Non-toxic coating concentrates for agricultural use

Abstract

The invention includes a non-toxic agricultural formulation comprising a concentrated liquid suspension of an organic phase and a suspended particulate material, and further includes an aqueous formulation comprising the concentrated liquid suspension and an agricultural treatment agent. In addition, the invention includes a method of treating an agricultural subject, comprising providing an agricultural formulation comprising a concentrated liquid suspension of an organic phase and a suspended particulate, and applying the agricultural formulation to the agricultural subject, thereby treating the agricultural subject.

Description

[0001] Related applications

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 62 / 359,191, filed July 6, 2016, and U.S. Provisional Patent Application No. 62 / 404,343, filed October 5, 2016. The entire contents of the above applications are incorporated herein by reference. Technical Field

[0003] This application relates to coating formulations for agricultural use. Background Technology

[0004] Agricultural chemicals used as fertilizers, pesticides, herbicides, etc., are easily eroded and leachable from treated soil and plants. For example, fertilizers applied to farmland may suffer runoff or loss due to rapid irrigation, rainfall, or other water contact. As another example, chemicals applied to foliage are easily lost due to erosion from treated plants. As yet another example, pre-emergence agents (i.e., those applied to the soil before the plants or weeds germinate) need to remain in the application site for a period of time. Loss of pre-emergence agents during the germination period due to microbial activity, photodegradation, chemical degradation, runoff due to water contact, etc., is undesirable, and it is advantageous to retain the agent in the top one or two inches of soil during this period. These issues are particularly important for optimizing the properties of agents that need to act over an extended period of time to achieve their desired effect, compared to agents that act immediately, such as pesticides that kill upon contact. Agricultural chemicals may be washed away by rainwater or may be easily removed without improved retention properties.

[0005] For example, it is critical to protect pre-harvested fruits / nuts / vegetables. Fruits or vegetables growing on trees and vines and bushes are susceptible to insect infestation and their tender skins are susceptible to sunburn, which reduces the overall yield of the product. In new farming methods, there is an effort to reduce or eliminate the amount of synthetic pesticides used, especially for fruits or vegetables that have edible skins. To help combat the pest problem, granules that form a barrier layer are often sprayed on these fruits or vegetables to prevent insect infestation and sunburn. In some other fruits, such as cherries and tomatoes, even the accumulation of water at the fruit stem causes water imbibition, resulting in an imbalance in the permeation of the interior of the fruit, causing unsightly cracking of the fruit skin. To prevent this, a breathable, benign, and rain-resistant barrier coating is needed. There is still a need in the art for non-toxic alternatives to pesticides that can be used to protect agricultural materials from insect, fungal, animal, drought conditions, air pollution damage, and sun damage. In addition, there is a need to improve herbicide performance by (1) enhancing the retention of active ingredients in the topsoil, (2) preventing leaching of active ingredients (i.e., slow release), and (3) protecting herbicides from photodegradation. Protection of pre-harvested fruits / nuts / vegetables is particularly needed due to the high value of the fruits / nuts / vegetables and the demand for organic products.

[0006] New generations of herbicides and other such agricultural treatment agents are biologically derived. For example, there are biological control agents that need to be delivered to an agricultural subject, where it is desirable for the agent to remain and / or be released in a controlled manner proximate to the agricultural subject. As used herein, the term "agricultural subject" is selected from the group consisting of a leaf, a fruit, a vegetable, a seed or seed coat, a stem, a post-harvest agricultural product, and soil, an agricultural growth medium or other agricultural substrate, as understood by one of ordinary skill in the art. Desirably, a delivery formulation that provides improved retention properties would be suitable for use with a biological control agent.

[0007] Advantageously, herbicides, pesticides, fungicides, plant growth regulators, insect pheromones, nutrients, and other agricultural treatment agents can also be used for direct spraying of fruits or vegetables and plants. For example, cacao pods can suffer from "black pod" disease, which is treated by spraying the pods with both a fungicide and a pesticide. Black pod disease is a plant disease caused by a Phytophthora type oomycete, such as Phytophthora infestans, the pathogen that caused the Irish potato famine. Enhanced retention of the treatment agent on the subject (e.g., cacao pod) can improve its efficacy and increase the efficiency of the treatment regimen. A naturally derived coating for cacao pods would also create a physical barrier (i.e., a barrier coating composition formed into, for example, a film) to deter pests and can reduce or eliminate the need for additional treatment agents.

[0008] Agricultural treatments (pesticides, fertilizers, plant growth regulators, etc.) are expensive and can cause environmental damage if misused. There is a need for materials and methods to improve efficiency and cost associated with the use of agricultural treatments, or to reduce or eliminate the need for agricultural treatments. SUMMARY

[0009] Disclosed herein in embodiments are non-toxic agricultural formulations comprising a concentrated liquid suspension of an organic phase and a suspended particulate material. In embodiments, the formulation forms a solidified coating on an agricultural object. In embodiments, the solidification is water resistant, rub resistant, or rain resistant. In embodiments, the solidified coating allows the suspended particulate material to remain on the agricultural object when subjected to adverse conditions, where adverse conditions can be conditions such as rainfall, rubbing, wind, water contact, and secondary agricultural treatments. In embodiments, the formulation is stable to phase separation. In embodiments, the formulation comprises food grade ingredients, or comprises organically produced ingredients, or comprises generally recognized as safe ingredients. In embodiments, the formulation consists essentially of organically produced ingredients, or consists essentially of generally recognized as safe ingredients. In embodiments, the concentrated liquid suspension contains only non-aqueous liquids. The organic phase of the formulation can be from about 40 to about 99% by weight of the formulation. The organic phase can comprise a drying oil, and the drying oil can be selected from the group consisting of linseed oil, raw linseed oil, boiled linseed oil, castor oil, castor oil glycidyl ether, tung oil, grape seed oil, safflower oil, linoleic acid, linolenic acid, oleic acid, sea buckthorn oil, sunflower oil, evening primrose oil, perilla oil, and walnut oil. In embodiments, the drying oil comprises alpha-linolenic acid, linoleic acid, or a combination thereof. In embodiments, the suspended particulate is from about 0.5 to about 50% of the formulation. The suspended particulate can be persistently suspended in the organic phase, or can be easily resuspended in the organic phase. In embodiments, the suspended particulate is selected from the group consisting of a clay mineral and an organically modified mineral. The clay mineral can be selected from the group consisting of a kaolin clay, a smectite clay, an illite clay, a chlorite clay, sepiolite, and attapulgite. In embodiments, the clay mineral can be a bentonite clay. In embodiments, the organically modified mineral is a clay mineral, and the organically modified mineral can be modified with an organic modifier selected from the group consisting of a fatty acid, a fatty amine, a fatty amide, a fatty ester, a fatty amine quaternary ammonium salt, a quaternary amine surfactant, cetyltrimethylammonium bromide, a fatty alcohol, decyl alcohol, dodecyl alcohol, linseed oil, alkenyl succinic anhydride, styrene maleic anhydride copolymer, rosin, turpentine, chitosan, and castor oil derivatives. In embodiments, the formulation further comprises a pesticide, a herbicide, a beneficial bacteria, a beneficial fungus, a plant growth regulator, a pheromone, a sunscreen, a biopesticide, or a nutrient. In embodiments, the formulation further comprises a plant extract or a plant oil. In embodiments, the formulation further comprises an additional particulate material. In embodiments, the additional particulate material can be selected from the group consisting of talc, calcium carbonate, gypsum, magnesium silicate, calcium silicate, corn starch, cellulose fiber, psyllium fiber, ethylene bis-stearamide, microcrystalline cellulose, stearic acid, oleic acid, a wax, carnauba wax, and beeswax, or it can be kaolin or titanium dioxide. In embodiments, the formulation further comprises a surfactant. The surfactant can be selected from the group consisting of an anionic, a cationic, a non-ionic, a biodegradable, a food grade, and an organic surfactant.In some embodiments, the formulation further includes an adjuvant selected from the group consisting of cellulose, polylactic acid, polyglycolic acid, and polylactic-glycolic acid. In some embodiments, the formulation further includes a salt or a curing additive.

[0010] The embodiments also disclose an aqueous formulation comprising the aforementioned concentrated liquid suspension and an agricultural treatment agent. The embodiments also disclose a coating agricultural treatment agent comprising the agricultural treatment agent and the aforementioned concentrated liquid suspension, wherein the concentrated liquid suspension is applied as a coating to the agricultural treatment agent. Furthermore, embodiments of plant products having surfaces treated with the aforementioned formulation are disclosed herein.

[0011] This document discloses methods for treating agricultural objects, including providing an agricultural formulation containing a concentrated liquid suspension of an organic phase and suspended particles, and applying the agricultural formulation to the agricultural object to treat it. In this embodiment, the method protects the agricultural object from pests or environmental damage. In this embodiment, the treatment includes non-lethal alteration of pest behavior. In this embodiment, the agricultural object is a soil surface or agricultural growth medium. In this embodiment, the soil surface is treated to produce beneficial effects selected from the group consisting of erosion control, nutrient retention, agricultural treatment agent retention, dust control, delivery of beneficial microorganisms, delivery of biopesticides, or increased growth of beneficial microorganisms. In this embodiment, the agricultural object is a plant surface. The plant surface can be selected from the group consisting of leaves, fruits, seeds, berries, nuts, grains, stems, and roots. The plant surface can be the surface of harvested products. In this embodiment, the agricultural object is an agricultural growth medium. In this embodiment, the agricultural formulation is applied to the agricultural object at a dosage rate of about 1 to about 200 lbs. per acre of crop. In this embodiment, the agricultural formulation is diluted with a solvent prior to the application step. This article also discloses a method for reducing the spore-based spread of fungal plant diseases by treating plant surfaces with the preparation described above, wherein the fungal plant diseases are caused by pathogenic fungal spores, and wherein contact with the preparation interferes with the ability of pathogenic fungal spores to spread through the air, thereby reducing the spore-based spread of fungal plant diseases. This article also discloses a method for reducing the spore-based spread of fungal plant diseases by applying the preparation described above to plant surfaces, wherein the fungal plant diseases are caused by pathogenic fungal spores, and wherein contact with the preparation interferes with the ability of pathogenic fungal spores to germinate on plant surfaces, thereby reducing the spore-based spread of fungal plant diseases. This article also discloses a method for treating plant infections by applying the preparation described above to plant surfaces where this is desired. Such treatment methods include infection prevention. Detailed Implementation

[0012] The present disclosure relates to non-toxic agricultural formulations that exist as concentrated liquid suspensions, where the formulations can form a solidified coating on an agricultural object. The concentrated liquid suspensions of the non-toxic agricultural formulations can be diluted in water to make a solution of the agricultural formulation for application by spraying, brushing, dipping, spreading, or irrigation. The agricultural formulations can be applied to various agricultural substrates or objects, such as agricultural surfaces, including plant surfaces (leaves, fruits, seeds, berries, nuts, grains, stems, roots, etc.), soil or agricultural growing media, and harvested plant products, such as fruits, vegetables, seeds, grains, stems, roots, etc. As used herein, a plant surface is the surface of a plant before or after harvest; a plant product is an agricultural product after harvest. Agricultural formulations and methods for treating agricultural substrates and objects are disclosed herein.

[0013] A. Agricultural formulation

[0014] In embodiments, the non-toxic agricultural formulation includes a vegetable oil that contains fatty acid or fatty ester functional groups that have at least one degree of unsaturation, such as mono-unsaturated and poly-unsaturated fats. In embodiments, the vegetable oil contains unsaturated fatty groups, such as alpha-linolenic acid, linoleic acid, and oleic acid, where these fatty groups can exist in the form of a fatty acid, a fatty acid salt, a fatty ester, a triglyceride, a diglyceride, a monoglyceride, or a fatty amide. In embodiments, the vegetable oil is a drying oil. As used herein, the term “drying oil” refers to a self-crosslinking oil consisting of triglycerides of fatty acids, or to a vegetable oil as described herein. Drying oils are characterized by having a high level of poly-unsaturated fatty acids, particularly alpha-linolenic acid. Examples include flaxseed oil (i.e., linseed oil, including boiled linseed oil (BLO) and raw linseed oil (RLO)), tung oil, canola oil, sunflower oil, safflower oil, soybean oil, fish oil, corn oil, dehydrated castor oil, tall oil, perilla oil, and walnut oil. As crosslinks between double bonds of adjacent chains form a polymer network in the presence of atmospheric oxygen, and the oil solidifies or “dries.” Drying oils form a hard, hydrophobic film on their own, so they are useful for coating surfaces or particles to prevent moisture. Drying oils as disclosed herein can also suspend particulate materials, for example particulate minerals, both so that the particulate materials do not separate from the drying oil (“permanent” suspension), and so that, if they are initially separated, the particulate materials are easily resuspended in the drying oil.

[0015] In embodiments, the oil phase of the concentrated liquid suspension includes drying oils, waxes, cellulose products, linseed oil, cooked linseed oil, castor oil, castor oil glycidyl ether, magnesium stearate, linseed oil, tung oil, grapeseed oil, safflower oil, linoleic acid, linolenic acid, oleic acid, sea privet oil, sunflower oil, corn oil, wheat germ oil, cottonseed oil, soybean oil, sesame oil, canola oil, evening primrose oil, perilla oil, and walnut oil. In embodiments, the oil phase of the concentrated liquid suspension contains a diluent, such as mineral oil, petroleum distillate, alcohol, terpenes, or glycols (such as glycerol or propylene glycol), to improve fluid handling properties or improve the flexibility of the dry film. Preferably, the oil phase contains α-linolenic acid, linoleic acid, or a combination thereof.

[0016] The concentrated liquid suspension contains particulate material in vegetable oil. In embodiments, the particulate material may be clay minerals. Clay minerals include, but are not limited to, the following types of clay: (a) kaolin clay (including minerals such as kaolinite, dickite, halloysite, and perlite (polymorphs of Al2Si2O5(OH)4)); (b) montmorillonite clay, including dioctahedral montmorillonite such as montmorillonite and montmorillonite, and trioctahedral montmorillonite such as soapstone; (c) illite clay, which includes clay mica; (d) chlorite clay; and (e) other clay types, such as sepiolite and attapulgite. In embodiments, the clay mineral may be bentonite clay.

[0017] In this embodiment, the particulate material may be an organically modified mineral, such as organoclay. For example, organoclay may include minerals modified with organic modifiers, such as bentonite, kaolin, zeolite, attapulgite, or talc. The organic modifiers may be fatty acids, fatty amines, fatty amides, fatty esters, fatty amine quaternary ammonium salts, quaternary ammonium surfactants, hexadecyltrimethylammonium bromide, fatty alcohols, decanol, dodecyl alcohol, linseed oil, alkenyl succinic anhydride (ASA), styrene-maleic anhydride (SMA) copolymers, rosin, rosin, chitosan, or castor oil derivatives (such as...). ).

[0018] In embodiments, the particulate material can be talc, calcium carbonate, gypsum, magnesium silicate, calcium silicate, corn starch, cellulose fiber, psyllium fiber, ethylene bis-stearamide, microcrystalline cellulose, stearic acid, paraffin, carnauba wax, or beeswax, where the particulate material is used alone or together as a mixture. In other embodiments, the particulate material can be a specific particle selected to form a barrier, for example, against moisture or against insect damage. In embodiments, the specific particle can include planar, high aspect ratio particles, such as clays, mica, and the like, which have the ability to form a flat, organized film when mixed with an appropriate binder. In certain embodiments, the particulate material of the formulation can be a non-clay mineral, such as mica, talc, silica, titanium dioxide, gypsum, calcium carbonate, aluminum phosphate, and the like. In preferred embodiments, the particulate material of the formulation can be bentonite, exfoliated bentonite, organoclay, kaolin, gypsum, zeolite, Fuller's earth, or diatomaceous earth.

[0019] In embodiments, the clay used for these applications can be exfoliated by using the methods described in WO 2013 / 123150 (PCT Application No. PCT / US13 / 2684, entitled "Processes for Clay Exfoliation and Uses Thereof"), the contents of which are incorporated herein by reference. Incorporation of particles into the barrier film provides additional benefits of reflecting or absorbing light and heat energy. Certain fruits and vegetables suffer crop reduction or economic loss due to exposure to environmental stresses such as excessive sunlight, freezing or frost conditions, oxidative damage, microbial or fungal growth, osmotic expansion and cracking under wet conditions, heat stress, and drying under low humidity or windy conditions. Incorporation of particles in the barrier film of the formulations of the present disclosure can reduce the damage caused by these stresses. These particles can be combined with additional high intensity pigments, such as titanium dioxide (Ti02), to provide a white or reflective surface that reduces heat absorption from sunlight, and thereby reduces sunburn or heat-induced damage. Ti02 can also enhance the ultraviolet (UV) light resistance of the surface of the agricultural object by absorbing or reflecting a large portion of the UV radiation that is incident on the surface of the agricultural object. Other sunscreen materials, such as conjugated organic compounds, can also be included.

[0020] The agricultural formulation is provided in the form of a concentrated liquid suspension comprising an oil-based continuous phase and suspended particles. The concentrated suspension is a liquid having a viscosity between about 10 cP and about 50,000 cP, as measured by a Brookfield LVDV-III+ rheometer using Spindle LV-3 at 30 rpm; alternatively, the concentrated suspension is a pasty fluid having a viscosity between about 50,000 cP and 500,000 cP, as measured by the same instrument under the same conditions. In embodiments, the concentrated suspension is a liquid having a viscosity between about 50 cP and about 5000 cP. In embodiments, the concentrated suspension is stable against separation of the particles from the oil-based continuous phase (i.e., phase separation) such that the suspension resists settling for at least 24 hours after it is mixed. In embodiments, the suspension resists settling for at least 90 days after it is mixed. In embodiments, the concentrated suspension comprises more oil-based liquid than suspended particles on a mass basis. In embodiments, the mass ratio of particles to oil-based liquid in the formulation ranges from 1 to 100 parts of particles per 100 parts of oil-based liquid. In embodiments, the concentrated liquid suspension is anhydrous.

[0021] In embodiments, the agricultural formulation includes a surfactant to improve the dispersibility of the particulate mineral in the oil phase and to improve the wetting of the formulation on an agricultural subject after dilution. As is known in the art, particulate materials such as minerals can be hydrophilic in nature, and thus they do not readily suspend in oil. In embodiments, the formulation therefore includes a surfactant or dispersant such as an ethoxylated alcohol, a sorbitan fatty ester, an alkyl polyglycoside, an ethylene oxide / propylene oxide (EO / PO) copolymer, guar gum, xanthan gum, soy lecithin, or an ethoxylated sorbitan stearate, which are known to facilitate stable suspension of the particulate mineral in the oil phase, allowing a long-lasting and stable concentrated liquid formulation to be obtained.

[0022] In embodiments, the agricultural formulation includes a dispersant or suspending agent to improve the dispersibility and dilution of the formulation in water, to improve the stability of the formulation after dilution, and to improve the wetting of the formulation on an agricultural subject after dilution. In embodiments, the concentrated liquid suspension includes a dispersant or suspending agent such as guar gum, xanthan gum, carboxymethylcellulose, carrageenan, alginate, gelatin, pectin, starch, hydroxypropyl guar gum, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl cellulose, hydroxyethyl cellulose, and ethyl cellulose. In embodiments, the dispersant or suspending agent is added to the agricultural formulation in an amount of about 0.01% to about 5% by weight. In embodiments, the dispersant or suspending agent is added to the agricultural formulation in an amount of about 0.1% to about 2% by weight. In embodiments, the dispersant or suspending agent is added to the agricultural formulation in an amount of about 0.1% to about 1% by weight.

[0023] In embodiments, the agricultural formulation includes one or more stabilizing additives, which can be added in amounts ranging from 0.1 wt% to 30 wt%, depending on the additive.

[0024] Without being bound by theory, it is understood that because the formulation includes domains of high-density material dispersed in a continuous domain of low-density material, gravity can drive the high-density material to settle to the bottom of the container and form a sediment. To overcome this problem, a stabilizing additive can be used to increase the viscosity of the continuous phase, thereby reducing the rate of settling, but this can make it difficult for the user to pour the formulation. As an alternative, an additive can be chosen that causes the continuous phase to exhibit pseudoplastic behavior (i.e., in which the viscosity decreases with increasing shear rate). Formulations containing such an additive exhibit a reduced rate of settling, but can still be easily poured because the shear rate characteristics of the settling are much less than those of the pouring, mixing, or other fluid transfer processes.

[0025] In embodiments, a stabilizing additive can be chosen that causes the continuous phase to form a fragile solid at low shear stress, but to transition to a liquid once a critical stress level is exceeded. The composition and concentration of the additive are chosen such that the critical stress is slightly greater than the shear stress associated with settling. Formulations containing such an additive exhibit essentially no settling, but once the fragile solid is broken by shaking, mixing, or other forms of mild agitation, the formulation flows freely. In embodiments, stabilizing additives that produce this behavior include one or more macromolecules containing weakly associating groups. The interactions between these weakly associating groups result in the formation of a network structure that extends throughout the formulation and is characterized by a yield stress. Ideally, the application of a shear stress that exceeds the yield stress breaks these associations, causing the network to collapse and the macroscopic flow of the formulation.

[0026] In embodiments, additives that are particularly well suited to exhibit these properties include non-ionic triblock copolymers, such as poloxamers, composed of a central hydrophobic chain (e.g., polyoxypropylene) between two hydrophilic chains (e.g., polyoxyethylene), such as those provided by the KOLLIPHOR® series of materials (BASF), and polyetheramines, such as the JEFFAMINE® series of polyether diamines in the ED series (Huntsman). In other embodiments, stabilizing additives that can be used can include castor oil derivatives, such as trihydroxystearin and related rheology modifiers (RHODOSOL® (Elementis Specialties) or (RHEOCIN®) or RHEOCIN (Elementis Specialties) or (RHEOCIN®) or RHEOCIN (BYK Additives and Instruments). Additives for these purposes may be added in doses ranging from 0.01 to 1 wt%, preferably from 0.05 to 0.3 wt%. In embodiments, stabilizing additives may be added to agricultural formulations at temperatures relatively high relative to the formulation temperature, while being mixed with high intensity, for example at temperatures ranging from 55 to 65°C.

[0027] In embodiments, stabilizing additives may include modified urea, urea-modified polyamide, urea-modified polyurethane, and hydroxyl-terminated polybutadiene resin. (Cray Valley)), glycol ethers (e.g., DOWANOL) TM Series (Dow Chemical), polyamide, polyesteramide, etc. For example, products such as... Products: Compounds of BYK 7411ES, BYK 431, BYK 430, and BYK 425 (BYK Additives and Instruments). These additives can be incorporated into the system at concentrations ranging from 0.1 to 4 wt%, preferably from 0.2 to 2 wt%. In embodiments, when using glycol ethers (e.g., DOWANOL) TM When using the Dowanol series (Dow Chemical), the selected glycol ether will preferably have high water solubility. For example, the usable dosage range of Dowanol TPM is from 3 to 5 wt%, and preferably 4 wt%. In other embodiments, the stabilizing additive may include surfactants derived from fatty acids, such as fatty acid polydiethanolamides: examples of these include cocamidodiethanolamine, laurylamide diethanolamine, soyamide diethanolamide, etc., representative versions of which can be found in Lubrizol's AMIDEX. TM CE, KD, and LSM products are found. In other embodiments, surfactants derived from fatty acids (such as polyglycerol esters of fatty acids) can be used as stabilizing additives. These fatty acid-derived additives can be added in doses ranging from 1 to 5 wt%, preferably in doses of 3%.

[0028] In this embodiment, the agricultural formulation includes or is primarily composed of biodegradable ingredients. In this embodiment, the agricultural formulation includes organically produced or “organic” ingredients as defined in the USDA National Organic Program (NOP) ingredient list. In this embodiment, the agricultural formulation includes food-grade ingredients as defined by guidance from the U.S. Food and Drug Administration (FDA). In this embodiment, the agricultural formulation includes inert ingredients as defined in the U.S. Environmental Protection Agency (EPA) Inert Ingredient List in sections 910-960 of 40 CFR 180. In this embodiment, the agricultural formulation includes FIFRA Minimum Risk Ingredients as defined in 40 CFR 152.25 under the Federal Insecticides, Fungicides and Rodenticides Act (FIFRA). In this embodiment, the agricultural formulation is non-toxic, naturally derived, and / or organic, and the formulation is intended to prevent damage to crops and the environment from insects, animals, fungi, and bacteria. In this embodiment, the formulation ingredients are derived from food-grade raw materials. In implementation, the formulation ingredients include materials that are generally considered safe by the U.S. Food and Drug Administration (“GRAS”), such as those listed under 201(s) and 409 of the Federal Food, Drug, and Cosmetic Act (FDCA) in 21 CFR 170.3 and 21 CFR 170.30, or are substantially composed of materials that are generally recognized as safe.

[0029] This concentrated liquid suspension offers numerous commercial advantages. For example, the highly concentrated product form minimizes the volume of product to be transported from the manufacturing site to the point of use. Storage capacity requirements are also minimized by employing this highly concentrated product form. Compared to solid, granular, or powder formulations, it also offers the following advantages: ease of handling as a liquid product, compatibility with automated pumping equipment, safer handling, reduced worker contact, and reduced dust formation. The minimal amount of water in the product can provide benefits in reducing product viscosity, decreasing the tendency for mold and bacterial growth, and lowering the product's freezing or pour point.

[0030] In some embodiments, the concentrated liquid suspension can be diluted with water or other solvents to reach or near the point of use to form a diluted liquid suspension, which can then be applied to agricultural objects by methods such as spraying, misting, atomizing, electrostatic spraying, dip coating, brushing, or broadcasting. Dilution to form the diluted suspension can be accomplished by inline mixing or batch mixing, and the diluted suspension can be processed and applied using conventional spraying equipment. The diluted suspension is formed as an oil-in-water emulsion or an oil-in-water suspension, wherein the oil phase includes drying oil.

[0031] When applied to an agricultural subject, the agricultural formulation forms a curable coating comprising the oil and the particulate material. In embodiments, the curing mechanism is based on the behavior of drying oils, where cross-linking occurs through atmospheric oxygen insertion between double bonds of adjacent fatty acid or triglyceride chains, forming a cured polymer network. The rate of curing can be increased by the use of curing additives, i.e. the use of additives that can speed up the rate of curing of drying oils, such as oxidizing agents or metal salts.

[0032] In embodiments, a concentrated suspension is made by mixing a surfactant, a drying oil, and particles, where the surfactant comprises from about 0.1 to about 15% by mass of the suspension. In embodiments, the suspension does not include water. In embodiments, the suspension includes less than 20% by mass of water. In embodiments, the concentrated suspension includes from about 40% to about 98% by mass of an oil phase. In embodiments, the concentrated suspension includes from about 50% to about 90% by mass of an oil phase. In embodiments, the concentrated suspension includes from about 60% to about 80% of an oil phase. In embodiments, the concentrated suspension includes from about 1% to about 50% by mass of suspended particles. In embodiments, the concentrated suspension includes from about 10% to about 40% by mass of suspended particles. In embodiments, the concentrated suspension includes from about 20% to about 35% by mass of suspended particles.

[0033] In embodiments, the agricultural formulations include or consist essentially of non-toxic ingredients, such that they have low toxicity to plants or animals. Low toxicity can be defined as having an LD 50 > 1000 mg / kg, or preferably an LD 50 > 5000 mg / kg. Toxicity is graded by the Hodge-Sterner scale based on the article “Tabulation of Toxicity Classes” by Harold Hodge and James Sterner, published in the American Industrial Hygiene Association Quarterly, Vol. 4, No. 10, 1949. In embodiments, the agricultural formulations can meet the description of Hodge-Sterner scale 1, 2, or 3; in preferred embodiments, the formulations can meet the description of Hodge-Sterner scale 1. In embodiments, the agricultural formulations include naturally derived ingredients, such as vegetable oils, triglycerides, and naturally occurring minerals.

[0034] In embodiments, the agricultural formulation can be applied such that it dries into a porous film, allowing transpiration by the plant. In embodiments, the porous film can be formed by incorporating or forming pores in the form of gas voids, or by incorporating porous minerals. In embodiments, the pores can be formed by dissolving or degrading a trace component of the coating, leaving a porous coating.

[0035] In embodiments, the agricultural formulations disclosed herein can be used as a carrier or adjuvant for delivering an agricultural treatment in fluid form to an agricultural subject. As used herein, the term "treatment" means to have a beneficial effect on the longevity, productivity, or other biological or economic aspects of an agricultural subject, and "agricultural treatment" means any chemical or biologically active ingredient used to perform such a treatment. The term "secondary agricultural treatment" means an agricultural treatment applied before or after treatment with the agricultural formulations disclosed herein. Non-limiting examples of agricultural treatments include pesticides, herbicides, fungicides, sulfur, copper oxide, plant growth regulators, plant hormones, pheromones, insecticidal soaps, insect pheromones, sunscreens, beneficial bacteria, beneficial fungi, Trichoderma, Bacillus thuringiensis (Bt), Aspergillus fungi, nematodes, RNAi; plant extracts and essential oils such as neem, clove, d-limonene, citrus extract, pinene, pine extract, capsaicin, camphor, geraniol; probiotics, beneficial bacteria or fungi, extracts from bacterial or fungal cultures, spinosyn A, spinosyn D, biopesticides, biofungicides, nematodes, biological control agents, and nutrients.

[0036] As used herein, the term "nutrient" or "nutrients" means those elements necessary for plant growth. The term "nutrients" includes both macronutrients and micronutrients. In addition to the essential elements for growth provided by air and water (carbon, hydrogen, oxygen), there are three primary macronutrients that plants require in large amounts (nitrogen, phosphorus, potassium), and several secondary and micronutrients that are required in lesser amounts or even only in trace amounts (calcium, magnesium, sulfur, boron, chlorine, copper, iron, manganese, molybdenum, zinc, etc.). Micronutrients can play particularly important roles in the plant life cycle, such as facilitating sugar transport, strengthening protein formation, increasing photosynthesis, enhancing root strength, enabling plant immunity, etc.

[0037] Leaf sprays containing nutrients can be used to provide essential nutrients to plants, for example, to correct nutrient deficiencies that limit plant growth or increase susceptibility to pests and pathogens. However, simple sprays currently in use are composed of one or more nutrients dissolved or dispersed in water; after application, these formulations are easily washed or brushed off the leaf surface. This susceptibility to washing or brushing reduces nutrient availability, and it increases the loss of these chemicals into local water supplies. In embodiments, the formulations disclosed herein contain nutrients and form a nutrient-containing film on the leaf that retains one or more nutrients. This property minimizes nutrient washing or brushing, extends the time available for plant uptake, and extends the residual activity of the nutrients. Examples of suitable nutrients include nitrogen, phosphorus, potassium, boron, copper, iron, manganese, molybdenum, zinc, chlorine, nickel, calcium, magnesium, sulfur, and silicon. The nutrients can be provided as salts, complexes, chelates, or organo-mineral compounds. The nutrients can be dissolved in the formulation, dispersed in the formulation, or adsorbed on a component of the formulation. In embodiments, for example, the nutrients can be adsorbed on clay present in the formulation. The dispersed nutrients can take the form of particles having an average particle size of less than 100 μ, less than 10 μ, or less than 1 μ.

[0038] In embodiments, the non-toxic agricultural formulation can be combined with pheromones that cause mating confusion in insects. The agricultural formulation containing the pheromones can be used to prevent insects from successfully reproducing or laying eggs, or to cause insects to deposit eggs in areas where the resulting larvae cannot survive. The agricultural treatment can include an agricultural chemical that can be formulated as a liquid, a solution, a dispersion, a paste, a gel, or an aerosol. The agricultural treatment can non-lethally alter the behavior of a pest. For example, the agricultural treatment can include a biological control agent that exerts a beneficial effect on an agricultural subject through its biological activity, for example, by competing with an agricultural pathogen for space or nutrients on the agricultural subject, or by antagonizing the growth of an agricultural pathogen, by inducing resistance in the agricultural subject, by acting as a natural enemy of an agricultural pest, by causing mating confusion, by causing excessive grooming behavior, or by other biologically-mediated processes. As used herein, an agricultural subject can include plant surfaces and seed surfaces (pre-harvest or post-harvest), plant products, and soil or agricultural growth medium surfaces.

[0039] As used herein, the term "agrochemical" refers to an active chemical ingredient used for agricultural purposes, such as a herbicide, a pesticide, a fungicide, a fertilizer, an insecticide, a probiotic, a nematicide, a plant growth regulator, a plant hormone, an insect hormone, a pheromone, a repellent, or a nutrient. For example, the formulation can act as a protective coating for plants, fruits, vegetables, leaves, berries, seeds, nuts, etc., while also delivering the agrochemical. In embodiments, the agrochemical can be a herbicide, such as dicamba, chlorimuron, and nicosulfuron; they can be an insecticide, such as imidacloprid, neonicotinoid, pyrethroid, chlorantraniliprole, or sulfoximine. In embodiments, the agrochemical can be a fungicide, such as azoxystrobin, calcium polysulfide, metalaxyl, chlorothalonil, chlozolinate, copper salts, cuprous oxide, metal dithiocarbamate complexes, ferbam, maneb, mefenoxam, myclobutanil, pyraclostrobin, prothioconazole, propiconazole, sulfur, thiophanate-methyl, trifloxystrobin, and triforine. In embodiments, the agrochemical can be an oil-soluble chemical, a water-soluble chemical, or a dispersible solid material.

[0040] In embodiments, the agricultural treatment can be a physical agent, such as a sunscreen or a moisture-retention agent. In embodiments, agents such as caffeine, benzoic acid, p-aminobenzoic acid, avobenzone, zinc oxide, and titanium dioxide can be used as sunscreens. In embodiments, humectants such as urea, glycerol, polyvinyl alcohol, ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, calcium chloride, and polyethylene glycol (PEG) can be used as moisture-retention agents.

[0041] In embodiments, the agricultural treatment agent can include a biological agent, such as a gram-positive bacteria, a gram-negative bacteria, a motile microbe, a non-motile microbe, a nodulation microbe, a soil microbe, a rhizosphere microbe, a fungus, etc.

[0042] In certain embodiments, the biological agent includes one or more beneficial microorganisms. As used herein, the term "microorganism" is interchangeable with "microbe" and refers to a microscopic, single-celled or multi-celled organism. Classes of microorganisms include, but are not limited to, organisms such as bacteria, fungi, algae, archaea, viruses, and protozoa. The use of microorganisms as agricultural treatment agents can provide agricultural benefits such as enhancing nitrogen fixation, suppressing disease, protecting plants from plant pathogens, inducing disease resistance in plants, improving nutrient uptake, promoting growth and productivity, improving tolerance to environmental stress, and the like. For example, in embodiments, microorganisms for agricultural treatment can provide direct protection to plants by infecting insect pests or plant pathogenic microorganisms that can attack the plants. As an example of such use, Beauveria bassiana, a fungus that naturally occurs in soil, can be used as an entomopathogen against insect pests. Alternatively, for example, in other embodiments, microorganisms for agricultural treatment can provide indirect protection to plants by competing with pathogenic species for nutrients, by limiting or eliminating nutrients required by pathogenic species or insect pests, or by producing antimicrobial compounds that have an adverse effect on pathogenic species. Yet in other embodiments, microorganisms for agricultural treatment can increase the supply or bioavailability of nutrients to plants. In other embodiments, microorganisms for agricultural treatment can stimulate beneficial biological activities within plants, for example, stimulate leaf growth, stimulate root growth, stimulate immune responses, cultivate tolerance to abiotic stress, and the like.

[0043] In embodiments, the agricultural treatment can include a biological agent such as a beneficial bacteria or fungus, for example, a fungus in mycorrhizal relationship with the roots of a plant, an entomopathogenic strain of fungus, Beauveria, Metarhizium, Isaria, Nomuraea, Tolypocladium, Lecanicillium, Entomophthora muscae, Beauveria bassiana, Pandora neoaphidis, Hirsutella thompsonii, Neozygites floridana, Paecilomyces fumosoroseus, Metarhizium anisopliae, Bacillus aspergillus fungi, Bacillus thuringiensis (Bt), and nematodes. In embodiments, the agricultural treatment agent can be a biopesticide as defined by the United States Environmental Protection Agency (EPA) (https: / / www.epa.gov / pesticides / biopesticides). In embodiments, the agricultural treatment agent can be produced by a bacterium, such as spinosyn A and spinosyn D produced by Saccharopolyspora spinosa.

[0044] In embodiments, the formulation can include a beneficial microbe that is a living microbe. A living microbe can be a replicable microbe, i.e., it is a living organism that is capable of replication. Alternatively, a beneficial microbe can be alive but not replicable, having beneficial properties that do not depend on its replication. For these living microbes, whether or not capable of replication, certain beneficial attributes thereof can arise from their ability to release beneficial substances that contribute to the health of a plant, including freedom from disease, or certain beneficial attributes thereof can arise from their ability to induce effects in a beneficial plant when consumed by another organism in relationship with such a plant. For example, a living beneficial microbe, whether or not replicable, can have a detrimental effect on a pest that would otherwise infest a plant, for example, if the pest consumes this microbe; thus, this detrimental effect on the pest has a beneficial effect on the plant that is susceptible to attack.

[0045] In embodiments, the formulation can include beneficial microorganisms that are non-viable microorganisms. Such microorganisms, while in some cases living organisms, are no longer alive in the formulation, and their beneficial properties do not depend on their viability. Non-viable microorganisms or substances derived from them can exert a beneficial effect, for example by providing beneficial substances that contribute to the health of a plant, including freedom from disease, or by inducing an effect in a beneficial plant when consumed by another organism with which such a plant is associated. For example, a microorganism such as Bacillus thuringiensis can damage the digestive tract of an insect that consumes it, even if the microorganism itself has died.

[0046] Non-viable materials, for example, compounds derived from living or non-viable microorganisms, can be included in the term "biopesticide." Such biopesticides can include materials (e.g., compounds, secretions, excretions, etc.) derived from living microorganisms; biopesticides can also include materials (e.g., compounds, secretions, excretions, or derivatives from the microorganism itself) derived from non-viable microorganisms.

[0047] In embodiments, the concentrated liquid suspension can include adjuvants such as cellulose polymers, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, starch, thermoplastic starch, polyethylene glycol, polylactic acid, polyglycolic acid, poly(lactic-co-glycolic acid), propylene glycol, block copolymers of ethylene oxide and propylene oxide, glycerol, can include osmotic inhibitors such as calcium chloride, terpenes, and vegetable oils. In embodiments, the dry oil-based agricultural formulation can include cellulose-based or cellulose-derived materials such as cellulose esters, cellulose acetate, diacetate cellulose, triacetate cellulose, cellulose acetate propionate, cellulose acetate butyrate, cellulose fibers, cellulose microfibers, cellulose nanofibers, cellulose ethers, ethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and the like. In embodiments, the cellulose-based or cellulose-derived material can be a cellulose-based polymer having a dry oil covalently attached thereto (e.g., via esterification). In embodiments, the cellulose-derived material can comprise a cellulose-based material as described above in combination with one or more functional groups that impart advantageous properties. In other embodiments, the non-toxic barrier coating composition for agricultural surfaces can be formed from a biodegradable composition including polyhydroxyalkanoates such as polyhydroxybutyrate.

[0048] B. Method of using the formulation

[0049] The present disclosure also relates to methods of using the non-toxic agricultural formulations in the form of concentrated liquid suspensions. The agricultural formulations can be applied to various agricultural substrates or objects, such as plant surfaces (leaves, fruits, seeds, berries, nuts, grains, stems, roots, etc.), soil or agricultural growing media, as well as harvested plant products, such as fruits, vegetables, seeds, grains, stems, roots, etc.

[0050] In embodiments, the soil surface can be treated to produce a beneficial effect selected from the group consisting of erosion control, nutrient retention, agricultural treatment agent retention, dust control, delivery of beneficial microorganisms, or increase in growth of beneficial microorganisms.

[0051] In embodiments, the non-toxic agricultural formulations can be used to form seed coatings (coats) to improve the properties of the seeds, such as viability, productivity, growth rate, germination time, resistance to insects, resistance to mold, dust control, resistance to active pesticide ingredient flaking, and resistance to moisture. When used as seed coatings, the formulations can provide protection against Rhizoctonia and Fusarium and soybean rust and nematodes, aphids, maggots, and worms. The formulations can reduce the dusting of the seed coating, be used for treatment improvement, safety, environmental pollution, and avoid non-target application. The seed coating can improve the dry flowability of the seed after treatment and avoid clumping; this results in less residue and less cleaning of equipment required. The seed coating can include rooting compounds, hormones, and plant growth regulators. In embodiments, the formulations can be diluted with water and applied to agricultural objects to form a solidified coating.

[0052] In embodiments, the non-toxic agricultural formulation can be applied to tropical crops such as cacao, coffee, papaya, mango, pineapple, avocado, melon, watermelon, and banana. In the example of cacao, the non-toxic agricultural formulation can prevent cacao pod borer (Conopomorpha cramerella) from destroying the crop. In addition, for cacao, the non-toxic agricultural formulation can prevent black pod rot infestation, for example involving organisms of the genus Phytophthora such as P. palmivora, P. megakarya, P. capsici, P. citrophthora, P. megasperma, P. katsurae, and the like. In addition, for cacao, the non-toxic agricultural formulation can prevent infestation of frosty pod and witches’ broom disease (WBD) involving organisms such as basidiomycete fungi, Moniliophthora roreri, Moniliophthora perniciosa, and the like. In coffee, the non-toxic agricultural formulation can prevent insects such as coffee berry borer or plant diseases such as coffee rust. In embodiments, the non-toxic agricultural formulation can prevent or reduce the spread of fungal infestations by reducing the ability of spores to air-borne. In embodiments, the non-toxic agricultural formulation can prevent or reduce the spread of fungal infestations by reducing the ability of air-borne spores to germinate on the surface of the plant. In embodiments, the non-toxic agricultural formulation can prevent or reduce the spread of fungal infestations by encapsulating the fungus on the surface of the plant or otherwise immobilizing it on the surface of the plant, preventing some or all of the microorganism from gaining access to the interior of the plant.

[0053] In embodiments, the non-toxic agricultural formulation can be applied to vegetable crops, such as zucchini, onions, celery, lettuce, spinach, pumpkin, tomatoes, eggplant, peppers, broccoli, cabbage, cucumbers, and the like. In embodiments, the non-toxic agricultural formulation can be applied to root crops, such as potatoes, sugar beets, carrots, radishes, ginger, and sweet potatoes. In embodiments, the non-toxic agricultural formulation can be applied to legume crops, such as beans, soybeans, and peanuts. In embodiments, the non-toxic agricultural formulation can be applied to cereal grains, such as corn, oats, wheat, sorghum, alfalfa, barley, and rice. In embodiments, the non-toxic agricultural formulation can be used to deter pests, such as corn earworms, navel orangeworms, and hickory shuckworms. In embodiments, the non-toxic agricultural formulation can be applied to tree nut crops, such as almonds, cashews, macadamia nuts, walnuts, hickory nuts, and pistachios. In embodiments, the non-toxic agricultural formulation can be applied to tree fruits, such as apples, pears, peaches, plums, cherries, lemons, oranges, grapefruits, pomelos, and limes. In embodiments, the non-toxic agricultural formulation can be applied to berry crops, such as strawberries, raspberries, blueberries, cranberries, blackberries, and elderberries. In embodiments, the non-toxic agricultural formulation can be applied to grapes used to produce table grapes, juice, or wine. In embodiments, the non-toxic agricultural formulation can be applied to turf grasses, lawns, golf courses, and ornamental plants.

[0054] In embodiments, the non-toxic agricultural formulation can be used to increase crop yield. Crop yield is determined by many factors, including plant health, availability of nutrients and water, pest stress, heat stress, environmental conditions, sunlight, and the microbiome surrounding the plant. The non-toxic agricultural formulation can affect certain of these factors when applied to a crop. In embodiments, the non-toxic agricultural formulation can decrease the water requirement of a crop by reducing water vapor loss into the atmosphere by transpiration.

[0055] In embodiments, the non-toxic agricultural formulation can be used to protect plants and crops from diseases caused by microorganisms, including but not limited to microorganisms such as fungi, molds, mildews, bacteria, viruses, and the like, including diseases such as Potato X virus (PVX) disease, Potato Y virus (PVY) disease, fusarium wilt, zebra chip, bacterial infection, phytoplasma disease, leaf spot, brown rot, gall disease, downy mildew, corn smut, apple rust, leaf curl, leaf spot, mosaic virus disease, oomycete disease, mistletoe, dwarf mistletoe, scab, blight, anthracnose, and the like. In embodiments, the non-toxic agricultural formulation can be used to protect plants and crops from insect-borne bacteria and viruses. As used herein, the term "infection" refers to the pathologic infestation of a plant by a microorganism or disease resulting therefrom. It will be appreciated that an infection can result from the invasion of a plant by a microorganism of exogenous origin, where the attachment or colonization of the plant by the microorganism results in plant pathology or disease through surface-oriented activity, through entry of the exogenous microorganism into the interior of the plant, or through other pathogenic behavior of the microorganism (e.g., toxin formation). It will also be appreciated that an infection can result from the pathologic activity of a microorganism of endogenous origin, through surface-oriented activity, through entry of the endogenous microorganism into the interior of the plant, or through other pathogenic behavior of the microorganism (e.g., toxin formation). For example, an infection can result when a microorganism initially present on the surface of a plant, whether the microorganism is initially exogenous or endogenous, with some or all of the microorganism entering the interior of the plant resulting in plant pathology. In certain embodiments, the non-toxic agricultural formulation can encapsulate or otherwise immobilize a potentially pathogenic microorganism on the surface of a plant, thereby preventing some or all of the microorganism from gaining access to the interior of the plant, in the prevention or amelioration or eradication of an infection (collectively "treatment of an infection"). In other embodiments, the non-toxic agricultural formulation can prevent the invasion of a plant by a potentially pathogenic microorganism of exogenous origin, in the treatment of an infection. In yet other embodiments, the non-toxic agricultural formulation can counteract or prevent surface-oriented activity or other behavior of a microorganism, such as toxin formation, in the treatment of an infection.

[0056] In embodiments, the non-toxic agricultural formulation can be used to protect plants and crops from insect and animal damage caused by elephant, grub, worm, slug, fly, fruit fly, mite, ant, spider, caterpillar, moth, grasshopper, locust, leafhopper, leaf roller, leafminer, aphid, psyllid, ant, beetle, bug, thrips, rabbit, deer, rodent, and the like. In embodiments, the non-toxic agricultural formulation can be used to protect plants and crops from environmental stress, such as excessive sunlight, freezing or frost conditions, oxidative damage, microbial or fungal growth, osmotic swelling and cracking under conditions of moisture, and drying under conditions of low humidity or high wind.

[0057] After preparation, the agricultural formulation can be delivered to a distribution point or point of use. The formulation can remain stable for a long period of time, such as 3-6 months or more. To apply to an agricultural subject, the concentrated liquid suspension can be diluted with a diluent, such as water, and sprayed onto the surface of the plant. In embodiments, the diluted liquid suspension can comprise from about 60 to about 99% water. In embodiments, in more detail, the agricultural formulation can be applied to an agricultural subject by spraying, brushing, misting, aerosol application, atomization, backpack spraying, dip coating, or irrigation on the agricultural subject. The spray solution can also be modified with a small amount of a flow aid to help the droplets disperse after spraying and to minimize aerosol drift to non-subject areas, such as a hydrophilic polymer, such as a high molecular weight water soluble polyacrylamide. In certain embodiments, the formulations are rub resistant or rub-off resistant, and / or they are water resistant. In other embodiments, a water soluble polymer or a wax, such as polyethylene glycol, can be added so that the film is easily removed after a few rinses.

[0058] In certain embodiments, the formulation can be applied to an agricultural subject, such as a plant, fruit, vegetable, and the like. For example, in embodiments, the formulation can be sprayed onto the surface of an agricultural subject, such as a fruit or vegetable or plant surface (trunk, leaf, foliage, branch, seed, berry, nut, root, and the like) or soil or other agricultural growing medium, where the formulation can comprise an active ingredient. The oil droplets comprising the active ingredient can coat the surface of the agricultural subject and form a cross-linked film upon drying. In embodiments, the non-toxic barrier coating can protect the plant from pests such as elephant trunk, maggot, worm, borer, slug, fly, fruit fly, moth, grasshopper, locust, leafhopper, leaf roller, aphid, ant, beetle, bed bug, thrips, rabbit, deer, rodent, and the like. In embodiments, the non-toxic barrier coating can protect the plant and crop from damage caused by diseases transmitted by insects. In embodiments, the non-toxic barrier coating can protect the plant from diseases such as fungus, mildew, mold, citrus greening disease, HLB disease, leaf spot, brown rot, gall disease, downy mildew, corn smut, apple rust, leaf curl, leaf spot, mosaic disease, scab, canker, and anthracnose.

[0059] In certain embodiments, the dry oil based agricultural formulation can be used to form a non-toxic barrier coating composition when applied to an agricultural subject (e.g., a plant, a fruit, a vegetable, etc.). For example, in embodiments, the formulation can be sprayed onto the surface of an agricultural subject, such as the surface of a fruit or vegetable or plant (trunk, leaf, foliage, seed, berry, nut, root, branch, etc.), where the formulation can be free of toxic ingredients such as pesticides. In embodiments, the non-toxic barrier coating composition can deter pest damage due to changes in the organoleptic recognition of the plant surface; for example, the treated plant surface can have different surface energy, slip resistance, compatibility with insect foot physiology, surface texture, odor profile, visual appearance, and thermal signature as compared to an untreated plant surface. This altered organoleptic performance can change the behavior of insects and animals such that they do not choose to eat or otherwise damage the treated plant. In embodiments, the non-toxic barrier coating composition can cause pests to perform grooming behavior, which can deter them from damaging the agricultural subject. In embodiments, the non-toxic barrier coating can immobilize pests that come into contact with the coating by adhering to the pests. The mechanical and rheological properties of the non-toxic barrier coating can be selected such that once the pests are adhered to the coating, they cannot dislodge themselves from the coating, nor can they remove the coating from the agricultural subject. Such pests can be present on the agricultural subject prior to the formation of the non-toxic barrier coating, or they can arrive at the agricultural subject after the coating has been established. In embodiments, the non-toxic barrier coating composition can act as a shield to protect the agricultural subject from insects, fungi, animals, drought conditions, air pollution damage, heat stress, and sunlight damage. As used herein, the term "barrier coating" or "barrier coating composition" can form as a continuous or discontinuous film, or can otherwise be applied in a desired thickness.

[0060] In embodiments, the non-toxic barrier coating formulation can be applied to an agricultural subject at a dosage rate of about 1 to about 200 lbs of formulation per acre of crop (based on undiluted). In embodiments, the non-toxic barrier coating formulation can be applied to an agricultural subject at a dosage rate of about 3 to about 100 lbs of formulation per acre of crop. In embodiments, the non-toxic barrier coating formulation can be applied to an agricultural subject at a dosage rate of about 10 to about 75 lbs of formulation per acre of crop.

[0061] Any of these benefits as described above are non-limiting examples of a desired therapeutic effect. The purpose of an agricultural treatment is to achieve a desired therapeutic effect, i.e., any effect that increases production of a pre-harvest agricultural product, or enhances the appearance, taste, durability, or other favorable properties of a post-harvest agricultural product. A material used for an agricultural treatment is an agricultural treatment agent. For example, a desired therapeutic effect can be a protective effect (e.g., protection from pests, fungi, sunburn, drought, ozone, acid rain, environmental toxins, etc.), or a nutrient effect (e.g., delivery of a fertilizer, growth hormone, plant nutrient, etc.), or a pre-harvest enhancement effect (e.g., providing an agent that includes improving a natural property of a pre-harvest product through genetic modification), or a post-harvest protective or enhancement effect (e.g., protecting the skin or surface of a post-harvest fruit, vegetable, or seed, or improving its appearance, taste, or commercial appeal). Certain fruits and vegetables suffer crop loss or economic loss due to exposure to environmental stress such as excessive sunlight, freezing or frost conditions, oxidative damage, microbial or fungal growth, osmotic swelling and cracking in wet conditions, and drying in low humidity or windy conditions. Reducing these crop losses and economic losses is another example of a desired therapeutic effect of a coating formulation. Other examples of desired therapeutic effects are well known to those of ordinary skill in the art. To achieve a desired therapeutic effect, a subject can be treated with a formulation for an exposure time that is believed to be appropriate to achieve the desired therapeutic effect. Exposure times for various formulations and subjects are well known to those of ordinary skill in the art. The exposure time can be pre-selected, or it can be determined post-exposure based on the degree to which the desired therapeutic effect is achieved, or based on other parameters that can be observed or determined by the skilled artisan.

[0062] In embodiments, the agricultural formulations and methods disclosed herein can extend the therapeutic effect of an active agricultural ingredient, such as a biological agent or an agricultural chemical. For example, the disclosed formulations can act to protect the active agricultural ingredient from dispersing or deactivating after contact with an agricultural subject. The agricultural formulations disclosed herein can deliver an agricultural chemical to an agricultural subject and keep it there; further, the agricultural formulations can protect the agricultural chemical from adverse conditions that can dilute or remove the agricultural chemical, such as rain, abrasion, wind, water contact, and secondary agricultural treatments (e.g., subsequent spraying or application or utilization of an agricultural treatment).

[0063] In embodiments, the agricultural formulations and methods disclosed herein can be used to deliver biological agents, such as beneficial bacteria, beneficial fungi, and / or biological control agents, to an agricultural subject, and / or to retain biological control agents on an agricultural subject. Biological control agents can include a variety of life forms, including plants, insects, and microorganisms, such as bacteria, fungi, and viruses. In embodiments, the agricultural formulations can include biological control agents in an amount from about 0.001% to about 10%. In embodiments, the agricultural formulations can include biological control agents in an amount from about 0.01% to about 1%. In embodiments, the agricultural formulations can include biological control agents in an amount from about 0.05% to about 0.5%. In embodiments, the biological control agents include at least one strain of Bacillus thuringiensis (Bt), or an endotoxin produced by Bt. The use of Bt has been proven to be safe and effective for insect control, and the delivery of Bt by the agricultural formulations and methods disclosed herein can improve or extend the effectiveness of insect control. Biological control can include the introduction, conservation, or augmentation of natural enemies of agricultural pests. The formulations and methods disclosed herein can function in biological control by delivering biological control agents to an agricultural subject in the form of a solid or liquid formulation, or by providing a barrier coating or film that assists the work of other biological control agents. In embodiments, the delivery of biological control agents by the agricultural formulations and methods disclosed herein can improve or extend the effectiveness of biological control agents by improving their rainfastness. In embodiments, a barrier coating, for example as described above, can include biological control agents in particulate form, thereby retaining the biological control agents near the agricultural surface, and / or releasing them in a predetermined, time-delayed manner.

[0064] In embodiments, biological control agents can be formulated in liquid or solid form. For example, suspensions of commercially available spores, toxins, fungal particles, viral particles, and the like can be sprayed onto crops like conventional insecticides to be used as biological control agents. Table 1 shows a non-exhaustive list of exemplary biological control agent formulations:

[0065] Table 1: Representative Microbial Insecticides

[0066]

[0067] (Table from:

[0068] https: / / www.cals.ncsu.edu / course / ent425 / text19 / biocontrol.html (2003)

[0069] The above-described formulations and methods for producing agricultural treatments including solid or liquid agricultural chemicals can also be applied to agricultural treatments including biological control agents that have been formulated into solids or liquids.

[0070] Examples

[0071] Materials

[0072] • Refined Linseed Oil, Cargill

[0073] • National Standard Bentonite 325, Bentonite Performance Minerals LLC

[0074] • Ecosense 919, DOW

[0075] • Crude Linseed Oil, Cargill

[0076] • Castor Oil Glycidyl Ether, CVC Specialty, Moorestown, NJ • Pluronic L121, BASF, Florham Park, NJ • Isopar M, ExxonMobil Chemical

[0077] • Gum Rosin, Sigma Aldrich, St. Louis, MO

[0078] • Arabica Coffee Tree, Amazon.com

[0079] • Decyl Glucoside, Dow Chemical Connection

[0080] • Linseed Oil, Sigma Aldrich, St. Louis, MO

[0081] • Triethylenetetramine (TETA), Sigma Aldrich, St. Louis, MO

[0082] • Span 85, Tokyo Chemical Industry (TCI)

[0083] • SugaNate 160, Colonial Chemical Co.

[0084] • Potassium Laurate, Viva Corporation

[0085] • Xanthan Gum, Cargill

[0086] • Geraniol, Sigma Aldrich, St. Louis, MO

[0087] • d-Limonene, Florida Chemical Co.

[0088] • Magnesium stearate, Sigma Aldrich, St. Louis, MO

[0089] • Microcrystalline cellulose, Sigma Aldrich, St. Louis, MO

[0090] • Castor oil, Sigma Aldrich, St. Louis, MO

[0091] • Bentonite, Sigma Aldrich, St. Louis, MO

[0092] • Titanium dioxide, J.T. Baker, Phillipsburg, NJ

[0093] • Precipitated calcium carbonate, Specialty Minerals Inc., New York, NY

[0094] • Other materials described in the Examples below

[0095] Example 1 : Preparation of a 1 : 1 mixture of linseed oil / colophony

[0096] Rosin was added to the linseed oil in a 1 : 1 weight ratio. The mixture was mixed and heated at over 60 °C for 2 hours to dissolve the rosin in the linseed oil.

[0097] Example 2: Preparation of linseed oil / castor oil glycidyl ether / triethylenetetramine

[0098] Linseed oil, castor oil glycidyl ether (GE35-H), and triethylenetetramine (TETA) were mixed in a 1 : 1 :0.05 ratio. The mixture was mixed with a vortexer (VWR Scientific Products, Mini Vortexer 945800) for approximately 10 seconds.

[0099] Example 3: Preparation of linseed oil / castor oil glycidyl ether / magnesium stearate / triethylenetetramine

[0100] Linseed oil, castor oil glycidyl ether (GE35-H), magnesium stearate, and triethylenetetramine (TETA) were mixed in a 1 : 1 :0.75:0.05 ratio. The mixture was mixed with a vortexer (VWR Scientific Products, Mini Vortexer 945800) for approximately 10 seconds.

[0101] Example 4: Method of treating agricultural products

[0102] The formulation of Example 5 (see below) can be applied to cocoa pods to reduce damage to the fruit caused by infestation by the cocoa pod borer (Conopomorpha cramerella). The formulation can be applied at various stages of pod growth, preferably within the time frame when the fruit skin is green, preferably after 2-4 weeks after the pod has started to grow on the plant. This application can be done using a standard spray duster such as a backpack sprayer. This method of application is particularly suitable for pre-harvest coating application on large fruits such as cocoa, pineapple, apple and papaya that grow on trees, although other methods of application such as conventional mechanical sprayers used in large agricultural fields of row crops can also be used. The formulation can remain on the cocoa pod skin for several weeks at a time, protecting the fruit from the cocoa pod borer. The coating should be pliable and allow the fruit to grow as desired, and a second application can be required a few weeks before harvest. After harvest, fruits with inedible skins such as cocoa pods do not require post-harvest washing to be processed. Other fruits and vegetables with edible skins such as papaya, mango, apple, cherry, tomato can require a simple post-harvest washing with mild soap to remove the coating.

[0103] This applied coating is expected to produce high yields of fruit with unblemished and intact skins, and free from infestation by pests. Coated fruits and vegetables are expected to be attractive to consumers, and safe to eat with only a general cleaning step by the consumer of these fruits and vegetables.

[0104] Example 5: Formulation for treating agricultural objects

[0105] Formulations were prepared by mixing the ingredients shown in Tables 2 and 3 below. Each formulation was a viscous but free-flowing liquid.

[0106] Table 2

[0107]

[0108] Table 3

[0109]

[0110] Example 6: Formulations comprising different surfactants

[0111] Several aqueous solutions of surfactants were prepared for incorporation into the formulations. Each solution was prepared at a 20% ratio by adding 2 grams of surfactant to 8 grams of tap water. A list of the surfactants tested and their hydrophilic-lipophilic balance (HLB) values is listed in Table 4 below:

[0112] Table 4

[0113]

[0114] From each 20% surfactant solution in Table 4, a 3.60 gram aliquot was taken and added to a separate vial containing 21.60 grams of raw linseed oil. The surfactant solution was vigorously stirred just prior to transfer to the vial containing linseed oil. After mixing the surfactant solution with the raw linseed oil, 10.80 grams of bentonite was added to each vial and stirred vigorously again. The final composition percentages for each sample vial were: 60% raw linseed oil, 30% bentonite, 8% water, and 2% surfactant; these samples are listed in Table 5.

[0115] The formulations were allowed to sit undisturbed for 65 hours and then their stability was assessed by rating how easily the settled bentonite could be re-dispersed. Each vial was gently inverted to observe the amount of bentonite settled at the bottom of the vial and the re-dispersibility of the settled bentonite. The inverted samples were rated on a scale of 1 to 5 for the amount of bentonite clumping, where 1 means "easily re-dispersible" and 5 means "difficult to re-disperse". Samples that were re-dispersible by the bentonite alone after inversion by gravity were noted. Each sample was then vigorously shaken by hand for about 5 seconds at a time and the settled bentonite was again assessed for re-dispersibility. The results are listed in Table 5 below.

[0116] Table 5

[0117]

[0118] Example 7: Formulations with bentonite or corn starch as granule type

[0119] The following formulations were prepared.

[0120] • Formulation #7a: 30% National Standard 325 bentonite, 70% raw linseed oil. To 21 g of raw linseed oil, add 9 g of National Standard 325 bentonite. Mix until uniform.

[0121] • Formulation #7b: 30% National Standard 325 bentonite, 10% Ecosense 919, 60% raw linseed oil. Prepare a 9:1 raw linseed oil: Ecosense 919 by combining 18 g of raw linseed oil (RLO) with 3 g of Ecosense 919 (ES). Mix until uniform. To 21 g of the 9:1 raw linseed oil: Ecosense 919 mixture, add 9 g of National Standard 325 bentonite. Mix until uniform.

[0122] • Formulation #7c: 30% industrial corn starch, 70% raw linseed oil. To 21 g of raw linseed oil, add 9 g of industrial corn starch. Mix until uniform.

[0123] • Formulation #7d: 30% National Standard 325, 10% Ecosense 919, 60% raw linseed oil. Prepare a 9: 1 raw linseed oil: Ecosense 919 by combining 18 g raw linseed oil (RLO) with 3 g Ecosense 919. Mix until uniform. To 21 g of the 9: 1 raw linseed oil: Ecosense 919 mixture, add 9 g of National Standard 325. Mix until uniform.

[0124]

[0125] The formulated 7a, 7b, 7c, and 7d samples were allowed to sit undisturbed for 2 hours and then observed for oil separation and any other settling phenomena. Next, the samples were inverted to determine the amount of effort required to resuspend the mixture. Water dispersibility testing was performed on the resuspendable formulations. To perform water dispersibility testing, 2 g of concentrate was mixed into 31.3 g of tap water and the sample was vortexed. The observations are recorded in Table 6.

[0126] Table 6

[0127]

[0128] Example 8: Formulations with different surfactants

[0129] The following formulations were prepared:

[0130] • Formulation #8a: 30% National Standard 325, 70% raw linseed oil. To 21 g of raw linseed oil, add 9 g of National Standard 325. Mix until uniform.

[0131] • Formulation #8b: 30% National Standard 325, 5% Pluronic L121, 65% raw linseed oil. Prepare a 19: 1 (raw linseed oil: Pluronic L121) mixture by combining 19.95 g raw linseed oil (RLO) with 1.05 g Pluronic L121. The Pluronic L121 material is 100% active, anhydrous. Mix until uniform. To 21 g of the oil / surfactant, add 9 g of National Standard 325 bentonite clay. Mix until uniform.

[0132]

[0133] • Formulation #8c: 30% National Standard 325, 10% Ecosense 919, 60% raw linseed oil. Prepare a 9: 1 raw linseed oil: Ecosense 919 by combining 18.9 g raw linseed oil (RLO) with 2.1 g Ecosense 919. Mix until uniform. To 21 g of the oil / surfactant, add 9 g of National Standard 325. Mix until uniform. The Ecosense 919 surfactant is 50% active and 50% water. ​​

[0134] • Formulation #8d: 30% National Standard 325, 10% Decyl Glucoside, 60% Raw Linseed Oil. A 9: 1 mixture of (Raw Linseed Oil: Decyl Glucoside) was prepared by combining 18.9 g of Raw Linseed Oil (RLO) with 2.1 g of Decyl Glucoside. Mix until uniform. To 21 g of oil / surfactant, add 9 g of National Standard 325 Bentonite Clay. Mix until uniform. The Decyl Glucoside surfactant was 50% active.

[0135] These formulations were tested according to the following protocol: Allow the sample to sit undisturbed for 24 hours. Next, measure the oil separation and any other settling phenomena. Then invert and determine the amount of effort required to resuspend the mixture. Following these steps, water dispersibility testing was performed on resuspendable formulations; mix 2 g of concentrate into 31.3 g of tap water and vortex the sample. The results of the testing are recorded in Table 7.

[0136] Table 7

[0137]

[0138] Example 9: Formulations with suspension additives

[0139] The following formulations were prepared:

[0140] • Formulation #9a: 30% National Standard 325, 10% Pluronic L121, 60% Raw Linseed Oil. Combine 18 g of Raw Linseed Oil (RLO) and 3 g of Pluronic L121. Mix until uniform.

[0141] To 21 g of oil / surfactant, add 9 g of National Standard 325. Mix until uniform.

[0142] • Formulation #9b: 30% National Standard 325, 10% Pluronic L121, 3% Magnesium Stearate, 57% Raw Linseed Oil. Combine 17.1 g of Raw Linseed Oil (RLO) and 3 g of Pluronic L121. Mix until uniform. Next, add 0.9 g of Magnesium Stearate. To 21 g of oil / surfactant, add 9 g of National Standard 325. Mix until uniform.

[0143] • Formulation #9c: 30% National Standard 325, 10% Pluronic L121, 3% Microcrystalline Cellulose (MCC),

[0144] 57% Raw Linseed Oil. Combine 17.1 g of Raw Linseed Oil (RLO) and 3 g of Pluronic L121. Mix until uniform. Next, add 0.9 g of MCC. To 21 g of oil / surfactant, add 9 g of National Standard 325 Bentonite Clay. Mix until uniform.

[0145] These formulations were tested according to the following protocol: the samples were allowed to sit undisturbed for 24 hours. Next, the oil separation and any other settling phenomena were measured. Then, the samples were inverted and the amount of effort required to resuspend the mixture was determined. At the end of these tests, the following results were observed: the sample containing magnesium stearate (#9b) had a greater viscosity and no layer of oil separation compared to sample #9a. The control sample 9a had a layer of oil separation. The sample containing MCC (#9c) showed less oil separation and was easier to resuspend than the control sample 9a.

[0146] Example 10: Agricultural formulation with insecticidal soap

[0147] A formulation suitable for agricultural application was prepared with the insecticidal soap potassium laurate. A 18.88 g aliquot of raw linseed oil was added to a 40 mL glass vial, followed by 1.60 g of SugaNate 160 and 1.60 g of a 40% Span 85 dispersion in water. These materials were shaken and vortexed together. Next, 0.32 g of a potassium laurate sample was added to the vial and shaken and vortexed again. Then, 0.32 g of a xanthan gum sample was added and the sample was shaken and vortexed once more. Finally, added to the concentrated form was 9.60 g of a bentonite sample in three one-third aliquots with shaking and vortexing between each addition. After all of the bentonite was added, the vial was placed on a bottle roller for 30 minutes to disperse any remaining solid clumps. The product made was a formulation containing insecticidal soap suitable for agricultural application. To make a solution for application to plants, a 1.0 g aliquot of the formulation was taken and added to a 20 mL vial containing 15.65 g of tap water. The vial was shaken and vortexed, then observed. After 1 to 2 minutes, the vial showed a stable dispersion in the water with no signs of solid settling or oil separation for at least 30 minutes.

[0148] Example 11 : Agricultural formulation with geraniol

[0149] A formulation suitable for agricultural application is prepared with geraniol, an essential oil that can act as a repellent. A 18.24 g aliquot of raw linseed oil is added to a 40 mL glass vial, followed by 1.60 g of SugaNate 160 and 1.60 g of a 40% Span 85 dispersion in water. These materials are shaken and vortexed together to ensure a well-mixed product. A 0.64 g sample of geraniol is added to the vial, and shaken and vortexed again. A 0.32 g sample of xanthan gum is then added, and the sample is shaken and vortexed once more. The final addition to the concentrate is a 9.60 g sample of bentonite clay, added in three equal portions with shaking and vortexing between each addition. After all of the bentonite has been added, the vial is placed on a roller for 30 minutes to disperse any remaining solid clumps. The product produced is a formulation suitable for agricultural application containing a repellent essential oil. To prepare a dilution for application on plants, a 1.0 g aliquot of the formulation is added to a 20 mL vial containing 15.65 g of tap water. The vial is shaken and vortexed, and then observed. After 30 minutes, the emulsion shows no signs of bentonite settling or oil separation.

[0150] Example 12: Agricultural formulation with d-limonene

[0151] A formulation suitable for agricultural application is prepared with d-limonene, a botanical essential oil insecticide. A 18.24 g aliquot of raw linseed oil is added to a 40 mL glass vial, followed by 1.60 g of SugaNate 160 and 1.60 g of a 40% Span 85 dispersion in water. These materials are shaken and vortexed together to ensure a well-mixed product. A 0.64 g sample of d-limonene is added to the vial, and shaken and vortexed again. A 0.32 g sample of xanthan gum is then added, and the sample is shaken and vortexed once more. The final addition to the concentrate is a 9.60 g sample of bentonite clay, added in three equal portions with shaking and vortexing between each addition. After all of the bentonite has been added, the vial is placed on a roller for 30 minutes to disperse any remaining solid clumps. The product produced is a formulation suitable for agricultural application containing d-limonene. To prepare a dilution for application on plants, a 1.0 g aliquot of the mixture is added to a 20 mL vial containing 15.65 g of tap water. The 20 mL vial is shaken and vortexed, and then observed. After 30 minutes, the emulsion shows no signs of bentonite settling or oil separation.

[0152] Example 13: Agricultural formulation with capsaicin

[0153] A formulation suitable for agricultural application is prepared using the biopesticide capsaicin. An 18.24 g aliquot of raw flax seed oil is added to a 40 mL glass vial followed by 1.60 g of SugaNate 160 and 1.60 g of a 40% Span 85 dispersion in water. These materials are shaken and vortexed together to ensure a well mixed product. To the vial is added 0.64 g of a Tobasco Chipotle Pepper Sauce (McIlhenny Company) sample having 1500-2500 heat units on the Scoville scale followed by more shaking and vortexing. The amount of capsaicin in the sauce is about 90-160 ppm based on the Scoville unit scale where 16 million Scoville units equals pure capsaicin. Then 0.32 g of a xanthan gum sample is added and the sample is shaken and vortexed once more. Finally added in concentrated form is 9.60 g of a bentonite sample in three one-third portions with shaking and vortexing between each addition. After all of the bentonite is added, the vial is placed on a roller for 30 minutes to disperse any remaining solid clumps. The product made is a formulation containing capsaicin suitable for agricultural application. To prepare a dilution for application on plants, a 1.0 g aliquot of the mixture is taken and added to a 20 mL vial containing 15.65 g of tap water. The 20 mL vial is shaken and vortexed and then observed. After 30 minutes, the emulsion shows no signs of bentonite settling or oil separation.

[0154] Example 14: Agricultural formulation with neem oil

[0155] A formulation suitable for agricultural application was prepared with neem oil, a plant oil used as an organic agricultural pesticide. A 15.68 g aliquot of raw linseed oil was added to a 40 mL glass vial, followed by 1.60 g of SugaNate 160 and 1.60 g of a 40% Span 85 dispersion in water. These materials were shaken and vortexed together to ensure a well-mixed product. A 3.20 g sample of neem oil (Blue Lily Organics) was added to the vial and shaken and vortexed again. Then a 0.32 g sample of xanthan gum was added and the sample was shaken and vortexed once more. The final addition to the concentrated form was a 9.60 g sample of bentonite clay, added in three equal portions with shaking and vortexing between each addition. After all of the bentonite clay was added, the vial was placed on a roller bottle apparatus for 30 minutes to disperse any remaining solid clumps. The product made was a neem oil-containing formulation suitable for agricultural application. To prepare a dilution for application on a plant, a 1.0 g aliquot of the mixture was taken and added to a 20 mL vial containing 15.65 g of tap water. The 20 mL vial was shaken and vortexed, then observed. After 30 minutes, the emulsion showed no signs of bentonite settling or oil separation.

[0156] Example 15: Rainfastness of agricultural formulation comprising neem oil

[0157] The rainfastness of the agricultural formulation of Example 14 was tested as follows. A comparative neem oil formulation was prepared by the following method: to a 20 mL vial was added 15.90 g of tap water, followed by 1.0 g of neem oil, 0.0175 g of potassium laurate, and 0.1134 g of 1.0 M sodium hydroxide (Sigma Aldrich). This comparative mixture was vortexed and considered stable enough for spraying. A 3 g aliquot of the comparative neem oil formulation was sprayed onto the surface of a weighed 5" x 3" acrylic sheet (Plaskolite brand) and then rolled with a paint roller. The acrylic sheet material was used as a model for a plant surface. On a separate weighed 5" x 3" acrylic sheet, a 3.0 g aliquot of the diluted agricultural formulation of Example 14 with neem oil was sprayed and rolled with a paint roller. Both treated acrylic sheets were allowed to dry for 18 hours so that the coating could cure, their weights were recorded, and then both sheets were sprayed with a spray bottle for 15 seconds to simulate rainfall. After the water spray, both sheets were placed in a forced air convection oven at 37 °C for 1.5 hours to dry, and their weights were recorded again. The sheet treated with the agricultural formulation of Example 14 containing neem oil retained 68% of the applied coating after the simulated rainfall, while the sheet treated with the comparative formulation of neem oil, potassium laurate, and sodium hydroxide retained no coating after the simulated rainfall.

[0158] Example 16: Agricultural formulation with camphor oil

[0159] A formulation suitable for agricultural application was prepared with white camphor oil, an essential oil used as an insect repellent. A 15.68 g aliquot of raw linseed oil was added to a 40 mL glass vial, followed by 1.60 g of SugaNate 160 and 1.60 g of a 40% Span 85 dispersion in water. These were shaken and vortexed together to ensure a well-mixed product. A 3.20 g sample of white camphor oil (Sigma Aldrich) was added to the vial and shaken and vortexed again. Then a 0.32 g sample of xanthan gum was added and the sample was shaken and vortexed once more. The final addition to the concentrated form was a 9.60 g sample of bentonite clay, added in three equal portions with shaking and vortexing between each addition. After all of the bentonite clay was added, the vial was placed on a roller for 30 minutes to disperse any remaining clumps of solid. The product made was a formulation containing white camphor oil suitable for agricultural application. To make a dilution for application on plants, a 1.0 g aliquot of the mixture was taken and added to a 20 mL vial containing 15.65 g of tap water. The 20 mL vial was shaken and vortexed, then observed. After 30 minutes, the emulsion showed no signs of bentonite settling or oil separation.

[0160] Example 17: Agricultural formulation with beneficial fungi

[0161] A formulation suitable for agricultural application is prepared with beneficial fungi. An 18.56 g aliquot of raw flax seed oil is added to a 40 mL glass vial, followed by a 1.60 g aliquot of product SugaNate 160 and a 1.60 g aliquot of a 40% Span 85 dispersion in water. These are shaken and vortexed together to ensure a well-mixed product. A 0.32 g sample of product "White Shark" (Plant Revolution Inc.) is added to the vial, and shaken and vortexed again. White Shark is a beneficial fungi powder containing 187,875 CFU / g of Trichoderma koningii and 125,250 CFU / g of Trichoderma harzianum. A 0.32 g sample of xanthan gum is then added, and the mixture is shaken and vortexed once more. A 9.60 g sample of bentonite clay is then added in three equal thirds, with shaking and vortexing between each addition. After all of the bentonite clay has been added, the vial is placed on a roller bottle for 30 minutes to disperse any remaining solid clumps. The product made is a formulation suitable for agricultural application containing beneficial fungi. To make a dilution for application on a plant, a 1.0 g aliquot of the mixture is taken and added to a 20 mL vial containing 15.65 g of tap water. The 20 mL vial is shaken and vortexed, and then observed. After 30 minutes, the emulsion shows no signs of bentonite or fungi spore powder settling or oil separation.

[0162] Example 18: Agricultural formulation with sulphur

[0163] A formulation suitable for agricultural application is prepared with elemental sulfur, which can be used as a fungicide. An 18.56 g aliquot of raw flax seed oil is added to a 40 mL glass vial, followed by a 1.60 g aliquot of SugaNate 160 and a 1.60 g aliquot of a 40% Span 85 dispersion in water. These are shaken and vortexed together to ensure a well-mixed product. A 0.32 g sample of elemental sulfur powder is added to the vial, and shaken and vortexed again. A 0.32 g sample of xanthan gum is then added, and the mixture is shaken and vortexed once more. A 9.60 g sample of bentonite clay is then added in three equal thirds, with shaking and vortexing between each addition. After all of the bentonite clay has been added, the vial is placed on a roller bottle for 30 minutes to disperse any remaining solid clumps. The product made is a formulation suitable for agricultural application containing beneficial fungi. To make a dilution for application on a plant, a 1.0 g aliquot of the mixture is taken and added to a 20 mL vial containing 15.65 g of tap water. The 20 mL vial is shaken and vortexed, and then observed. After 30 minutes, the emulsion shows no signs of bentonite or fungi spore powder settling or oil separation.

[0164] Example 19: Rainfastness of agricultural formulation with geraniol

[0165] The rainfastness of the agricultural formulation of Example 11 was tested as follows. A comparative geraniol formulation was prepared by the following method: To a 20 mL vial was added 15.90 g of tap water, followed by 1.0 g of geraniol, 0.0175 g of potassium laurate, and 0.1134 g of 1.0 M sodium hydroxide (Sigma Aldrich). This comparative mixture was vortexed and deemed stable enough for spraying. 3 g of the comparative geraniol formulation was sprayed onto the surface of a weighed 5" x 3" acrylic sheet (Plaskolite brand) and then rolled with a paint roller. On a separate weighed 5" x 3" acrylic sheet, 3.0 g of the diluted agricultural formulation of Example 11 with geraniol was sprayed in small portions and rolled with a paint roller. Both treated acrylic sheets were allowed to dry for 18 hours so that the coating could cure, their weights were recorded, and then both sheets were sprayed with water for 15 seconds from a spray bottle to simulate rainfall. After the water was sprayed, both sheets were placed in a forced air convection oven at 37 °C for 1.5 hours to dry, and their weights were recorded again. The sheet treated with the agricultural formulation of Example 11 containing geraniol retained 34.5% of the applied coating after the simulated rainfall, while the sheet treated with the comparative formulation of geraniol, potassium laurate, and sodium hydroxide left no coating after the simulated rainfall.

[0166] Example 20: Rainfastness of agricultural formulation with d-limonene

[0167] The rainfastness of the agricultural formulation of Example 12 was tested as follows. A comparative d-limonene formulation was prepared by the following method: To a 20 mL vial was added 15.90 g of tap water, followed by 1.0 g of d-limonene, 0.0175 g of potassium laurate, and 0.1134 g of 1.0 M sodium hydroxide (Sigma Aldrich). This comparative mixture was vortexed and deemed stable enough for spraying. 3 g of the comparative d-limonene formulation was sprayed onto the surface of a weighed 5" x 3" acrylic sheet (Plaskolite brand) and then rolled with a paint roller. On a separate weighed 5" x 3" acrylic sheet, 3.0 g of the diluted agricultural formulation of Example 12 with d-limonene was sprayed in small portions and rolled with a paint roller. Both treated acrylic sheets were allowed to dry for 18 hours so that the coating could cure, their weights were recorded, and then both sheets were sprayed with water for 15 seconds from a spray bottle to simulate rainfall. After the water was sprayed, both sheets were placed in a forced air convection oven at 37 °C for 1.5 hours to dry, and their weights were recorded again. The sheet treated with the agricultural formulation of Example 12 containing d-limonene retained 53.9% of the applied coating after the simulated rainfall, while the sheet treated with the comparative formulation of d-limonene, potassium laurate, and sodium hydroxide left no coating after the simulated rainfall.

[0168] Example 21 : Agricultural formulation

[0169] A formulation suitable for agricultural application was prepared as follows. A 18.88 g aliquot of raw flax seed oil was added to a 40 mL glass vial followed by 1.60 g of SugaNate 160 and 1.60 g of a 40% Span 85 dispersion in water. These materials were shaken and vortexed together. Then 0.32 g of the xanthan gum sample was added and the mixture was shaken and vortexed again. Then 9.60 g of the bentonite sample was added in three portions of one-third each with shaking and vortexing between each addition. After all of the bentonite was added, the vial was placed on a roller for 30 minutes to disperse any remaining solid clumps. The product made was a formulation suitable for agricultural application in the form of a fluid suspension. To prepare a dilution for application on a plant, a 1.0 g aliquot of the mixture was taken and added to a 20 mL vial containing 15.65 g of tap water. The 20 mL vial was shaken and vortexed and then observed. After 30 minutes, the emulsion showed no signs of solid settling or oil separation.

[0170] Example 22: Rainfastness of agricultural formulation with Trichoderma

[0171] The rainfastness of the agricultural formulation of Example 17 was tested as follows. A comparative Trichoderma formulation (Example 22a) was prepared as follows: to a 20 mL vial was added 14.85 g of tap water followed by 0.15 g of the product “White Shark” (Plant Revolution Inc.). This comparative mixture was vortexed and considered stable enough for spraying. Then, 3 g of this comparative Trichoderma formulation was sprayed onto the surface of a 5” x 3” sheet of acrylic (Plaskolite brand). On two separate 5” x 3” sheets of acrylic, 3 g of the diluted agricultural formulation of Example 17 (samples a and b) with Trichoderma was sprayed onto each surface. All of the treated acrylic sheets were placed in a convection-free oven at 37 °C for 1.5 hours to dry. An optical image of each sheet was taken using an optical microscope (Zeiss AxioImager.A1M). Then, each sheet was exposed to simulated rainfall by spraying water for 15 seconds using a spray bottle. After the water was sprayed, the sheets were placed in a convection-free oven at 37 °C for 1.5 hours to dry. An image of each sheet was taken again using the optical microscope. The particle distribution in each acrylic sheet was analyzed using ImageJ software (National Institutes of Health) and the results are summarized in Table 8. The sheets treated with the diluted agricultural formulation of Example 17 containing Trichoderma retained 81-86% of the applied particles after simulated rainfall, while the sheets treated with the comparative formulation of Trichoderma retained only 8% of the applied particles after simulated rainfall.

[0172] Table 8

[0173]

[0174] Example 23: Agricultural formulation

[0175] Several surfactant products were evaluated by incorporating each surfactant into an agricultural formulation sample. Eight formulation samples were prepared using the ingredients listed in Table 9 below:

[0176] Table 9

[0177]

[0178] To prepare the samples, first 40 mL vials were filled with raw linseed oil (Cargill) in the amounts listed in Table 9. After the linseed oil was added, a small portion of each surfactant product was added to the corresponding 40 mL vial as listed in Table 9 in the calculated amount so that there would be 2% active surfactant ingredient in the final sample formulation. The dispersion of 40% Span 85 (Millipore) was then shaken vigorously and then added to each individual vial in a 1.60 gram amount. Each sample vial was then shaken and vortexed together to ensure a well mixed product. After this, 0.32 grams of xanthan gum was added to each vial and each vial was shaken and vortexed. The final addition to each vial was 9.60 grams of the bentonite sample added in three one-third portions with shaking and vortexing between each addition. After all of the bentonite was added, each vial was placed on a roller for 30 minutes to disperse any remaining solid clumps. After 30 minutes, each vial was removed and a 1.0 gram portion was taken from each mixture and added to a 20 mL vial containing 15.65 grams of tap water to form a diluted sample. The diluted sample was shaken and vortexed vigorously and observed. The concentrated samples were left overnight.

[0179] Then, a control was prepared in the same manner using 18.72 grams of raw linseed oil, 1.60 grams of a 40% Span 85 dispersion in water, 1.60 grams of water, 0.48 grams of xanthan gum, and 9.60 grams of bentonite. After 30 minutes on a roller, a 1.0 gram portion was removed and added to a 20 mL vial containing 15.65 grams of tap water to form a diluted sample. The diluted sample was shaken and vortexed vigorously and observed. The concentrated sample was left overnight.

[0180] The diluted samples were evaluated to determine if the bentonite was still dispersed or had settled, and if the oil was still dispersed throughout the sample or had become separated at the top. A good result is that both the clay and the oil are uniformly dispersed throughout the water. The results are listed in Table 10 below:

[0181] Table 10

[0182]

[0183] The concentrated formulations were allowed to sit undisturbed for 71 hours, and then evaluated for stability by assessing how easily the settled bentonite could be re-dispersed. Each vial was gently inverted to observe the extent to which the bentonite at the bottom had become compacted and the re-dispersibility of the bentonite. The inverted samples were scored with a "dispersibility" value between 1 and 5, where 1 means "easily dispersible" and 5 means "not dispersible." Samples in which the bentonite was re-dispersible by simply inverting the vial were noted. Each sample was then shaken vigorously by hand for about 5 seconds at a time, and re-evaluated for whether the settled bentonite would re-disperse. The results are listed in Table 11 below:

[0184] Table 11

[0185]

[0186] Example 24: Seed coating with agricultural formulation

[0187] Burpee Pea Super Snappy seeds were coated with 3%, 10%, and 16% (w / w) aqueous mixtures of the agricultural formulation of Example 21 in water; the coated seeds were then air dried at 22°C. The seeds (six replicates of each coating type) were planted in Conrad Fafard Organic Potting Mix and watered daily. Germination rate was determined by the % of planted seeds that germinated, and was recorded after different amounts of time, as shown in Table 12.

[0188] Table 12 Germination Rate

[0189] Days after planting Control (no coating) 3% coating 10% coating 16% coating 3 0％ 67％ 67％ 33％ 4 17％ 83％ 67％ 50％ 5 50％ 100％ 67％ 50％ 6 50％ 100％ 67％ 50％ 7 50％ 100％ 67％ 67％ 10 50％ 100％ 67％ 67％ 11 50％ 100％ 67％ 67％ 12 50％ 100％ 67％ 67％

[0190] Example 25: Agricultural formulation with stabilizer

[0191] Several different additives were evaluated to determine their ability to stabilize the formulation when diluted with water. To prepare these formulations, 18.88 grams of raw flaxseed oil (Cargill) was added to 14 separate vials, followed by 1.60 gram aliquots of the product SugaNate 160 (Colonial Chemical Company) and 1.60 gram aliquots of a 40% dispersion of Span 85 (Millipore) in water. These materials were shaken and vortexed together to ensure a well-mixed product. A single 0.32 gram sample of each emulsion stabilizer (as listed in Table 13) was weighed out and added to each vial. After each vial was added its respective emulsion stabilizer, the sample was again shaken and vortexed. Then, 9.60 g of bentonite was added in three equal portions, with shaking and vortexing between each addition. After all of the bentonite was added to the vial, it was placed on a roller for 30 minutes to disperse any remaining clumps of solid. After 30 minutes, each vial was removed and then a 1.0 gram aliquot was removed from each mixture and added to a 20 mL vial containing 15.65 grams of tap water to form a diluted sample. The diluted samples were shaken and vortexed vigorously and observed.

[0192] The diluted samples were evaluated to determine if the bentonite was still dispersed or if settling had occurred, and if the oil was still dispersed throughout the sample or had become separated at the top. A good result is where both the clay and the oil are uniformly dispersed throughout the water. The results are listed in Table 13 below:

[0193] Table 13

[0194]

[0195] Example 26: Trichoderma spore germination in agricultural formulation

[0196] Example 17 was compared to a control formulation to assess the viability of the Trichoderma spores contained in each formulation. A control Trichoderma formulation was prepared as follows: To 14.85 g of tap water in a 20 mL vial was added 0.15 g of the product "White Shark" containing Trichoderma. This control mixture was vortexed and deemed stable enough for spraying. Then, 1 g of this control Trichoderma formulation was sprayed onto the surface of a 1" x 3" glass slide. On a separate 1" x 3" glass slide, 1 g of the diluted agricultural formulation of Example 17 was sprayed onto the surface. Both treated glass slides were then placed in a convection-free oven at 37 °C for 1.5 hours to dry. After this drying was complete, a 0.2 g aliquot of a 0.02% aqueous solution of Potato Dextrose Agar ("PDA", Sigma Aldrich) was pipetted onto each previously coated glass slide. Each glass slide was then placed on top of a separate 200 mL container, and then each container was secured inside a separate 1 L container using adhesive. 60 g of tap water was placed inside each 1 L container to create a high humidity environment for Trichoderma spore proliferation and to reduce the rate of evaporation of the PDA medium. Both prepared 1 L containers were sealed with a lid and incubated in a convection-free oven at 25 °C for 3 days. After 3 days, the slides were removed from the oven and examined for Trichoderma spore germination by observing colony formation using a Zeiss AxioImager.A1M microscope. Both the control Trichoderma formulation and the formulation of Example 17 exhibited signs of Trichoderma germination as evidenced by the appearance of branching hyphae.

[0197] Example 27: Trichoderma spore germination in agricultural formulation after simulated rainfall

[0198] To test whether the control and experimental samples had viable spores after exposure to simulated rainfall, the experiment of Example 26 was replicated. A control Trichoderma formulation was prepared as described in Example 26. A test formulation was prepared as described in Example 17. Each formulation was applied to a glass slide and dried as described in Example 26. After this drying was complete, each glass slide was then exposed to simulated rainfall by spraying with a spray bottle for 15 seconds. After the water was sprayed, both slides were placed in a convection-free oven at 37 °C for 1.5 hours to dry.

[0199] After drying, a 0.2 g aliquot of a 0.02% aqueous solution of Potato Dextrose Agar was applied to each slide and incubated as described in Example 26. After 3 days, the samples were examined for spore germination as described in Example 26. The glass slide treated with the agricultural formulation of Example 17 containing Trichoderma showed germination (as evidenced by the appearance of branching hyphae) even after simulated rainfall, while the glass slide treated with the comparative formulation of Trichoderma did not exhibit any Trichoderma germination after simulated rainfall.

[0200] Example 28-32 Materials:

[0201] In addition to the materials described previously, Examples 28-32 also used the following materials:

[0202] • Raw Linseed Oil (RLO), (CAS # 67746-08-1) (Cargill)

[0203] • Bentonite (Sodium Bentonite Clay) (CAS # 1302-78-9) (BPM / Halliburton)

[0204] • Jarfactant 325N, alkyl polyglycoside surfactant, with an alkyl chain length of 9-11 carbon units (CAS # 132778-08-6) (Jarchem)

[0205] • Span 85 (Sorbitan Trioleate) (CAS # 26266-58-0)

[0206] • F108 (PEG-PPG-PEG triblock copolymer and surfactant) (CAS # 9003-11-6) (Sigma-Millipore)

[0207] • Water (tap water from Cambridge, MA) (all water is tap water unless specifically noted)

[0208] • Ammonium Hydroxide: 30% solution of ammonia and water (CAS # 1336-21-6)

[0209] • DOWANOL TM TPM (Tripropylene Glycol Methyl Ether) (Dow Chemicals)

[0210] • R (non-hygroscopic castor oil derivative) (Elementis Specialties)

[0211] • Break Thru SP133 (polyglycerol ester and fatty acid ester based additive) (Evonik) • HPMC - Hydroxypropyl Methylcellulose (Methocel E15 LV, CAS # 9004-54-3) (Dow Chemical Company)

[0212] • • Break Thru SP133 (polyglycerol ester and fatty acid ester based additive) (Evonik)

[0213] • HPMC - Hydroxypropyl Methylcellulose (Methocel E15 LV, CAS # 9004-54-3) (Dow Chemical Company)

[0214] • Example 28: Formulation preparation • Break Thru SP133 (polyglycerol ester and fatty acid ester based additive) (Evonik) • HPMC - Hydroxypropyl Methylcellulose (Methocel E15 LV, CAS # 9004-54-3) (Dow Chemical Company)

[0215] The agricultural formulations were prepared as concentrates in large and small batches (small < 250 g) using the reagents listed in Table 14 below in the amounts specified.

[0216] Table 14

[0217] Component wt% Small batch wt (g) Large batch wt (g) RLO 54.7 43.76 2461.50 Jarfactant 325N 2.0 1.60 90.00 Span 85 2.0 1.60 90.00 Water 2.27 1.81 102.00 Bentonite 38.2 30.56 1719.00 Pluronic F108 0.5 0.40 22.50 Ammonium hydroxide 0.333 0.27 15.00 Total 100 80.00 4500.00

[0218] To prepare the above formulations, a polymer solution was first prepared. The appropriate amount of F108 was weighed out according to the amounts specified in Table 14. An appropriate amount of water was added to a mixing vessel (e.g., a beaker for large solutions or a centrifuge tube for small solutions) so that an 18.2% solution of F108 could be made. Then, the F108 was gradually added and mixed into the water, taking care to fully incorporate the F108 into the water without adhering to the walls of the vessel. When a centrifuge tube mixing vessel was used, it was then capped and placed on a lab roller at approximately 70% full speed. When a beaker-sized mixing vessel was used, it was mixed using a lab mixer with a fan blade mixing shaft appropriate for the size of the mixing vessel. The F108 was mixed into the water until no solid polymer remained, only water and foam. When clumps began to form, additional stirring and breaking up with a spatula was performed to ensure complete dissolution. After it was verified that no more solid polymer remained (usually after several hours of mixing), the mixing vessel was removed from the mixing apparatus and allowed to sit undisturbed for a period of time to allow the foam on the solution to relax back to a fully liquid form; this rest period took several hours, sometimes overnight.

[0219] After the F108 solution was prepared, an appropriate amount of bentonite was weighed into a designated solids container. Then, the solids container was shaken to break up any solid clumps. Then, an appropriate amount of RLO, F108 solution, and Jarfactant 325N were combined, and an appropriate amount of NaOH solution was added. These liquids were briefly mixed until uniform using an overhead mixer with fan shaft blades. After the RLO was combined with the aqueous reagents, an appropriate amount of Span 85 was added to the stirred sample. All of the liquid reagents were mixed thoroughly before this mixture was combined with the solids. During the addition process, the solid material was gradually added and mixed thoroughly.

[0220] Example 29: Sedimentation stability

[0221] Sedimentation stability tests were performed on the formulation prepared according to Example 28. For the test, a 12" column of freshly formulated formulation was filled into a 1" diameter transparent plastic cylinder. Sedimentation of the aqueous phase in the concentrate resulted in a clear fluid layer at the top of the column and a dense concentrate layer at the bottom. The thickness of the clear fluid layer was determined visually. The thickness of the dense concentrate layer was determined by two methods: pouring the fluid out of the tube and noting the height of the column from which non-pourable material remained, or sinking a weight into the column and noting the depth to which the weight stopped penetrating the fluid. Sedimentation measurements were performed periodically until the sum of the clear and dense layers reached approximately 100%; see Table 15 below.

[0222] Table 15

[0223] The thickness of the clear and dense layers over time (as a percentage of the original formulation height).

[0224] Time [days] Clear % Dense % Example 31 : Stabilize formulation with R (Elementis Specialties) 0.0 0％ 0％ 3.7 4％ 4.7 5％ 5.7 7％ 6.7 9％ 34％ 9.8 12％ 10.7 13％ 13.0 14％ 13.9 13％ 75％ 16.7 15％ 20.1 15％ 20.8 16％ 86％

[0225] Example 30: Use of DOWANOL TM TPM stable formulations to resist settling

[0226] The agricultural formulation prepared according to Example 28 was used in the following experiments. 200 g of the agricultural formulation was added to a beaker. Then, 8 g (4 wt%) of Dowanol TPM (Dow) was added while stirring at 300 rpm. Mixing continued for 10 minutes. The resulting mixture was a pourable fluid with pseudoplastic properties. The yield stress at 0.1 rpm was measured using a Brookfield YR-1 rheometer. The yield stress was 12.7 Pa. The formulation was then subjected to a sedimentation stability test according to Example 29. After 7 days, a clarified layer with a thickness equal to 3% of the original column height was observed.

[0227] Example 32: Formulation preparation Component

[0228] The agricultural formulation prepared according to Example 28 was used in the following experiments. 200g of the agricultural formulation was added to each of three beakers. Then, sufficient [amount missing] was added to each beaker. R (Elementis Specialties) to achieve R concentrations were 0.05 wt%, 0.1 wt%, or 0.3 wt%, while stirring at 300 rpm. Mixing continued for 10 minutes while heating at 60°C. Upon cooling to room temperature, the resulting mixture was a pourable fluid with pseudoplastic properties. Sedimentation stability tests were performed on all formulations according to Example 29. After 7 days, no sedimentation was observed in any of the tested formulations.

[0229] wt%

[0230] Agricultural formulations were prepared as concentrates in small batches (small < 250 g) using the reagents listed in Table 16 below in the amounts indicated.

[0231] Table 16

[0232] wt (g) RLO Jarfactant 325N Span 85 54.05 43.24 Water 2.0 1.60 Bentonite 2.0 1.60 HPMC 2.5 2.00 Break Thru SP 133 38.2 30.56 Total 0.25 0.20 ​ 1.00 0.80 ​ 100 80.00

[0233] To prepare the above formulation, first weigh the appropriate amounts of HPMC and Bentonite into a sealable container; then seal the container and shake to promote homogeneity. Next, combine the appropriate amounts of water and Jarfactant 325N in a beaker and agitate to promote dissolution of the Jarfactant 325N. After agitation, add the RLO to the sample and also add the appropriate amounts of Break-Thru SP 133 and Span 85. Then, mix all the liquid reagents thoroughly on a lab overhead mixer with a small fan blade attachment, then combine the mixture with the solids. Add the solid materials gradually with a spatula while stirring the mixture; once all the solids have been added, start a 10 min timer and scrape the walls of the beaker (as well as the stirring shaft) with the spatula to prevent any clumps of clay from going unmixed.

[0234] Equivalents

[0235] While specific embodiments of the subject application have been disclosed herein, the above specification is illustrative and not restrictive. While the application has been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details can be made therein without departing from the spirit of the application as encompassed by the scope of the appended claims. Numerous variations of the application will become apparent to those skilled in the art once the nature of the application has been discussed above. Unless otherwise specified, all numbers concerning quantities of ingredients, reaction conditions, and so on, used in this specification and claims are to be understood as modified by the term "about." Accordingly, unless otherwise specified, numerical parameters set forth in this specification and claims are approximations. Therefore, these numerical values, as stated elsewhere in this specification and claims, are approximations. It is intended that the application be construed as including all such approximations.

Claims

1. A non-toxic agricultural formulation of a concentrated liquid suspension comprising a surfactant, an oil phase, and a suspended particulate material, the oil phase being a drying oil, wherein the particulate material is clay mineral particles, wherein the clay mineral particles are suspended in the drying oil, and wherein, the clay mineral particles are not organically modified and are bentonite clay mineral particles; wherein the amount of the oil phase is 40% to 90% by weight of the formulation; and wherein the drying oil is linseed oil wherein the amount of the particulate material is 10% to 40% by weight of the formulation; wherein the amount of the surfactant is 0.1 to 15% by weight of the formulation; and wherein the formulation is pesticide-free.

2. The formulation of claim 1, wherein, the formulation forms a solidified coating on an agricultural subject.

3. The formulation of claim 1, further comprising a plant extract.

4. The formulation of claim 1, further comprising an additional particulate material.

5. The formulation of claim 4, wherein, the additional particulate material is selected from the group consisting of talc, calcium carbonate, gypsum, magnesium silicate, calcium silicate, corn starch, cellulose fiber, psyllium fiber, ethylene bis-stearamide, microcrystalline cellulose, stearic acid, paraffin wax, carnauba wax, or beeswax.

6. The formulation of claim 4, wherein, the additional particulate material is selected from the group consisting of kaolin and titanium dioxide.

7. The formulation of claim 1, wherein, the surfactant is selected from the group consisting of anionic, cationic, non-ionic, biodegradable, food-grade, and organic surfactants.

8. The formulation of claim 1, wherein the surfactant is selected from the group consisting of ethoxylated alcohols, sorbitan fatty esters, alkyl polyglycosides, ethylene oxide / propylene oxide (EO / PO) copolymers, guar gum, xanthan gum, soy lecithin, or ethoxylated sorbitan stearate.

9. The formulation of claim 1, further comprising an adjuvant selected from the group consisting of cellulose, polylactic acid, polyglycolic acid, and polylactic-glycolic acid.

10. The formulation of claim 1, further comprising a salt.

11. The formulation of claim 1, further comprising a solidification additive.

12. The formulation of claim 1, wherein, the formulation is anhydrous.

13. The formulation of claim 1, wherein, the linseed oil is raw linseed oil or boiled linseed oil.

14. The formulation of claim 1, wherein, the amount of the particulate material is 20% to 35% by weight of the formulation.

15. A coated agricultural treatment comprising an agricultural treatment and the formulation of claim 1, wherein the formulation is applied as a coating to the agricultural treatment.

16. A method of preventing damage to an agricultural subject by a pest, wherein the agricultural subject is a plant surface, the method comprising: coating the agricultural subject with the formulation of claim 1, wherein the formulation forms a coating on the agricultural subject, and wherein the coating prevents pest damage, wherein the pest damage is caused by an insect or an animal.

17. The method of claim 16, wherein, the plant surface is a surface selected from the group consisting of a leaf, a fruit, a stem, and a root.

18. The method of claim 16, wherein, the plant surface is a surface of a seed.

19. The method of claim 16, wherein, the plant surface is a surface selected from the group consisting of a berry, a nut, and a grain.

20. The method of claim 16, wherein, the plant surface is a surface of a harvested product.

21. The method of claim 16, wherein, the pest is an insect.

22. The method of claim 16, wherein, the coating prevents the pest by causing a change in the plant surface that is recognized by the senses.

23. The method of claim 22, wherein, The plant surface has a characteristic selected from the group consisting of different surface energy, slip resistance, compatibility with insect foot physiology, surface texture, odor profile, visual appearance, and thermal signature when compared to an untreated plant surface.

24. The method of claim 22, wherein, The altered sensory recognition alters the behavior of a pest, wherein the pest is an insect.

25. The method of claim 24, wherein, The behavior is feeding behavior or grooming behavior.

26. The method of claim 21, wherein, The coating immobilizes the insect by adhering to the pest.

27. The method of claim 21, wherein, The insect is unable to wriggle free from the coating.

28. The method of claim 22, wherein, The insect is unable to remove the coating from the agricultural object.

29. The method of claim 16, wherein, The agricultural object is a fruit or a vegetable.

30. The method of claim 16, wherein, The plant surface is a leaf.

31. The method of claim 16, wherein, The plant surface is a berry.

32. The method of claim 16, wherein, The agricultural object is coated by spraying the object with the formulation.

33. The method of claim 16, wherein, The coating is applied such that it forms a porous film.

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