 10% sodium thiosulphate solution. 400 g solid polyvinyl alcohol (PVA) was added with rapid stirring and brought to the boil to produce a 2% PVA solution.

Application of second coating [00205] To form the deformable core of granules suitable for application using a seed drill, 25 kg of core coated with the first coating was combined with 25 kg dry blend (1 : 1 core: second coating) and 5 L binder in a seed coater, and circulated to coat with the second coating.

2. Preparation of granules

Exterior coating

Trial of exterior coatings

[00206] Eleven exterior coatings were trialled. The exterior coatings comprised the following particulate materials. 1. Microsilica (Microsilica 600)

2. Microsilica (Ballance BSil)

3. Hydrophilic fumed silica (Aerosil 200)

4. Amorphous silica (Tixosil 38A)

5. Kaolin and T1O2 (FP 24001 Bayer) 6. Kaolin and Ti0₂ (FP 24003 Bayer)

7. Gypsum (Soil Life)

8. Zeolite

9. Talc

10. Attapulgite (a magnesium aluminium phyllosilicate) 11. Bentonite (Calben grade)

Application of exterior coating

[00207] While continuing to circulate the core in the seed coater, 3% by weight of particulate material was added. The granules were circulated for at least 30 seconds to embed the particulate material into the surface of the deformable core to form the exterior coating of the granule. The surface of the exterior coating of the granules was rounded off. Drying

[00208] The granules were dried using a fluid bed dryer at an air temperature of 27°C and an airflow setting of 47-52 cu ft/min. Granules were dried to a moisture content of 12.5-24%. Fines below 1 mm and above 4 mm in size were screened out, and discarded. 3. Performance testing

Flowability

[00209] The granules were processed through an Allan seed drill. The Allan seed drill forces the granules through a tight aperture. The degree of smearing of the granules as they exited the seed drill was assessed. Compression

[00210] This test assessed the resistance of the granule to deformation under compression.

[00211] The granules were subjected to a hand compression test whereby the granules were squeezed hard and then released . If the granules remained free-flowing the granules received a high score. If the squeezed granules formed as a lump the granules receive a low score.

Condensation

[00212] This test assessed the ability of the granules to retain the internal moisture thus protecting the shelf life of the product. A score of 10 was given when the granules remain dry, and score of 1 was given when the granules were wet having absorbed moisture to their surrounds.

Urea resistance

[00213] This test assessed the compatibility of the granules with urea. Urea typically softens materials it is in contact with, destroying the structural integrity of that material. The flow of the granules after storage with urea for one hour was assessed by observing physical deformities in the granules, and determining flowability by pouring the granules through a 10 mm funnel. A score of 10 was given when the granules were entirely urea- resistant.

4. Results

[00214] The results of the performance testing are shown in Table 1.

Material

Exterior

Trial description Urea

coating Flow Compression Condensation

No. (particle resistance material

size) Microsilica

600

1 Microsilica (>99% of 10 10 8 6

particles <50

pm)

Ballance BSil

2 Microsilica 9 9 8 6

(<50 μητι)

Hydrophilic Aerosil 200

3 6 6 8 4

fumed silica (12 pm)

Tixosil 38A

Amorphous

4 (60 m - 6 7 7 3

silica

estimated)

FP 24001

(Bayer)

5 Kaolin + T1O2 6 6 2 3

(<50 m - estimated)

FP 24003

(Bayer)

6 Kaolin + T1O2 6 6 2 3

(<50 pm - estimated)

Soil Life^®

7 Gypsum (<200 m - 5 5 3 3

estimated)

8 Zeolite (>200 pm) 5 5 2 3

(<50 pm -

9 Talc 5 5 4 - estimated)

magnesium

aluminium

10 Attapulgite phyllosilicate 5 5 1 0

(<300 pm - estimated)

Calben grade

11 Bentonite (<250 pm - 1 0 0 0

estimated)

Table 1: Results of performance testing of granules comprising various exterior coating materials. [00215] This example demonstrates suitable particulate materials for use in the exterior coating of the granules of the invention.

EXAMPLE 2

[00216] This example assesses the efficacy of granules of the invention for establishing amber disease in grass grub larvae under different soil moisture conditions.

[00217] Infection of larvae with S. entomophila ("amber disease") is an effective method for biological control of grass grubs.

1. Methods

[00218] Granules were prepared as described for Example 1. A first binder comprising 2% by weight Poval^® 405 PVA was used to apply the second coating (4 L first binder per 50 kg granules). A second binder comprising 2% by weight Poval^® 105 ( 1 L second binder per 50 kg granules) was used to apply microsilica (1.5 kg per 50 kg granules) to form the exterior coating of the granules.

[00219] To form granules suitable for drill application, 25 kg zeolite coated with the first coating was coated with 25 kg of the second coating material (1 : 1 core:second coating). To form granules suitable for broadcast application on to soil, 10 kg of zeolite coated with the first coating was coated with 40 kg second coating (1 :4 core:second coating).

Glasshouse pot trial

[00220] A glasshouse pot trial was conducted in a constant environment room using two litre plastic containers to contain samples. Treatment conditions are summarised in Table 2.

[00221] A Wakanui silt loam passed through a 4 mm sieve was used. For the 20% and 28% soil moisture treatments (1, 2, and 5-9), 2000 g soil was moderately compacted into the pots. Because of the lower bulk of the drier soil, 2200 g of soil was used for the 12% initial soil moisture treatments (3 and 4). Six ryegrass plants (3-4 leaves) were

transplanted into each pot prior to application of grass grubs and granules.

Equivalent Initial soil

No. Granule application rate moisture Watering regime

1 No granules NA 20% Maintain at 20%

2 Drill 30 kg/ha 20% Maintain at 20%

3 Broadcast 120 kg/ha 12% Allow to dry 4 Broadcast 120 kg/ha 12% Maintain at 12%

5 Broadcast 120 kg/ha 20% Allow to dry

6 Broadcast 120 kg/ha 20% Maintain at 20%

7 Broadcast 120 kg/ha 28% Drench

8 Broadcast 120 kg/ha 28% Maintain at 28%

9 Broadcast 120 kg/ha 28% Allow to dry

Table 2: Treatment conditions for pot trial.

[00222] The broadcast granule was applied evenly across the surface of each pot at a rate equivalent to 120 kg/ha (0.348 grams per pot; 6.84 x 10^s cfu/g). The drill granules were applied at a rate equivalent to 30 kg/ha (0.087 grams per pot; 1.00 x 10⁹ cfu/g) in one offset diagonal line across the pot to a depth of 25-30 mm. This approximated the distance grubs could be expected to move in the field when drilled granules are applied at 15 cm coulter spacing.

[00223] Field-collected, third instar grass grub larvae (average weight 0.133 g) were subjected to a 3-day pre-trial feeding test to select healthy grubs. Six grubs were placed in each pot (equivalent of 210 grubs/m²) after application of granules in the drill pots, but before application for the broadcast pots.

[00224] Treatments 1, 2, 4, 6 and 8 were watered every six days to maintain their initial soil moisture for the duration of the trial. Individual pots were weighed at each watering and sufficient water was added to bring the soil moisture to 2% above the initial soil moisture for that pot. Water was applied evenly across the soil surface of each pot in such a manner that there was no ponding on the soil surface in the pots and water did not drain out of the pots.

[00225] At 6, 8, 12 and 24 days post-application, the treatment pots were watered three times with 120 ml water over a period of 1-2 hours simulating a cloud burst deluge or irrigation event equivalent to 13 mm of rainfall.

Amber disease assessment

[00226] Five weeks post-application of granules, the number of live and dead grubs in each pot was counted. Live grubs were subjected to standard visual and feeding assays to determine amber disease levels. Briefly, larvae were separated in individual cells of a tray, each cell comprising a 2x2x2 cube of carrot. Trays were sealed and incubated at 15°C. Grass grubs were considered positive for amber disease if they ceased feeding within 3-7 days.

2. Results

[00227] All granule treatments caused significant amber disease in grass grub larvae compared with the no granule control as shown in Table 3.

Granule Initial soil Final soil Mean amber disease p-value

moisture moisture (+/- SEM) (relative to no granule

treatment 1)

1 No granules 20% 20% 7.6 +/- 2.9

2 Drill 20% 20% 88.2 +/- 3.7 <0.001

3 Broadcast 12% 6% 11.7 +/- 3.5 NS

4 Broadcast 12% 12% 49.6 +/- 5.6 <0.001

5 Broadcast 20% 11% 29.1 +/- 5.0 0.001

6 Broadcast 20% 20% 72.8 +/- 5.0 <0.001

7 Broadcast 28% 74.1 +/- 5.4 <0.001

8 Broadcast 28% 28% 79.1 +/- 4.8 <0.001

9 Broadcast 28% 17% 56.6 +/- 5.9 <0.001

Table 3: Amber disease in grass grub larvae recovered from pots treated with granules of the invention.

[00228] This example demonstrates that the granules of the invention deliver an effective amount of biological material to soil, even when the soil moisture content is low.

EXAMPLE 3

[00229] This example assesses the efficacy of granules of the invention applied to soil at different application rates.

1. Methods

[00230] Granules suitable for drill and broadcast application were prepared as described for Example 2. Broadcast granules were loaded with different amounts of S. entomophila innoculum : 6.66 x 10¹³ cfu/100 kg (lx), 1.33 x 10¹⁴ cfu/100 kg (2x) or 3.33 x 10¹³ cfu/100 kg (2x). Field trial

[00231] Field trials were conducted at sites in South Waikato, South Otago and

Canterbury, New Zealand. At each site, the trials were carried out in a randomised block design with six replicates per treatment. The treatments are described in Table 4. [00232] Six replicates of each treatment were arranged in a randomised block design at each site. Broadcast granules (1 :4) were applied manually using a Solo 421 granule spreader in both directions (3.3 m swaths) at rates of 60, 120 or 240 kg/ha. Drill treatments were applied using a proprietary gravity feed triple disc drill utilising a Duncan metering system and fitted with press wheels at a rate of 30 kg/ha.

Application rate Serratia application

No. Granule (kg/ha) rate (cfu/ha)

1 Drill 30 4 x 10¹³

2 Broadcast 60 4 x 10¹³

3 Broadcast 120 8 x 10¹³

4 Broadcast 60 8 x 10¹³

5 Broadcast 120 4 x 10¹³

6a Broadcast 240 8 x 10¹³

6b Broadcast 120 1.6 x 10¹⁴

Control - no

7 0 0

treatment

Table 4: Treatment conditions for field trial.

[00233] Six weeks post-application, the level of amber disease in grass grubs was assessed. At least 50 grass grub larvae were recovered from each plot by random spade sampling and amber disease determined as described for Example 3. 2. Results

[00234] All granule treatments at all application rates and granule innoculum loadings caused significant amber disease in grass grub larvae compared with the control treatment as shown in Table 5.

Granule (S. Application Serratia Mean amber p-value entomophila rate application disease (+/- (relative to loading) (kg/ha) rate (cfu/ha) SEM) control)

1 Drill 30 4 x 10¹³ 13.6 +/- 1.7 <0.001

Broadcast

60 4 x 10¹³ 7.2 +/- 1.6 <0.001

(lx) Broadcast

3 120 8 x 10¹³ 12.0 +/- 2.5 <0.001

(lx)

Broadcast

4 60 8 x 10¹³ 7.9 +/- 1.7 <0.001

(2x)

Broadcast

5 120 4 x 10¹³ 6.6 +/- 1.9 <0.001

(0.5x)

Broadcast

6a 240 8 x 10¹³ 14.8 +/- 3.1 <0.001

(0.5x)

Broadcast

6b 120 1.6 x 10¹⁴ 27.3 +/- 6.2 <0.001

(2x)

7 Control - no

/ 0 0 1.0 +/- 0.4

treatment

Table 5: Mean amber disease in grass grub larvae recovered from plots at three sites treated with granules of the invention six weeks post-application.

[00235] This example demonstrates efficacy of the granules of the invention for delivering biological material to soil to control pests when applied at different application rates, innoculum loadings and using both broadcast and drill application methods.

EXAMPLE 4

[00236] This example assesses the long term stability of granules of the invention.

[00237] Granules suitable for drill application were prepared according to the method described for Example 2. The granules were packed into 15 kg TGT bags and stored for approximately 3-4 months at ambient temperature. The bags were then stored for a further six months at 4°C.

[00238] Bacterial viability of granules sampled from four individual bags was measured at the time of manufacture and after nine months total storage. Two samples from each bag were tested. The results are shown in Table 6.

Sample At manufacture 9 months storage 9 months storage

(bag) (cfu/g) (replicate 1) (replicate 2)

1 1.2 x 10⁹ 1.4 x 10⁹ 1.1 x 10⁹

2 1.1 x 10⁹ 8.0 x 10^s 9.1 x 10⁸

3 1.1 x 10⁹ 7.4 x 10⁸ 6.3 x 10⁸

4 1.0 x 10⁹ 1.0 x 10⁹ 1.5 x 10⁹

Table 6: Viability of bacteria in granules of the invention at manufacture and after nine months storage. [00239] This example demonstrates that biological material in granules of the invention retains and/or increases viability during storage.

EXAMPLE 5

[00240] This example demonstrates granules of the invention comprising various biological materials. This example also assesses the viability of the biological materials in the granules of the invention after storage.

[00241] Granules suitable for drill application comprising various biological materials were prepared as follows. 5 g xanthan gum was mixed with 5 g canola oil and 115 g broth comprising the biological material to form a gel (first coating). 325g zeolite was placed into a cake mixer and blended with the first coating to form 500 g first-coated material. The first-coated material was transferred to a CIMBRIA CC-Lab seed coater and 500 g second coating (comprising 343.75 g gypsum, 125 g bentonite and 31.25 g potato starch) was added with approximately 50 ml. 2% PVA (grade BF17W) as binder to form the second- coated material. 25 g microsilica was subsequently added to form an exterior coating on the granules.

[00242] The granules were stored in a 20°C incubator for 5 weeks.

[00243] The viability of the bacteria in the granules was measured at the time of manufacture and after 5 weeks storage. The results are shown in Table 7.

Species of Description of Viability Viability after %

biological biological after 5 weeks at survival material material manufacture 20 °C (cfu per

(cfu per g) g)

Pseudomonas Gram negative 3.46xl0⁷ 2.31xl0⁷ 67% chloraphis Non spore forming

Burkholderia Gram negative 1.75x10^s 3.95x10^s 225% terricola Non spore forming

Rhizobium Gram negative 9.35xl0⁶ 9.18xl0⁷ 981% leguminosarum Non-spore forming

biovar TA1

Serratia Gram negative l. lxlO⁹ 3.76xl0⁹ 316% proteomaculans Non spore forming

Penicillium Fungi 1.85 x 10^s 1.20x10^s 65% janczewskii Spore forming

Beauveria Fungi 1.80x10^s 2.20xl0⁷ 12% bassiana Spore forming Metarhizium Fungi 2.95xl0⁶ < 10² - anisopliae Spore forming

Bacillus subtilis Gram positive 1.05xl0⁷ 3.60xl0⁷ 343%

Spore forming

Serratia SE: 1.15xl0⁹ 4.40x10^s 38% entomophila and

Metarhizium

anisopliae MA: 3.7xl0⁵ 2.50xl0⁶ 675%

Table 7: Viability of microorganisms in granules of the invention at manufacture and after 5 weeks storage at 20°C.

[00244] This example demonstrates that the biological material in granules of the invention retains and/or increases viability during storage.

EXAMPLE 6

[00245] This example describes the preparation of granules comprising Serratia entomophila. The performance of granules prepared using various binders was tested and compared to prior art granules lacking an exterior coating. [00246] Granules suitable for drill application comprising alternative binders were prepared according to the method described for Example 5. The same binder was used to apply the second coating and the microsilica for each granule.

[00247] Prior art granules that did not have an exterior coating were prepared according to the method described in Example 8 (formulation 9) of WO 2009061221. Briefly, a first coating was prepared comprising 15 g xanthan gum, 15 g salad and cooking oils and 230 ml. S. entomophila broth to form a gel. 650 g zeolite was coated with the gel to form a gel- coated material. 50 g of bentonite and talc mixed at a 1 : 1 ratio was coated on the gel coated material. A further 50 g talc was added to the granules. The granules were tested for hardness, compressibility and swellability. The results are shown in Table 8. [00248] Hardness of at least 20 granules from each batch was determined using an

Instron model 4204 with third party computer interface and 100 Newton load cell. Granules were observed during testing and the point where the outer core split was recorded as the crush point.

[00249] A compression modulus calculated from the slope of force applied vs

compression distance was also determined. The compression modulus refers to the slope of the straight line section of the compression curve prior to the crush point. [00250] Swellability was determined by measuring adsorption of moisture by the granules. A lOcmxlOcm fine mesh bag was weighed and 10 g granules added to the bag. The bags were placed onto the surface of 2 paper towels wetted with 100ml water. Bags were collected after 2 hours, blotted dry and re-weighed. The weight of water absorbed by the granules was calculated as the difference between the dry weight and weight of the granules minus the weight of the bag.

Exterior Binder Type of Hardness Compression Swell- Water coating binder (N) Modulus ability activity

(N/mm) (mg

water)

Microsilica Xanthan gum Poly- 5.88 39.36 3598 0.881 electrolyte

Polysaccharide

Microsilica Maltodextrin Poly4.73 53.46 2867 0.885 saccharide

Microsilica Carboxy Cellulose 3.68 44.36 3592 0.751 methylcellulose

Microsilica Pre-gel Potato Starch 4.43 46.95 3218 0.669 starch

Microsilica PVAIcohol Polyvinyl 4.35 75.35 2903 0.946

(BF17W) alcohol

Microsilica Gelatin Protein 8.92 72.17 3257 0.938

Microsilica Methylcellulose Cellulose 6.17 62.78 - 0.532

None None - 7.399 124.08 - 0.993

Table 8: Performance testing of granules of the invention compared with granules lacking an exterior coating.

[00251] This example demonstrates describes granules of the invention comprising a range of different binders.

Claims

Granules comprising

a) a deformable core,

b) a binder incorporated within and/or coated on the deformable core, and

c) an exterior coating that at least partially coats the deformable core comprising a particulate material, the particulate material comprising particles having a mean size of from about 0.1 m to about 50 m.

Granules according to claim 1 wherein the deformable core comprises

a) a substrate,

b) a first coating that at least partially coats the substrate, the first coating comprising biological material, and

c) a second coating that at least partially coats the first coating, the second coating comprising at least one particulate desiccant and a binder.

Granules according to claim 2 wherein the first coating comprises biological material, a biodegradable polymer and/or a non-cytotoxic oil.

Granules according to claim 3 wherein the biodegradable polymer is a polysaccharide.

Granules according to any one of claims 2 to 4 wherein the biological material comprises one or more microorganisms.

Granules according to any one of claims 2 to 5 wherein the particulate desiccant is selected from the group comprising a phyllosilicate, a sulphate mineral, an

aluminosilicate, a clay mineral, a calcium salt, a volcanic glass, a silicate, or a combination of any two or more thereof.

Granules according to any one of claims 2 to 6 wherein the particulate desiccant comprises bentonite, gypsum, or bentonite and gypsum.

Granules according to any one of claims 2 to 7 wherein the second coating further comprises a disintegrant, preferably a pre-gelatinised starch, most preferably potato starch.

Granules according to any one of claims 2 to 8 wherein the substrate is selected from the group comprising a clay granule, a silicate mineral, an aluminosilicate mineral, vermiculite, a fertiliser granule, or a combination of any two or more thereof.

10. Granules according to any one of claims 1 to 9 wherein the particulate material has a mean size of about 1 to about 30 μηη, preferably about 5 to about 20 μηη.

11. Granules according to any one of claims 1 to 10 wherein the particulate material has a) a D90% of from about 2 to about 20 μιτι, or

b) a D50% of from about 1 to about 5 μηη.

12. Granules according to any one of claims 1 to 11 wherein the particulate material is selected from the group comprising a phyllosilicate, an aluminosilicate, a clay mineral, a sulphate mineral, a silicate, a silica, or a combination of any two or more thereof.

13. Granules according to claim 12 wherein the particulate material is microsilica.

14. Granules according to any one of claims 1 to 13 wherein the granules comprise a second binder.

15. Granules according to any one of claims 1 to 14 wherein the binder and/or the second binder comprise a polymeric compound selected from the group comprising a polyhydroxyl compound, a polymer or copolymer of a C 1-C6 alkyl substituted with one or more groups selected from the group comprising lactams or 2-pyrollidone, shellac resin, a disaccharide, a polyelectrolyte, a polyethylene glycol, a polyethylene oxide, a polyacrylamide, a polyester, a cellulose, a lignin, a biodegradable gum, an

oligopeptide, a polypeptide or a latex.

16. Granules according to claim 15 wherein the polymeric compound has an average

molecular weight of from about 50 kDa to about 200 kDa, preferably from about 50 kDa to about 100 kDa, most preferably from about 70 to about 90 kDa.

17. Granules according to claim 15 or claim 16 wherein the polymeric compound is a

polyhydroxyl compound.

18. Granules according to any one of claims 15 to 17 wherein the polyhydroxyl compound has a degree of hydrolysis of from about 80 mol% to about 100 mol%, preferably from about 90mol% to about 100mol%.

19. Granules according to any one of claims 15 to 18 wherein the polyhydroxyl compound is polyvinyl alcohol.

20. Granules according to any one of claims 15 to 18 wherein the polyhydroxyl compound is a polysaccharide selected from the group comprising a starch, a dextrin, chitosan, a gum or a synthetic polysaccharide.

21. Gra nules according to claim 15 or claim 16 wherein the polymeric compound is a polymer or copolymer of

a) a C2-C6 hydroxyalkyl, and

b) a C2-C10 hyd roxyalkyl, optionally substituted with acyl and/or optiona lly comprising an ether moiety, for example, methacrylic acid-ethyl acrylate copolymer.

22. Granules according to claim 15 or claim 16 wherein the polymeric compound is

polyvinylpyrollidone.

23. Granules according to a ny one of claims 1 to 22 wherein the granules a re substantially resista nt to deformation upon application of a pressure of up to about 0.5 to about 4 kg/cm².

24. Granules according to a ny one of claims 1 to 23 wherein the granules have a hardness of at least about 0.5 N .

25. Granules according to a ny one of claims 1 to 24 wherein the biological material retains at least about 10% viability after five weeks storage at ambient temperature.

26. Granules according to a ny one of claims 1 to 25 wherein the colony forming units (cfu) of the biological material per gram of granules after five weeks storage at ambient temperature is at least about 10% of the cfu of biological material per gram of freshly prepared granules.

27. An agricultural composition comprising granules of any one of claims 1 to 26.

28. A method of producing a granule, the method comprising

a) providing a deformable core comprising a binder incorporated within and/or coated on the deformable core, and

b) at least partially coating the deformable core with a particulate material comprising particles having a mean size of from about 0.1 μηη to about 50 μηη to form a coated granule.

29. A method according to claim 28 wherein the deformable core is formed by

d) providing a substrate,

e) coating the substrate with a first coating comprising biological material to form a first coated material, and

f) coating the first coated material with a second coating comprising at least one

particulate desiccant and with a binder to form the deformable core.

30. A method according to claim 29 wherein the first coated material is coated with alternating layers of the second coating and the binder.

31. A method according to claim 29 or claim 30 wherein the deformable core is coated with a second binder.

32. A method according to claim 31 wherein the second binder is less soluble in water than the first binder.

33. A method according to any one of claims 30 to 32 wherein the first binder or second binder has a viscosity of about 1 to about 300 cP.

34. A method according to any one of claims 28 to 33 wherein the first binder or second binder has a pH of about pH 4 to about pH 6.

35. A method according to any one of claims 28 to 34 wherein the first binder or second binder comprises from about 0.5% to about 5% w/v of a polymeric compound, preferably a polyhydroxyl compound, most preferably a polyvinyl alcohol.

36. A method of distributing granules on to or into soil to control a pest, preferably an insect pest, the method comprising

a) supplying granules of any one of claims 1 to 26 to a distribution device, and b) applying the granules on to or into soil using the distribution device.