Non-aqueous nitrification inhibitor composition and methods and use thereof

Abstract

The subject matter disclosed herein generally relates to non-aqueous nitrification inhibitor compositions comprising thiram, dicyandiamide, a stabilizer, an emulsifier, a surfactant, a dispersant, and water, which are all present in certain amounts. Specifically, this non-aqueous nitrification inhibitor composition is used for improving plant growth and health by minimizing any nitrogen loss due to volatilization, leaching and dentrification.

Description

[0001] NON-AQUEOUS NITRIFICATION INHIBITOR COMPOSITION AND METHODS AND USE THEREOF

[0002] FIELD OF THE INVENTION

[0003] The subject matter disclosed herein generally relates to non-aqueous nitrification inhibitor compositions comprising thiram, dicyandiamide, a stabilizer, an emulsifier, a surfactant, a dispersant, and water, which are all present in certain amounts. Specifically, this non-aqueous nitrification inhibitor composition is in the form of an emulsion and can be used for improving plant growth and health by minimizing any nitrogen loss due to volatilization, leaching and dentri fi cation.

[0004] BACKGROUND

[0005] Nitrogen (N) fertilizer added to the soil is readily transformed through a number of biological and chemical processes, including nitrification, leaching, and evaporation. Typically, the nitrogen fertilizer is applied to the soil either in liquid or in solid form. However, maintaining adequate levels of concentration of nitrogen in the soil over time is difficult due to the solubility of nitrogen and nitrogen-containing compounds (such as urea) in water. Rainwater in contact with the soil can flush nitrogen or nitrogen-containing compounds into surrounding waterways. Not only does a significant percentage of nitrogen fertilizer flow to aquatic systems by the runoff of ammonium (NH4+) and nitrate (NO3 ) but also the atmosphere is affected by gaseous N emissions. As a result, the level of nitrogen available for uptake by the targeted plant is reduced, requiring the addition of more nitrogen-rich fertilizer to compensate for the loss of agriculturally active nitrogen available to the plants.

[0006] One transformation responsible for the reduction of available nitrogen to the targeted plant is nitrification. Nitrification is a chemical process by which the nitrogen fertilizer is transformed, e.g., bacteria in the soil metabolizes the ammonium form of nitrogen to nitrite and nitrate forms (which are more susceptible to nitrogen loss through leaching or volatilization via denitrification). One method of controlling the rate of nitrification is the employment of nitrogen nutrient use efficiency enhancing compounds: the so-called nitrification inhibitors. These inhibitors are able to inhibit nitrogen loss by depressing the Nitrosomonas bacteria that catalyzes the microbial oxidation of ammonia (NH4+) to nitrite (NO2"). The microbial activity can be successfully suppressed by these compounds for a certain period (several weeks or months) depending on soil moisture and / or soil type. For example, nitrification inhibitors generally are more effective in sandy soils or soil low in organic matter and / or when exposed to low temperatures.

[0007] Due to the various factors controlling both the rate of nitrification and the activity of the inhibitor, the number of applications of the nitrification inhibitor can vary. In regions where the soil type and / or climate zone requires multiple applications of the nitrification inhibitor resistance against these single active agents has begun to emerge. The overuse and / or continuous use of these single active agents results in a decrease in inhibitory efficacy against living nitrifying soil organisms such as bacteria and arachaea.

[0008] Thus, there is a constant need to improve the current nitrification inhibitor containing compositions. For example, it would be highly desirable to develop nitrification inhibitor containing compositions that are able to increase the life expectancy of nitrogen in the soil to assure more consistent levels of nitrogen during the growing season. Such nitrification inhibitor compositions would not only be able to provide healthy plants and / or crops, but at the same time would also be able to limit the amount of nitrogen carried into the waterways via leaching and dentrification and / or the atmosphere via volatilization.

[0009] SUMMARY OF THE INVENTION

[0010] In one aspect, the subject matter described herein is directed to a non-aqueous nitrification inhibitor composition comprising thiram, dicyandiamide (DCD), a stabilizer present in an amount of from about 1% to about 3% by weight, an emulsifier present in an amount of from about 1% to about 4% by weight, a surfactant present in an amount of from about 1% to about 3% by weight, a dispersant or wetting agent present in an amount of from about 1.5% to about 2.5% by weight, and water present in an amount of from about 15% to about 30% by weight, wherein thiram and DCD are present in a combined amount of from about 10 % to about 20 % by weight and all weights are based on the composition being 100%. In some embodiments, thiram and DCD are present in synergistically effective amounts.

[0011] In one aspect, the subject matter described herein is directed to an agricultural product comprising the non-aqueous nitrification inhibitor composition as described herein.

[0012] In another aspect, the subject matter described herein is directed to methods of fertilizing soil and / or improving plant / crop growth and / or health comprising applying a non-aqueous nitrification inhibitor composition or agricultural composition as disclosed herein to the soil. These and other aspects are fully described below.

[0013] DETAILED DESCRIPTION

[0014] The presently disclosed subject matter will now be described more fully hereinafter. However, many modifications and other embodiments of the presently disclosed subject matter set forth herein will come to mind to one skilled in the art to which the presently disclosed subject matter pertains having the benefit of the teachings presented in the foregoing descriptions. Therefore, it is to be understood that the presently disclosed subject matter is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. In other words, the subject matter described herein covers all alternatives, modifications, and equivalents. In the event that one or more of the incorporated literature, patents, and similar materials differs from or contradicts this application, including but not limited to defined terms, term usage, described techniques, or the like, this application controls. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in this field. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety.

[0015] The current invention relates to non-aqueous nitrification inhibitor compositions comprising fungicide thiram and nitrification inhibitor dicyandiamide (DCD) as active agents for inhibiting nitrification in the soil and to increase nutrient uptake. When these active agents are combined with a stabilizer, an emulsifier, a surfactant, a dispersant, and water these compositions provide protection against volatility, leaching, and dentrification in below-ground and aboveground applications. In addition to protecting against nitrogen loss, these non-aqueous nitrification inhibitor compositions keep nitrogen available longer in the root zone of plants / crops, thereby promoting healthy crops and maximizing yield potential.

[0016] Not to be bound by theory, but it is believed that by combining a fungicide and nitrification inhibitor as disclosed herein a synergistic effect is produced. Specifically, the non-aqueous nitrification composition disclosed herein is believed to reduce the population of bacteria responsible for converting ammonium to nitrate Nitrosomonas) and nitrite to nitrate Nitrobacter) in soil. This new synergistic pair of fungicide and nitrification inhibitor will protect against denitrification and leaching by retaining fertilizer (N) in the ammonium form (NHZ) for longer. Ammonium is a positively charged ion, which can be held on negatively charged sites in soil, present in clays, and organic matter. This negatively charged anion nitrate (NCh ) can be converted to N2O or N2 gases under anaerobic conditions or can leach below the root zone with rain-drained soils. In addition to protecting against denitrification and leaching of nitrogen, the disclosed nonaqueous nitrification inhibitors also promote an increase in plant health and crop yield by providing a continuous nitrogen source at the root zone of plants / crops.

[0017] Current produces on the market such as Thiram SC and CVA Elite Protect provide a combination of thiram and DCD as suspended concentrates and solid powder products. However, these products exhibit several drawbacks such as

[0018] In addition, most fungicides, including thiram, are water insoluble and require organic solvents prior to its use in agriculture. However, the use of organic solvents increases the cost of such thiram-containing products and may present potential health and / or environmental hazards.

[0019] Alternatively, water-insoluble organic fungicides can also be used in the form of an emulsion by first dissolving the fungicide in an organic solvent to make a solution, and then emulsifying the solution in water. However, such emulsions tend to be unstable. This instability causes the risk that crystals of the organic fungicide might precipitate out when the material is diluted with water. In addition, any minor changes in the formulation, such as the addition of another biocide, may cause the emulsion to break, resulting in phase separation.

[0020] As such, it is desirable to have a non-aqueous nitrification inhibitor composition of thiram, DCD, a stabilizer, an emulsifier, a surfactant, a dispersant, and water to prolong the protection of nitrification, which translates it into better yield and higher profit benefits. A non-aqueous nitrification inhibitor composition as disclosed herein containing a thiram / DCD combination is a improvement over current products for achieving long-lasting reduced populations of Nitrosomonas and Nitrobacter bacteria in the soil. Such non-aqueous nitrification inhibitor compositions are described in more detail below.

[0021] Definitions

[0022] As used herein, the term “non-aqueous” refers to a composition that is not water-based, meaning that the continuous phase of the carrier component in the composition is not water. Here, the disclosed nitrification inhibitor composition is in the form of an inverted emulsion, which contains water but not as a continuous phase. Hence, the disclosed nitrification inhibitor composition is not water-based. As used herein, “nitrification inhibitor” refers to a property of a compound to inhibit oxidation of ammonia to nitrite / nitrate.

[0023] As used herein, “fungicide” refers to biocidal chemical compounds used to kill parasitic fungi or their spores. Fungicides disclosed herein are non-systemic fungicides often referred to as contact fungicides, which do not penetrate into the plant tissue and are only effective before the pathogens infect the plant.

[0024] The term “synergistic effect” is understood to be defined according to Colby’s formula (Colby, S. R., “Calculating synergistic and antagonistic responses of herbicide combinations,” Weeds, 15, pp. 20-22, 1967).

[0025] As used herein, the term “surfactant” means an amphiphilic compound that comprises a hydrophilic moiety and hydrophobic moiety that lowers the surface tension of a liquid causes the lowering of the interfacial tension between two liquids.

[0026] As used herein, the term “emulsifier” is a substance that stabilizes an emulsion. An emulsion is a mixture of two or more liquids that are normally immiscible owing to liquid-liquid phase separation. Emulsions are part of a more general class of two-phase systems of matter called colloids.

[0027] As used herein, the term “dispersant” or a “dispersing agent” is a substance, that is added to a suspension of solid or liquid particles in a liquid to improve the separation of the particles and to prevent their settling or clumping.

[0028] As used herein, the term “synergistically effective” refers to an effect that is obtained from two different chemicals (e.g., a fungicide and a nitrification inhibitor) that is greater than the sum of their individual effects at the same doses. For example, the effective amount of the composition disclosed herein comprises a synergistically effective amount of thiram and DCD such that nitrification is reduced by at least 10% more compared to the sum of the individual nitrification inhibition of thiram and DCD by itself.

[0029] As used herein, the term “effective amount” refers to an amount of a mixture of components (i.e., fungicide / nitrification inhibitor) and / or the amount of each component in the mixture (i.e., fungicide or nitrification inhibitor), which is sufficient for achieving nitrification inhibition as described below. More exemplary information about amounts, ways of application and suitable ratios to be used is given below. A skilled artisan is well aware of the fact that such an amount can vary in a broad range and is dependent on various factors, e.g., weather, target species, locus, mode of application, soil type, treated cultivated plant or material and the climatic conditions.

[0030] Throughout this specification and the claims, the words “comprise,” “comprises,” and “comprising” are used in a nonexclusive sense, except where the context requires otherwise, and are synonymous with “including,” “containing,” or “characterized by,” meaning that it is open- ended and does not exclude additional, unrecited elements or method steps.

[0031] As used herein, the transitional phrase “consisting essentially of’ limits the scope of a claim to the specified materials or steps “and those that do not materially affect the basic and novel character! stic(s)” of the claimed invention.

[0032] As used therein, the transitional phrase “consisting of’ excludes any element, step, or ingredient not specified in the claim.

[0033] As used herein, the term “about,” when referring to a value, is meant to encompass variations of in some embodiments ± 5%, in some embodiments ± 2%, in some embodiments ± 1%, in some embodiments ± 0.5%, and in some embodiments ± 0. 1% from the specified amount, as such variations are appropriate to perform the disclosed methods or employ the disclosed compositions.

[0034] As used herein, the term “soil” is to be understood as a natural body comprised of living (e.g., microorganisms (such as bacteria and fungi), animals and plants) and non-living matter (e.g., minerals and organic matter (e.g., organic compounds in varying degrees of decomposition), liquid, and gases) that occurs on the land surface, and is characterized by soil horizons that are distinguishable from the initial material as a result of various physical, chemical, biological, and anthropogenic processes. From an agricultural point of view, soils are predominantly regarded as the anchor and primary nutrient base for plants (plant habitat).

[0035] As used herein, the term “fertilizer” is to be understood as chemical compounds applied to promote plant and fruit growth. Fertilizers are typically applied either through the soil (for uptake by plant roots) or by foliar feeding (for uptake through leaves). The term “fertilizer” can be subdivided into two major categories: a) organic fertilizers (composed of decayed plant / animal matter) and b) inorganic fertilizers (composed of chemicals and minerals). Organic fertilizers include manure, slurry, worm castings, peat, seaweed, sewage, and guano. Green manure crops are also regularly grown to add nutrients (especially nitrogen) to the soil. Manufactured organic fertilizers include compost, blood meal, bone meal, and seaweed extracts. Further examples are enzymatically digested proteins, fish meal, and feather meal. The decomposing crop residue from prior years is another source of fertility. In addition, naturally occurring minerals such as mine rock phosphate, sulfate of potash, and limestone are also considered inorganic fertilizers. Inorganic fertilizers are usually manufactured through chemical processes (such as the Haber- Bosch process), also using naturally occurring deposits, while chemically altering them (e.g., concentrated triple superphosphate). Naturally occurring inorganic fertilizers include Chilean sodium nitrate, mine rock phosphate, and limestone.

[0036] As used herein, the term “manure” is organic matter used as organic fertilizer in agriculture. Depending on its structure, manure can be divided into liquid manure, semi-liquid manure, stable or solid manure, and straw manure. Depending on its origin, manure can be divided into manure derived from animals or plants. Common forms of animal manure include feces, urine, farm slurry (liquid manure), or farmyard manure (FYM), whereas FYM also contains a certain amount of plant material (typically straw), which may have been used as bedding for animals. Animals from which manure can be used comprise horses, cattle, pigs, sheep, chickens, turkeys, rabbits, and guano from seabirds and bats. The application rates of animal manure when used as fertilizer highly depends on the origin (type of animals). Plant manures may derive from any kind of plant, whereas the plant may also be grown explicitly for the purpose of plowing them in (e.g., leguminous plants), thus improving the structure and fertility of the soil. Furthermore, plant matter used as manure may include the contents of the rumens of slaughtered ruminants, spent hops (left over from brewing beer), or seaweed.

[0037] As used herein, the term “seed” comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, seedlings, and similar forms. The seed used can be seed of the useful plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods.

[0038] As used herein, the term “organic solvent” refers to a non-aqueous solvent that solvates the nitrification inhibitor and / or fungicide to the degree as described elsewhere herein.

[0039] As used herein, the term “oil-in-water (O / W) emulsion” is an emulsion that is composed of an oil phase dispersed in an aqueous phase and is often referred to as a direct emulsion. Stabilization of O / W emulsion is often performed with hydrophilic-hydrophobic particles. The hydrophilic end of the emulsifier molecule has an affinity for water, and the hydrophobic end is drawn to the fat / oil. Vigorously mixing the emulsifier with the water and oil creates a stable emulsion.

[0040] As used herein, the term “water-in-oil (W / O) emulsion” is an emulsion that is composed of an aqueous phase dispersed in the oil phase. A water-in-oil emulsion is much fattier than a direct emulsion and is also referred to as an “inverted emulsion.”

[0041] Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limit of the range and any other stated or intervening value in that stated range, is encompassed. The upper and lower limits of these small ranges which may independently be included in the smaller ranges is also encompassed, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

[0042] Additional definitions may follow below.

[0043] II. Non-aqueous Nitrification Inhibitor Composition

[0044] In some embodiments, the subject matter described herein is directed to non-aqueous nitrification inhibitor compositions comprising thiram and DCD as active agents. Herein “active agent” is referred to compounds that elicit the desirable effect, e.g., providing nitrogen to plants to promote plant growth / health and reduce loss of nitrogen, when administered in an effective amount. In some embodiments, thiram and DCD are present in synergistically effective amounts. In addition to these active agents, the non-aqueous nitrification inhibitor composition comprises a stabilizer, an emulsifier, a surfactant, and a dispersant.

[0045] In some embodiments, the non-aqueous nitrification inhibitor composition disclosed further comprises water and an oil, which allow the composition to be in the form of an emulsion. A skilled artisan would generally be aware of general methods for forming the various types of emulsions, i.e., inverted emulsion. Once the emulsion has been formed components such as the stabilizer, emulsifier, surfactant and dispersant would be dissolved and / or miscible with the water and / or the oil, which make up the emulsion.

[0046] The remaining active agents thiram and DCD, however, are not dissolved and / or miscible with the water and / or oil, which make up the emulsion. More specifically, the non-aqueous nitrification inhibitor composition comprises thiram and DCD in a solid or solidified form, which disperse throughout the emulsion made up of water and an oil comprising a stabilizer, an emulsifier, a surfactant, and a dispersant.

[0047] The disclosed non-aqueous nitrification inhibitor composition exhibits various benefits such as (a) reducing nitrogen loss in the soil due to leaching and / or dentrification; and (b) promote an increase in plant health / growth and crop yield. Without being bound to theory, it was surprising and unexpected to observe such benefits for the disclosed non-aqueous nitrification inhibitor composition (in the form of an inverted emulsion). Each component of the non-aqueous nitrification inhibitor composition is described in more detail below.

[0048] Thiram is the simplest thiuram disulfide and is the oxidized dimer of dimethyldi thiocarbamate and has the following stereochemical structures:

[0049] It is used as a fungicide, ectoparasiticide to prevent fungal diseases in seed and crops and similarly as an animal repellent to protect fruit trees and ornamentals from damage by rabbits, rodents and deer. It is effective against Stem gall of coriander, damping off, smut of millet, neck rot of onion, etc. Thiram applications are most effective before disease development.

[0050] When used as a fungicide, thiram is a multisite fungicide (Group M3) that inhibits spore germination and mycelium growth by interfering with various enzymes involved in the respiration process. Its ability to act on many sites of the biochemical process ensures that thiram remains at low risk for resistance development and retains its efficacy against many fungi.

[0051] Thiram can be used in a variety of applications. For example, thiram is characterized as a non-systemic fungicide and can therefore be used to prevent crop damage in the field and to protect harvested crops (apples, peaches, and strawberries) from deterioration in storage or transport. It is also used as a seed protectant (e.g., small seeded vegetables, large seeded vegetables, cereal grains and other seeds, coniferous seeds, cotton seed, ornamental seeds, and soybeans) and to protect turf from fungal diseases. In addition, thiram is used as an animal repellent to protect crops from damage by rabbits, rodents, and deer. Exemplary commercially available formulations of thiram include soluble concentrate and ready-to-use liquid formulations, e.g., Thiram SC.

[0052] Dicyandiamide (DCD) is a nitrification inhibitor. It has the following chemical structure:

[0053] Dicyandiamide (DCD) is commonly used in fertilizer formulations as a nitrification inhibitor to slow the release of nitrogen (N) into plant available forms that are also more prone to losses. DCD exhibits various advantages over other nitrification inhibitors such as its reduced volatility, its efficient decomposition in the soil to NEE and CO2 in a slow release manner, and its inhibition of the first stage of nitrification, i.e., the oxidation of NHC to NCh' by rendering the bacteria’s enzyme ineffective.

[0054] DCD is an active ingredient in many mainstream enhanced-efficiency fertilizer products used in the U.S. including Guardian® products, Agrotain® Plus, and Super U®. DCD in these products is intended to inhibit the activity of the Nitrosomonas bacteria, allowing for the stabilization of ammonium-N in the root zone, improving plants’ access to available nitrogen over the growing season. As a result, the addition of DCD has the potential to increase crop yields as well as reduce nitrogen loss through nitrification.

[0055] In some embodiments, the non-aqueous nitrification composition comprises thiram in an amount of from about 0.01% w / w to about 20% w / w, from about 0.1% w / w to about 18% w / w, from about 1% w / w to about 18% w / w, from about 1% to about 15%, from about 5% w / w to about 15% w / w, from about 7% w / w to about 13% w / w, from about 8% w / w to about 12% w / w, from about 9% w / w to about 11% w / w, from about 9.5% w / w to about 10.5% w / w of the composition. In some embodiments, the non-aqueous nitrification composition comprises thiram in an amount of from about 10.0% w / w to about 20% w / w of the composition. In some embodiments, the nonaqueous nitrification composition comprises thiram in an amount less than about 50% w / w, about 45% w / w, about 40% w / w, about 35% w / w, about 30% w / w, 25% w / w, less than about 23% w / w, less than about 22% w / w, less than about 21% w / w, less than about 20% w / w, less than about 18% w / w, less than about 15% w / w, less than about 12% w / w, or less than about 10% w / w of the composition. In some embodiments, the compositions comprise thiram in an amount of at least about 1% w / w, at least about 5% w / w, at least about 7% w / w, at least about 10% w / w, at least about 12% w / w, at least about 15% w / w, at least about 18% w / w, or at least about 20% w / w of the composition.

[0056] In some embodiments, the non-aqueous nitrification composition comprise DCD in an amount of from about 0.01% w / w to about 20% w / w, from about 0.1% w / w to about 18% w / w, from about 1% w / w to about 18% w / w, from about 5% w / w to about 15% w / w, from about 7% w / w to about 13% w / w, from about 8% w / w to about 12% w / w, from about 9% w / w to about 11% w / w, from about 9.5% w / w to about 10.5% w / w of the composition. In some embodiments, the non-aqueous nitrification composition comprises DCD in an amount of from about 10.0% w / w to about 20% w / w of the composition. In some embodiments, the non-aqueous nitrification composition comprises DCD in an amount less than about 25% w / w, less than about 23% w / w, less than about 22% w / w, less than about 21% w / w, less than about 20% w / w, less than about 18% w / w, less than about 15% w / w, less than about 12% w / w, or less than about 10% w / w of the composition.

[0057] In some embodiments, the non-aqueous nitrification compositions comprises a combined amount of thiram and DCD of from about 1 % w / w to about 25% w / w, from about 3% w / w to about 24% w / w from about 5% w / w to about 23% w / w, from about 7% w / w to about 22% w / w, from about 10% w / w to about 21% w / w, from about 10% w / w to about 20.5% w / w, from about 10% w / w to about 20% w / w, from about 12% w / w to about 20% w / w, from about 15% w / w to about 20% w / w, or from about 18% w / w to about 20% w / w of the composition. In some embodiments, the non-aqueous nitrification composition comprises a combined amount of thiram and DCD of from about 12% w / w to about 21% w / w, 15% w / w to about 21% w / w, 17% w / w to about 21% w / w, or 19% w / w to about 21% w / w of the composition. In some embodiments, the non-aqueous nitrification composition comprises a combined amount of thiram and DCD of at least about 10% w / w, about 12% w / w, about 14% w / w, about 16% w / w, about 18% w / w, or about 20% w / w of the composition. In addition, or as an alternative, the non-aqueous nitrification composition comprises a combined amount of thiram and DCD of no more than about 25% w / w, about 24% w / w, about 23% w / w, about 22% w / w, about 21% w / w, about 20% w / w, about 18% w / w, about 16% w / w, about 14% w / w, or about 12% w / w of the composition. The amount of thiram and DCD as active agents can vary. In some embodiments, thiram and DCD are present in the non-aqueous nitrification inhibitor composition at a weight ratio of from about 1: 10 to about 10: 1, about 1 :5 to about 5: 1, about 1 :3 to about 3: 1, about 1 :2 to about

[0058] 2: 1, or about 1 : 1 of thiram:DCD. In some embodiments, the amount of thiram is greater than the amount of DCD present in the composition. In such specific embodiments, DCD and thiram are present as a weight ratio of 1 (DCD):1 (Thiram); 1 (DCD):2 (Thiram); 1 (DCD):3 (Thiram). In certain embodiments, the ratio of DCD to thiram is about 1-3 (thiram): ! (DCD). In certain embodiments, the ratio of thiram to DCD is about 1.0-2.5 (thiram): 1 (DCD). In certain embodiments, the ratio of thiram to DCD is about 1.0-1.5 (thiram): ! (DCD). In certain embodiments, the ratio of thiram to DCD is about 1.0-1.25 (thiram): 1 (DCD). In certain embodiments, the ratio of thiram to DCD is about 1.0-1.15 (thiram): 1 (DCD). In certain embodiments, the ratio of thiram to DCD is about 1.0-1.05 (thiram): ! (DCD). In certain embodiments, the ratio of thiram to DCD is about 1 (thiram): 1 (DCD).

[0059] The non-aqueous nitrification inhibitor composition also comprises a stabilizer. Exemplary stabilizers include, but are not limited to, PVP, PVA, HMPC, SLS, TPGS, Tween 80, Poloxamer

[0060] 188, Capryol 90, Solutol HS 15, and / or Bentone. In some embodiments, the stabilizer is Bentone. The amount of stabilizer present in the non-aqueous nitrification inhibitor composition can vary. In some embodiments, the amount of stabilizer is from about 0.1% to about 5%, from about 0.5% to about 4%, from about 0.75% to about 3%, from about 1% to about 3%, from about 1% to about 2.5%, from about 1% to about 2%, from about 1.3% to about 1.7%, from about 1.3% to about 1.6%, or from about 1.3% to about 1.5% by weight, based on the total weight of the non-aqueous nitrification inhibitor composition. In some embodiments, amount of stabilizer present in the nonaqueous nitrification inhibitor composition is at least about 0.1%, at least about 0.25%, at least about 0.5%, at least about 0.75%, at least about 1.0%, at least about 1.15%, at least about 1.25%, at least about 1.30%, at least about 1.35%, at least about 1.40%, at least about 1.45%, or at least about 1.50% by weight based on the total weight of the non-aqueous nitrification inhibitor composition. In addition, or in the alternative, the amount of stabilizer present in the non-aqueous nitrification inhibitor composition is less than about 3.0%, less than about 2.75%, less than about 2.50%, less than about 2.25%, less than about 2.0%, less than about 1.75, less than about 1.65, or less than about 1.4% by weight based on the total weight of the non-aqueous nitrification inhibitor composition. The non-aqueous nitrification inhibitor composition also comprises an emulsifier. Exemplary emulsifiers include, but are not limited to, nonionic surfactant types such as ethoxylated nonylphenol, branched (Igepal® CO430; CAS No. 68412-54-4); alcohol ethoxylate C9-11 (Berol 266; CAS No. 68439-46-3); alcohols, coco, ethoxylated (Genapol® C200; CAS No. 61791-13-7); alcohol alkoxylate (POE4) Lutensol ®XL 40 (CAS No. 166736-08-9), and a combination thereof In some embodiments, the emulsifier is Igepal CO430. The amount of emulsifier present in the non-aqueous nitrification inhibitor composition can vary. In some embodiments, the amount of emulsifier is from about 0.1% to about 5%, from about 0.5% to about 4%, from about 0.75% to about 4%, from about 1% to about 4%, from about 1.5% to about 3.5%, from about 1.5% to about 3%, from about 1.5% to about 2.5%, from about 1.75% to about 2.25%, or from about 1.8% to about 2.20% by weight, based on the total weight of the non-aqueous nitrification inhibitor composition. In some embodiments, the amount of emulsifier present in the non-aqueous nitrification inhibitor composition is at least about 0.1%, at least about 0.25%, at least about 0.5%, at least about 0.75%, at least about 1.0%, at least about 1.25%, at least about 1.50%, at least about 1.75%, at least about 2.0%, at least about 2.25%, at least about 2.30%, or at least about 2.50% by weight based on the total weight of the non-aqueous nitrification inhibitor composition. In addition, or in the alternative, the amount of emulsifier present in the non-aqueous nitrification inhibitor composition is less than about 4.0%, less than about 3.75%, less than about 3.50%, less than about 3.25%, less than about 3.0%, less than about 2.75%, less than about 2.50%, or less than about 2.4% by weight based on the total weight of the non-aqueous nitrification inhibitor composition.

[0061] The non-aqueous nitrification inhibitor composition also comprises a surfactant. In some embodiments, a non-ionic surfactant selected from the group consisting of fatty alcohol ethoxylate, alkyl phenol ethoxylate and fatty acid alkoxylate. In some embodiments, the non-ionic surfactant is a fatty alcohol ethoxylate. In some embodiments, the fatty alcohol ethoxylate is (Genamin® C100; CAS No. 68155-27-1). Additional exemplary surfactants include, but are not limited to, sodium dodecyl sulphate such as (SDS); polyoxymethylene tridecyl ether phosphate (Rhodafac® RS-610; CAS No. 9046-01-9); ethylene oxide-propylene oxide polymer monobutyl ether (Antarox® B848; CAS No. 221045-17-6); polyethylene glycol esters of fatty acids (Alkamuls VO / 2003; CAS No. 220037-02-5); 4-dodecylbenzenesulfonic acid and salts thereof (e.g., dodecylbenzenesulfonate, sodium salt, etc ), and a combination thereof. The amount of surfactant present in the non-aqueous nitrification inhibitor composition can vary. The amount of surfactant is from about 0.1% to about 5%, from about 0.5% to about 4%, from about 0.75% to about 4%, from about 1% to about 4%, from about 1.5% to about 3.5%, from about 1.5% to about 3%, from about 1.5% to about 2.5%, from about 1.75% to about 2.25%, or from about 1.8% to about 2.20% by weight, based on the total weight of the non-aqueous nitrification inhibitor composition. In some embodiments, amount of surfactant present in the nonaqueous nitrification inhibitor composition is at least about 0.1%, at least about 0.25%, at least about 0.5%, at least about 0.75%, at least about 1.0%, at least about 1.25%, at least about 1.50%, at least about 1.75%, at least about 2.0%, at least about 2.25%, at least about 2.30%, or at least about 2.50% by weight based on the total weight of the non-aqueous nitrification inhibitor composition. In addition, or in the alternative, the amount of surfactant present in the non-aqueous nitrification inhibitor composition is less than about 4.0%, less than about 3.75%, less than about 3.50%, less than about 3.25%, less than about 3.0%, less than about 2.75%, less than about 2.50%, or less than about 2.4% by weight based on the total weight of the non-aqueous nitrification inhibitor composition.

[0062] The non-aqueous nitrification inhibitor composition also comprises a dispersant or wetting agent. Exemplary dispersants or wetting agents include, but are not limited to, polycarboxylic acid such as (TAMOL™ 945; 2-propenoic acid, homopolymer, sodium salt (CAS No. 9003-04-7); residual monomers; and water); polyether polycarboxylates, sodium salts, such as (Rheosperse™ 3840); polyacrylates such as poly(acrylic acid) (DOLAPIX PC 21); polyphosphates such as PHOSPHOLAN®E 9NP; lignosulfonate such as ALTABIO® 200; lignosulfonic acid, sodium salt such as KRAFTSPERSE® 25M, polyacrylates, sodium salt such as DISPEX® AA4140; diethylene glycol monobutyl ether such as EDAPLAN® 470; amphiphilic polyethylene oxide (PEO)-polypropylene oxide (PPO)-polyethylene oxide (PEO) block copolymer such as ANT AROX® L-64 and as TERGITOL™ L-64 and as (PLURONIC® P104; CAS No.53637-25- 5), and a combination thereof. In some embodiments, the dispersant is Rheosperse™ 3840. The amount of dispersant present in the non-aqueous nitrification inhibitor composition can vary. In some embodiments, the amount of dispersant is from about 0.1% to about 5%, from about 0.5% to about 4%, from about 0.75% to about 4%, from about 1% to about 4%, from about 1.0% to about 3.0%, from about 1.5% to about 3%, from about 1.5% to about 2.5%, from about 1.5% to about 2.25%, or from about 1.5% to about 2.0% by weight, based on the total weight of the non- aqueous nitrification inhibitor composition. Tn some embodiments, amount of dispersant or wetting agent present in the non-aqueous nitrification inhibitor composition is at least about 0.1%, at least about 0.25%, at least about 0.5%, at least about 0.75%, at least about 1.0%, at least about 1.25%, at least about 1.50%, at least about 1.75%, at least about 2.0%, at least about 2.25%, at least about 2.30%, or at least about 2.50% by weight based on the total weight of the non-aqueous nitrification inhibitor composition. In addition, or in the alternative, the amount of dispersant or wetting agent present in the non-aqueous nitrification inhibitor composition is less than about 4.0%, less than about 3.75%, less than about 3.50%, less than about 3.25%, less than about 3.0%, less than about 2.75%, less than about 2.50%, 2.25% or less than about 2.1% by weight based on the total weight of the non-aqueous nitrification inhibitor composition.

[0063] In some embodiments, the amount of stabilizer is less than the amount of emulsifier. In some embodiments, the amount of stabilizer is less than the amount of surfactant. In some embodiments, the amount of stabilizer is less than the amount of dispersing agent or wetting agent. In some embodiments, the amount of stabilizer is less than each individual amount of emulsifier, surfactant and dispersant or wetting agent.

[0064] In some embodiments, the amount of dispersant or wetting agent is less than the amount of emulsifier. In some embodiments, the amount of dispersant or wetting agent is less than the amount of surfactant. In some embodiments, the amount of dispersant or wetting agent is less than each individual amount of emulsifier and surfactant.

[0065] Another aspect of the current disclosure relates to non-aqueous nitrification inhibitor compositions being in the form of an emulsion. As already mentioned above, these non-aqueous nitrification inhibitor compositions further comprise water and an oil. Specifically, the emulsion is selected from an oil-in-water emulsion (O / W) or a water-in-oil (W / O) emulsion. A skilled artisan would generally be aware on methods to prepare such emulsions based on current knowledge in the prior art. The function of the water and oil present the non-aqueous nitrification inhibitor is twofold, namely (a) generate the emulsion; and / or (b) solubilize the stabilizer, emulsifier, surfactant, and dispersant present in the disclosed composition. In some embodiments, the nonaqueous nitrification inhibitor composition is in the form of a water-in-oil (W / O) emulsion, i.e., an inverted emulsion. In such an emulsion the amount of water is less than the amount of oil.

[0066] The amount of water in the non-aqueous nitrification inhibitor composition can vary. In some embodiments, the amount of water ranges from about 0.01% to about 35%, from about 0.1% to about 30%, from about 1% to about 30%, from about 5% to about 30%, from about 10% to about 30%, from about 15% to about 30%, from about 20% to about 30, from about 22% to about 27%, or from about 22% to about 24% by weight, based on the total weight of the non-aqueous nitrification inhibitor composition. In some embodiments, the amount of water present in the nonaqueous nitrification inhibitor composition is at least about 0.1%, about 1%, about 5%, about 8%, about 10%, about 12%, about 15%, about 18%, about 20%, or at least about 25% by weight, based on the total weight of the composition. In addition, or in the alternative, the amount of water present in the non-aqueous nitrification inhibitor composition is less than about 35%, about 32%, about 30%, about 28%, about 25%, about 22%, about 20%, about 18%, about 15%, about 12%, or less than about 10% by weight, based on the total weight of the composition.

[0067] The amount of oil can vary. In some embodiments, the amount of oil ranges from about 1% to about 65%, from about 5% to about 60%, from about 10% to about 55%, from about 20% to about 55%, from about 30% to about 55%, from about 40% to about 55%, from about 42% to about 50%, or from about 45% to about 50% by weight, based on the total weight of the composition. The type of oil used in the emulsion can vary. For example, the oil can be a natural oil (i.e., obtained from natural sources) or a synthetic oil (i.e., prepared in the laboratory). Exemplary natural oils include, but are not limited to, mineral-based oil, petroleum-based oil, vegetable-based oil, and / or plant-derived oil. In some embodiments, the oil is a petroleum-based oil, for example isoparaffinic hydrocarbon Exxsol D60 (petroleum distillates, hydrotreated light, CAS No. 64742-47-8) or a lubricating oil (e.g., petroleum lubrication oil, C15-30, hydrotreated neutral-oil based; Cas No. 72623-86).

[0068] In some embodiments, the non-aqueous nitrification inhibitor composition disclosed herein (which is in the form of an inverted emulsion) further comprises water in an amount of from about 15% to about 30% by weight and / or and oil in an amount of from about 40% to about 50% by weight based on the total weight of the non-aqueous nitrification inhibitor composition.

[0069] In a certain embodiment, the non-aqueous nitrification inhibitor composition disclosed herein comprises thiram, dicyandiamide (DCD), a stabilizer present in an amount of from about 1% to about 3% by weight; an emulsifier present in an amount of from about 1% to about 4% by weight; a surfactant present in an amount of from about 1% to about 3% by weight; and a dispersant or wetting agent present in an amount of from about 1.5% to about 2.5% by weight. In such an embodiment, the combined amount of thiram and DCD ranges from about 10 % to about 20 % by weight and all weights are based on the composition being 100%. In such an embodiment, the nonaqueous nitrification inhibitor composition further comprises water in an amount of from about 15% to about 30% by weight, based on the total weight of the non-aqueous nitrification inhibitor composition. In such an embodiment, the non-aqueous nitrification inhibitor composition further comprises an oil present in an amount of from about 40% to about 50% by weight, based on the total weight of the non-aqueous nitrification inhibitor composition. As mentioned above, the oil and water are needed in the non-aqueous nitrification inhibitor composition to form the inverted emulsion.

[0070] Another aspect of the disclosed non-aqueous nitrification inhibitor composition relates to thiram and DCD being in a solid or solidified form dispersed throughout the emulsion comprising water, oil, stabilizer, emulsifier, surfactant, and dispersant. In such an embodiment, the shape of the solid or solidified form of the thiram and DCD is round (e.g., spherical or egg shaped) but should not be limited thereto. Additional shapes include cubic, rectangular and / or irregular.

[0071] In some embodiments, active agents thiram and DCD are present in the non-aqueous nitrification inhibitor composition in the form of granules, pellets, or a powder. In some embodiments, active agents thiram and DCD are present in the non-aqueous nitrification inhibitor composition in the form of a powder. In such embodiments, the powder comprises a homogenous mixture of thiram and DCD particles.

[0072] In some embodiments, active agents thiram and DCD are present in the non-aqueous nitrification inhibitor composition in the form of a granule or pellet. In such embodiments, each granule or pellet contains thiram and DCD, which are homogenously dispersed throughout such granule or pellet.

[0073] Granulation of thiram and DCD can be carried out using any known granulation method in the art. In some embodiments, granulation of thiram and DCD can be achieved using dry granulation methods such as compaction granulation methods. During this physical process, finely divided nutrient particles are homogenized into composite granules without compromising the chemical stability and / or structural integrity of thiram and DCD used. In some embodiments, granulation of thiram and DCD can be achieved via pan granulation, drum granulation, extrusion, palletization, granular crumble but should not be limited thereto.

[0074] The mean particle size (D50) of the powder particles, granules and / or pellets can vary. In some embodiments, the mean particle size (D50) is from about 1 pm to about 1000 pm, from about 10 pm to about 500 pm, from about 10 pm to about 250 pm, from about 10 pm to about 100 pm, or from about 10 pm to about 50 pm. In some embodiments, the mean particle size of the powder particles, granules and / or pellets is at least about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 125 pm, about 150 pm, about 175 pm, about 200 pm, about 225 pm, about 250 pm, about 275 pm, about 300 pm, about 325 pm, about 350 pm, about 375 pm, about 400 pm, about 450 pm, or at least about 500 pm. In addition, or in the alternative, the mean particle size of the powder particles, granules and / or pellets is less than about 1000 pm, about 900 pm, about 800 pm, about 700 pm, about 600 pm, about 500 pm, about 400 pm, about 300 pm, less than about 275 pm, less than about 250 pm, less than about 225 pm, less than about 200 pm, less than about 275 pm, less than about 250 pm, less than about 225 pm, less than about 200 pm, less than about 275 pm, less than about 250 pm, less than about 225 pm, less than about 200 pm, less than about 175 pm, less than about 150 pm, less than about 125 pm, less than about 100 pm, less than about 75 pm, or less than about 50 pm.

[0075] In some embodiments, the non-aqueous nitrification inhibitor composition contains granules, pellets, and / or powder particles having a particle size ranging from about 10 to about 500, from about 50 to about 450, from about 75 to about 400, from about 100 to about 350, from about 100 to about 300, from about 125 to about 275, from about 125 to about 250, from about 150 to about 230, from about 150 to about 200 or from about 150 to about 175 Size Guide Number (SGN).

[0076] In some embodiments, the non-aqueous nitrification inhibitor composition contains granules, pellets, or powder particles having an average mesh size ranging from about 1 to about 635, from about 35 to about 635, from about 60 to about 635, from about 100 to about 635, from about 140 to about 635, from about 200 to about 500, from about 230 to about 450, from about 250 to about 400, from about 250 to about 375, from about 275 to about 325, or from about 300 to about 325 US mesh. In some embodiments, the non-aqueous nitrification inhibitor composition contains granules, pellets, or powder particles having an average mesh size ranging from about 10 to about 635, from about 10 to about 535, from about 10 to about 475, from about 12 to about 450, from about 14 to about 425, from about 16 to about 400, from about 18 to about 400, or from about 20 to about 400 US mesh.

[0077] In some embodiments, the non-aqueous nitrification inhibitor composition contains granules, pellets, and / or powder particles made of DCD and thiram having a uniformity index (UI) ranging between about 30-40, 30-50, 35-45, 40-60, 40-50, or 50-60 (indicating that the granules are uniform in size).

[0078] In some embodiments, the non-aqueous nitrification inhibitor composition contains granules, pellets, and / or powder particles made of DCD and thiram having a particle density ranging from about 10-150 lbs / ft3, 30-100 lbs / ft3, from about 45-85 lbs / ft3, or from about 45-60 lbs / ft3.

[0079] In some embodiments, the non-aqueous nitrification inhibitor composition has a bulk density of from about 10-150 lbs / ft3, 30-100 lbs / ft3, from about 45-75 lbs / ft3, from about 50-70 lbs / ft3or from about 60-70 lbs / ft3. In some embodiments, the bulk density is a “loose” bulk density.

[0080] In some embodiments, the non-aqueous nitrification inhibitor composition contains granules, pellets, and / or powder particles made of DCD and thiram having a moisture holding capacity ranging from 2.3 wt % to 6.5 wt %, including exemplary values of 2.4 wt %, 2.5 wt %, 2.6 wt %, 2.7 wt %, 2.8 wt %, 2.9 wt %, 3.0 wt %, 3.1 wt %, 3.2 wt %, 3.3 wt %, 3.4 wt %, 3.5 wt %, 3.6 wt %, 3.7 wt %, 3.8 wt %, 3.9 wt %, 4 wt %, 4.1 wt %, 4.2 wt %, 4.3 wt %, 4.4 wt %, 4.5 wt %, 4.6 wt %, 4.7 wt %, 4.8 wt %, 4.9 wt %, 5 wt %, 5.1 wt %, 5.2 wt %, 5.3 wt %, 5.4 wt %, 5.5 wt %, 5.6 wt %, 5.7 wt %, 5.8 wt %, 5.9 wt %, 6 wt %, 6.1 wt %, 6.2 wt %, 6.3 wt %, and 6.4 wt %.

[0081] Another aspect of the current disclosure relates to the various benefits observed from the non-aqueous nitrification inhibitor composition disclosed herein. Without being bound to theory, embodiments of the non-aqueous nitrification inhibitor composition can provide a surprising increase in nitrogen availability for plants / crops to increase plant / crops health and yield potential as well as protecting against nitrogen loss to keep nitrogen available longer in the root zone of plants.

[0082] In some embodiments, the non-aqueous nitrification inhibitor composition inhibits nitrification in the soil by at least about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or at least by 95% compared to soil that is untreated.

[0083] In some embodiments, the non-aqueous nitrification inhibitor composition reduces leaching of nitrogen within the soil by at least about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or at least by 95% compared to soil that is untreated.

[0084] In some embodiments, the non-aqueous nitrification inhibitor composition reduces dentrification of nitrogen within the soil by at least about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or at least by 95% compared to soil that is untreated.

[0085] In some embodiments, the non-aqueous nitrification inhibitor composition increases plant health and / or crop yield of plants and / or crops by at least about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or at least by 95% compared to plants and / or crops which are untreated.

[0086] The plants and / or crops include plants such as cereals, fruit trees, fruit bushes, grains, legumes and combinations thereof. Exemplary crops include, but are not limited to, rye, oats, maize, rice, sorghum, triticale, oilseed rape, rice, soybeans, sugar beet, sugar cane, turf, fruit trees, palm trees, coconut trees or other nuts, grapes, fruit bushes, fruit plants; beet, fodder beet, pomes, stone fruit, apples, pears, plums, peaches, almonds, cherries, and berries, for example strawberries, raspberries and blackberries; leguminous plants such as beans, lentils, peas, soybeans, peanuts; oil plants, for example rape, mustard, sunflowers; cucurbitaceae, for example marrows, cucumbers, melons; fibre plants, for example cotton, flax, hemp, jute; citrus fruit, for example oranges, lemons, grapefruit and mandarins; vegetables, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, sweet potatoes, yams, paprika; as well as ornamentals, such as flowers, shrubs, broad leaved trees and evergreens, for example conifers, cereals, wheat, barley, oats, winter wheat, spring wheat, winter barley, spring barley, triticale, cereal rye, winter durum wheat, spring durum wheat, winter oat, spring oat, fodder cereals, ray-grass, cocksfoot, fescue, timothy, grass for seed and grassland and any combination thereof.

[0087] III. Formulation

[0088] Formulations comprising the non-aqueous nitrification inhibitor composition can be in any useful form. Specifically, the non-aqueous nitrification inhibitor composition is already in the form of an inverted emulsion, wherein granules of thiram and DCD are dispersed throughout. Such an emulsion can be formulated as a ready-to-use solution or suspension concentrate. For purposes of the present disclosure, “ready-to-use” refers to compositions that are not in a concentrate form but rather which may be applied without modification of the relative amounts of components within the product. In embodiments, compositions and formulations are provided in concentrates for enduse tank-mixing.

[0089] The formulations include those which are ready-for-use and can be applied with a suitable apparatus to the plant, and commercial concentrates which have to be diluted with water prior to use, e.g., a tank-mix. Customary applications are, for example, dilution in water and subsequent spraying of the resulting spray liquid, application after dilution in oil, or direct application without dilution.

[0090] Formulations can include solvents. Suitable organic solvents include all polar and nonpolar organic solvents usually employed for formulation purposes. Preferably the solvents are selected from ketones, e.g., methyl-isobutyl-ketone and cyclohexanone, amides, e.g., dimethyl formamide, and alkanecarboxylic acid amides, e.g., N,N-dimethyl decaneamide and N,N-dimethyl octanamide, furthermore cyclic solvents, e.g., N-methyl-pyrrolidone, N-octyl-pyrrolidone, N- dodecylpyrrolidone, N-octyl-caprolactame, N-dodecyl-caprolactame and butyrolactone, furthermore strong polar solvents, e.g., dimethylsulfoxide, mineral oils, e.g., white spirit, petroleum, alkyl benzenes and spindle oil, also esters, e.g., propyleneglycol-monomethylether acetate, adipic acid dibutylester, acetic acid hexylester, acetic acid heptylester, citric acid tri-n- butylester and phthalic acid di-n-butylester, and also alcohols, e.g., benzyl alcohol and 1 -methoxy - 2-propanol. Useful liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or dichloromethane, aliphatic hydrocarbons such as cyclohexane or paraffins, for example, mineral oil fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulphoxide, and also water. The solvent can be present in an amount from about 1% to about 99% w / w, for example, about 5% w / w to about 75% w / w, about 15% w / w to about 70% w / w, about 25% w / w to about 65% w / w, about 35% w / w to about 60% w / w, about 40% w / w to about 55% w / w, or about 45% w / w to about 50% w / w, based on the composition being 100%.

[0091] Formulations can include carriers and fillers. A carrier is a natural or synthetic, organic or inorganic substance for admixing or combining with the compositions for better applicability, in particular for application to plants or plant parts. The carrier, which may be solid or liquid, is generally inert and should be suitable for use in agriculture. Useful solid or liquid carriers include, for example, ammonium salts and natural rock dusts, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock dusts, such as finely divided silica, alumina and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohols, especially butanol, organic solvents, mineral and vegetable oils, and derivatives thereof. Mixtures of such carriers can likewise be used.

[0092] Suitable solid fillers and carriers include inorganic particles, e.g., carbonates, silicates, sulphates and oxides with an average particle size of between 0.005 and 20 pm, preferably of between 0.02 to 10 pm, for example, ammonium sulphate, ammonium phosphate, urea, calcium carbonate, calcium sulphate, magnesium sulphate, magnesium oxide, aluminum oxide, silicium dioxide, so-called fine-particle silica, silica gels, natural or synthetic silicates, and alumosilicates and plant products like cereal flour, wood powder / sawdust and cellulose powder.

[0093] Useful solid carriers include, for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic meals, and also granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.

[0094] Useful liquefied gaseous extenders or carriers are those liquids which are gaseous at standard temperature and under standard pressure, for example, aerosol propellants such as halohydrocarbons, and also butane, propane, nitrogen and carbon dioxide.

[0095] Formulations can include other additional components, for example, protective colloids, binders, extenders, adhesives, tackifiers, thickeners, thixotropic substances, penetrants, stabilizers, sequestrants, surfactants, complexing agents, etc. In general, the compositions can be combined with any solid or liquid additive commonly used for formulation purposes.

[0096] In the formulations, it is possible to use tackifiers such as carboxymethylcellulose, and natural and synthetic polymers in the form of powders, granules or lattices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Further additives may be mineral and vegetable oils. If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. The formulations can further comprise additional surfactants besides the surfactant present in the non-aqueous nitrification inhibitor composition. Useful surfactants are emulsifiers and / or foam formers, dispersants or wetting agents having ionic or nonionic properties, or mixtures of these surfactants. Examples of these are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols, and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example, alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, aryl sulphonates, protein hydrolysates, lignosulphite waste liquors and methylcellulose. The presence of a surfactant is necessary if one of the active ingredients and / or one of the inert carriers is insoluble in water and when application is effected in water. The proportion of surfactants is between about 5% and about 40% by weight of the composition. In some embodiments, the proportion of surfactants is between about 10% and about 30%> or between about 15% and about 25% by weight of the composition. In some embodiments, the proportion of surfactant is less than about 40%, less than about 30%, less than about 25%, less than about 20%, less than about 10%, or less than about 5% by weight of the composition. In some embodiments, the proportion of surfactants is more than about 5%, more than about 10%, more than about 20%, more than about 25%, or more than about 30% by weight of the composition.

[0097] Suitable surfactants (adjuvants, emulsifiers, dispersants, protective colloids, wetting agent and adhesive) include all common ionic and non-ionic substances, for example, ethoxylated nonylphenols, polyalkylene glycolether of linear or branched alcohols, reaction products of alkyl phenols with ethylene oxide and / or propylene oxide, reaction products of fatty acid amines with ethylene oxide and / or propylene oxide, fatty acid esters, alkyl sulfonates, alkyl sulphates, alkyl ethersulphates, alkyl etherphosphates, arylsulphate, ethoxylated arylalkylphenols (e.g., tristyryl- phenol-ethoxylates, ethoxylated and propoxylated arylalkylphenols like sulphated or phosphated arylalkylphenol-ethoxylates and -ethoxy- and -propoxylates). Further examples are natural and synthetic, water soluble polymers, e.g., lignosulphonates, gelatine, gum arabic, phospholipides, starch, hydrophobic modified starch and cellulose derivatives, in particular cellulose ester and cellulose ether, polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid and co-polymeri sates of (meth)acrylic acid and (meth)acrylic acid esters, and co-poly meri sates of methacrylic acid and methacrylic acid esters which are neutralized with alkalimetal hydroxide and also condensation products of optionally substituted naphthalene sulfonic acid salts with formaldehyde.

[0098] The formulations may comprise colorants and dyes. Dyes include inorganic pigments, for example, iron oxide, titanium oxide and Prussian blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum, and zinc.

[0099] Antifoams which may be present in the formulations include, e.g., silicone emulsions, long- chain alcohols, fatty acids and their salts as well as fluoroorganic substances and mixtures thereof.

[0100] Thickeners include polysaccharides, e.g., xanthan gum or veegum, silicates, e.g., attapulgite, bentonite and fine-particle silica.

[0101] The amounts of active ingredients (i.e., thiram and DCD) in the formulations are generally between 0.05 and 99% by weight, between 0.01 and 98% by weight, between 0.1 and 95% by weight, between 0.5 and 90% by weight, between 10 and 70% by weight, between 20 and 60%, or between 25 and 50% by weight, based on the weight of the formulation. In some embodiments, the amounts of active ingredients is preferably between 0.1 and 95% by weight, more preferably between 0.5 and 90% by weight, and most preferably between 10 and 70% by weight. Depending on the formulation and desired route of application, one of ordinary skill in the art can determine appropriate amounts of active ingredients and additives, and the amount of active ingredient(s) and additive(s) in the formulations may vary in a broad range. The concentration of the active ingredients in the application forms is generally between 0.000001 and 95% by weight, between 0.0001 and 20%, between 0.0001 and 10%, between 0.0001 and 2%, between 0.001 and 2%, between 0.01 and 1.5%, or between 0.1 and 1% by weight of active ingredients. Alternatively, a formulation can contain active ingredients at a concentration from 1 mole / liter to about 10,000 moles / liter, or from about 2 moles / liter to about 5,000 moles / liter, or from about 3 moles / liter to about 3,000 moles / liter, or from about 4 moles / liter to about 2,000 moles / liter, or from about 5 moles / liter to about 500 moles / liter, or from about 5 moles / liter to about 200 moles / liter, or from about 5 moles / liter to about 100 moles / liter, or from about 5 moles / liter to about 50 moles / liter, or from about 5 moles / liter to about 15 moles / liter, or from about 5 moles / liter to about 10 moles / liter. The formulations mentioned can be prepared in a manner known, for example, by mixing the active ingredients with at least one customary extender, solvent or diluent, adjuvant, emulsifier, dispersant, and / or binder or fixative, wetting agent, water repellent, if appropriate, desiccants and UV stabilizers, and, if appropriate, dyes and pigments, antifoams, preservatives, such bronopol in an amount of about 0.04%, inorganic and organic thickeners, adhesives, gibberellins, further processing auxiliaries, and also water.

[0102] III. Agricultural Composition

[0103] Any of the described compositions or formulations disclosed herein can be combined with one or more other agricultural products, selected from the group consisting of fertilizer, agriculturally active compounds, seed, compounds having urease inhibition activity, nitrification inhibition activity, pesticides, herbicides, insecticides, fungicides, miticides, and the like.

[0104] The amount of the disclosed composition or formulation and agricultural product present in the agricultural composition can vary. In some embodiments, disclosed composition or formulation and agricultural product are present in the agricultural composition at a weight ratio of from about 1 : 1000 to about 1000: 1, 1 : 100 to about 100:1, 1 : 10 to about 10:1, about 1 :5 to about 5: 1, about 1 :3 to about 3: 1, about 1 :2 to about 2: 1, or about 1: 1 of composition or formulation:agricultural product.

[0105] In some embodiments, the described composition or formulation may be mixed with the fertilizer products, applied as a surface coating to the fertilizer products, or otherwise thoroughly mixed with the fertilizer products. In some embodiments, in such combined agricultural compositions, the fertilizer is in the form of particles having an average diameter of from about powder size (less than about 0.001 cm) to about 10 mm, more preferably from about 0.1 mm to about 5 mm, and still more preferably from about 0.15 mm to about 3 mm. The composition or formulation of the invention can be present in such combined agricultural compositions at a level of about 0.001 g to about 20 g per 100 g fertilizer, about 0.01 to 7 g per 100 g fertilizer, about 0.08 g to about 5 g per 100 g fertilizer, or about 0.09 g to about 2 g per 100 g fertilizer. In the case of the combined fertilizer / composition agricultural products, the combined agricultural composition can be applied at a level so that the amount of the composition of the invention applied is about 10-150 g per acre of soil, about 30-125 g per acre, or about 40-120 g per acre of soil. The combined agricultural composition can likewise be applied as liquid dispersions or as dry granulated products, at the discretion of the user. When the composition or formulation of the invention is used as a coating, the agricultural composition can comprise between about 0.005% and about 15% by weight of the coated fertilizer product, about 0.01% and about 10% by weight of the coated fertilizer product, about 0.05% and about 2% by weight of the coated fertilizer product or about 0.5% and about 1% by weight of the coated fertilizer product.

[0106] A. Fertilizers

[0107] In some embodiments, the agricultural product is a fertilizer. The fertilizer can be a solid fertilizer, such as, but not limited to, a granular fertilizer, and the composition or formulation of the invention can be applied to the fertilizer as a liquid dispersion. The fertilizer can be in liquid form, and the composition or formulation of the invention can be mixed with the liquid fertilizer. The fertilizers can be selected from the group consisting of starter fertilizers, phosphate-based fertilizers, fertilizers containing nitrogen, fertilizers containing phosphorus, fertilizers containing potassium, fertilizers containing calcium, fertilizers containing magnesium, fertilizers containing boron, fertilizers containing chlorine, fertilizers containing zinc, fertilizers containing manganese, fertilizers containing copper, fertilizers containing urea and ammonium nitrite, and / or fertilizers containing molybdenum materials. In some embodiments, the fertilizer is or contains urea, and / or ammonia, including anhydrous ammonia fertilizer. For example, in some embodiments, the fertilizer is UAN-32 (which is a solution of ammonium nitrate and urea). In some embodiments, the fertilizer comprises plant-available nitrogen, phosphorous, potassium, sulfur, calcium, magnesium, or micronutrients. In some embodiments, the fertilizer is solid, granular, a fluid suspension, a gas, or a solutionized fertilizer. In some embodiments, the fertilizer comprises a micronutrient. A micronutrient is an essential element required by a plant in small quantities. In some embodiments, the fertilizer comprises a metal ion selected from the group consisting of: Fe, Mn, Mg, Zn, Cu, Ni, Co, Mo, V, and Ca. In some embodiments, the fertilizer comprises gypsum, Kieserite Group member, potassium product, potassium magnesium sulfate, elemental sulfur, or potassium magnesium sulfate. Such fertilizers may be granular, liquid, gaseous, or mixtures (e.g., suspensions of solid fertilizer particles in liquid material).

[0108] In some embodiments, the composition or formulation of the invention is combined with any suitable liquid or dry fertilizer for application to fields and / or crops.

[0109] The described composition or formulation of the invention can be applied with the application of a fertilizer. The composition or formulation of the invention can be applied prior to, subsequent to, or simultaneously with the application of fertilizers. Fertilizer compositions containing the composition or formulation of the invention can be applied in any manner which will benefit the crop of interest. In some embodiments, a fertilizer composition is applied to growth mediums in a band or row application. In some embodiments, the compositions are applied to or throughout the growth medium prior to seeding or transplanting the desired crop plant. In some embodiments, the compositions can be applied to the root zone of growing plants.

[0110] B. Seed

[0111] Some embodiments describe agricultural seeds coated with one or more of the described compositions or formulations of the invention. The composition or formulation of the invention can be present in the seed product at a level of from about 0.001-10%, about 0.004%-2%, about 0.01% to about 1%, or from about 0.1% to about 1% by weight (or no more than about 10%, about 9%, about 8%, about 7% about 6%, about 5%, about 4%, about 3%, about 2%, about 1%, about 0.5%, about 0.1%, about 0.01% or no more than 0.001%), based upon the total weight of the coated seed product. A seed can be, but is not limited to, wheat, barley, oat, triticale, rye, rice, maize, soya bean, cotton, or oilseed rape.

[0112] C. Other

[0113] Some embodiments describe urease-inhibiting compounds, nitrification inhibiting compounds, pesticides, herbicides, insecticides, and / or miticides in combination with one or more of the described compositions of the invention. As used herein, “pesticide” refers to any agent with pesticidal activity (e.g., herbicides, insecticides) and is preferably selected from the group consisting of insecticides, herbicides, and mixtures thereof, but normally excluding materials which assertedly have plant-fertilizing effect, for example sodium borate and zinc compounds such as zinc oxide, zinc sulfate, and zinc chloride. For an unlimited list of pesticides, see “Farm Chemicals Handbook 2000, 2004” (Meister Publishing Co, Willoughby, Ohio), which is hereby incorporated by reference in its entirety.

[0114] Exemplary herbicides include, but are not limited to, acetochlor, alachlor, aminopyralid, atrazine, benoxacor, bromoxynil, carfentrazone, chlorsulfuron, clodinafop, clopyralid, dicamba, diclofop-methyl, dimethenamid, fenoxaprop, flucarbazone, flufenacet, flumetsulam, flumiclorac, fluroxypyr, glufosinate-ammonium, glyphosate, halosulfuron-methyl, imazamethabenz, imazamox, imazapyr, imazaquin, imazethapyr, isoxaflutole, quinclorac, MCPA, MCP amine, MCP ester, mefenoxam, mesotrione, metolachlor, s-metolachlor, metribuzin, metsulfuron methyl, nicosulfuron, paraquat, pendimethalin, picloram, primisulfuron, propoxycarbazone, prosulfuron, pyraflufen ethyl, rimsulfuron, simazine, sulfosulfuron, thifensulfuron, topramezone, tralkoxydim, triallate, triasulfuron, tribenuron, triclopyr, trifluralin, 2,4-D, 2,4-D amine, 2,4-D ester and the like.

[0115] Exemplary insecticides include, but are not limited to, 1,2 di chloropropane, 1,3 di chloropropene, abamectin, acephate, acequinocyl, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha cypermethrin, alpha ecdysone, amidithion, amidoflumet, aminocarb, amiton, amitraz, anabasine, arsenous oxide, athidathion, azadirachtin, azamethiphos, azinphos ethyl, azinphos methyl, azobenzene, azocyclotin, azothoate, barium hexafluorosilicate, barthrin, benclothiaz, bendiocarb, benfuracarb, benoxafos, bensultap, benzoximate, benzyl benzoate, beta cyfluthrin, beta cypermethrin, bifenazate, bifenthrin, binapacryl, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid, bromfenvinfos, bromo DDT, bromocyclen, bromophos, bromophos ethyl, bromopropylate, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, chinomethionat, chlorantraniliprole, chlorbenside, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenethol, chlorfenson, chlorfensulphide, chlorfenvinphos, chlorfluazuron, chlormephos, chlorobenzilate, chloroform, chloromebuform, chloromethiuron, chloropicrin, chloropropylate, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos methyl, chlorthiophos, chromafenozide, cinerin I, cinerin II, cismethrin, cloethocarb, clofentezine, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, cruentaren A & B, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyclethrin, cycloprothrin, cyenopyrafen, cyflumetofen, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyphenothrin, cyromazine, cythioate, d-limonene, dazomet, DBCP, DCIP, DDT, decarbofuran, deltamethrin, demephion, demephion O, demephion S, demeton, demeton methyl, demeton O, demeton O methyl, demeton S, demeton S methyl, demeton S methyl sulphon, diafenthiuron, dialifos, diamidafos, diazinon, dicapthon, dichlofenthion, dichlofluanid, dichlorvos, dicofol, dicresyl, dicrotophos, dicyclanil, dieldrin, dienochlor, diflovidazin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinobuton, dinocap, dinocap 4, dinocap 6, dinocton, dinopenton, dinoprop, dinosam, dinosulfon, dinotefuran, dinoterbon, diofenolan, dioxabenzofos, dioxacarb, dioxathion, diphenyl sulfone, disulfiram, disulfoton, dithicrofos, DNOC, dofenapyn, doramectin, ecdysterone, emamectin, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate methyl, ethoprophos, ethyl DDD, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etoxazole, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenazaquin, fenbutatin oxide, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenothiocarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fenpyroximate, fenson, fensulfothion, fenthion, fenthion ethyl, fentrifanil, fenvalerate, fipronil, flonicamid, fluacrypyrim, fluazuron, flubendiamide, flubenzimine, flucofuron, flucycloxuron, flucythrinate, fluenetil, flufenerim, flufenoxuron, flufenprox, flumethrin, fluorbenside, fluvalinate, fonofos, formetanate, formothion, formparanate, fosmethilan, fospirate, fosthiazate, fosthietan, furathiocarb, furethrin, furfural, gamma cyhalothrin, gamma HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, hexythiazox, HHDN, hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imicyafos, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isamidofos, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lambda cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfen, mesulfenfos, metaflumizone, metam, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methylchloroform, methylene chloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, MNAF, monocrotophos, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nikkomycins, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton methyl, oxydeprofos, oxy di sulfoton, paradichlorobenzene, parathion, parathion methyl, penfluron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phosphocarb, phoxim, phoxim methyl, pirimetaphos, pirimicarb, pirimiphos ethyl, pirimiphos methyl, potassium arsenite, potassium thiocyanate, pp' DDT, prallethrin, precocene T, precocene II, precocene III, primidophos, proclonol, profenofos, profluthrin, promacyl, promecarb, propaphos, propargite, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbute, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos, quinalphos methyl, quinothion, quantifies, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silafluofen, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulcofuron, sulfiram, sulfluramid, sulfotep, sulfur, sulfuryl fluoride, sulprofos, tau fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetradifon, tetramethrin, tetranactin, tetrasul, theta cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb, thiofanox, thiometon, thionazin, thioquinox, thiosultap, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate, triazophos, trichlorfon, trichlormetaphos 3, trichloronat, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, vaniliprole, vaniliprole, XMC, xylylcarb, zeta cypermethrin and zolaprofos.

[0116] Exemplary classes of miticides include, but are not limited to, botanical acaricides, bridged diphenyl acaricides, carbamate acaricides, oxime carbamate acaricides, carbazate acaricides, dinitrophenol acaricides, formamidine acaricides, isoxaline acaricides, macrocyclic lactone acaricides, avermectin acaricides, milbemycin acaricides, milbemycin acaricides, mite growth regulators, organochlorine acaricides, organophosphate acaricides, organothiophosphate acaricides, phosphonate acaricides, phosphoarmidothiolate acaricies, organitin acaricides, phenyl sulfonamide acaricides, pyrazolecarboxamide acaricdes, pyrethroid ether acaricide, quaternary ammonium acaricides, oyrethroid ester acaricides, pyrrole acaricides, quinoxaline acaricides, methoxyacrylate strobilurin acaricides, teronic acid acaricides, thiasolidine acaricides, thiocarbamate acaricides, thiourea acaricides, and unclassified acaricides. Examples of miticides for these classes include, but are not limited to, to botanical acaricides - carvacrol, sanguinarine; bridged diphenyl acaricides - azobenzene, benzoximate, benzyl, benzoate, bromopropylate, chlorbenside, chlorfenethol, chlorfenson, chlorfensulphide, chlorobenzilate, chloropropylate, cyflumetofen, DDT, dicofol, diphenyl, sulfone, dofenapyn, fenson, fentrifanil, fluorbenside, genit, hexachlorophene, phenproxide, proclonol, tetradifon, tetrasul; carbamate acaricides - benomyl, carbanolate, carbaryl, carbofuran, methiocarb, metolcarb, promacyl, propoxur; oxime carbamate acaricides - aldicarb, butocarboxim, oxamyl, thiocarboxime, thiofanox; carbazate acaricides - bifenazate; dinitrophenol acaricides - binapacryl, dinex, dinobuton, dinocap, dinocap-4, dinocap- 6, dinocton, dinopenton, dinosulfon, dinoterbon, DNOC; formamidine acaricides - amitraz, chlordimeform, chloromebuform, formetanate, formparanate, medimeform, semiamitraz; isoxazoline acaricides - afoxolaner, fluralaner, lotilaner, sarolaner; macrocyclic lactone acaricides - tetranactin; avermectin acaricides - abamectin, doramectin, eprinomectin, ivermectin, selamectin; milbemycin acaricides - milbemectin, milbemycin, oxime, moxidectin; mite growth regulators - clofentezine, cyromazine, diflovidazin, dofenapyn, fluazuron, flubenzimine, flucycloxuron, flufenoxuron, hexythiazox; organochlorine acaricides - bromociclen, camphechlor, DDT, dienochlor, endosulfan, lindane; organophosphate acaricides - chlorfenvinphos, crotoxyphos, dichlorvos, heptenophos, mevinphos, monocrotophos, naled, TEPP, tetrachlorvinphos; organothiophosphate acaricides - amidithion, amiton, azinphos-ethyl, azinphos-m ethyl, azothoate, benoxafos, bromophos, bromophos-ethyl, carbophenothion, chlorpyrifos, chlorthiophos, coumaphos, cyanthoate, demeton, demeton-O, demeton-S, demeton- methyl, demeton-O-methyl, demeton-S-methyl, demeton-S-methylsulphon, dialifos, diazinon, dimethoate, dioxathion, disulfoton, endothion, ethion, ethoate-methyl, formothion, malathion, mecarbam, methacrifos, omethoate, oxydeprofos, oxy di sulfoton, parathion, phenkapton, phorate, phosalone, phosmet, phostin, phoxim, pirimiphos-methyl, prothidathion, prothoate, pyrimitate, quinalphos, quintiofos, sophamide, sulfotep, thiometon, triazophos, trifenofos, vamidothion; phosphonate acaricides - trichlorfon; phosphoramidothioate acaricides - isocarbophos, methamidophos, propetamphos; phosphorodiamide acaricides - dimefox, mipafox, schradan; organotin acaricides - azocyclotin, cyhexatin, fenbutatin, oxide, phostin; phenyl sulfamide acaricides - dichlofluanid; phthalimide acaricides - dialifos, phosmet; pyrazole acaricides - cyenopyrafen, fenpyroximate; phenylpyrazole acaricides - acetoprole, fipronil, vaniliprole; pyrazolecarboxamide acaricides - pyflubumide, tebufenpyrad; pyrethroid ester acaricides - acrinathrin, bifenthrin, brofluthrinate, cyhalothrin, cypermethrin, alpha-cypermethrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, tau-fluvalinate, permethrin; pyrethroid ether acaricides - halfenprox; pyrimidinamine acaricides - pyrimidifen; pyrrole acaricides - chlorfenapyr; quaternary ammonium acaricides - sanguinarine; quinoxaline acaricides - chinomethionat, thioquinox; methoxyacrylate strobilurin acaricides - bifujunzhi, fluacrypyrim, flufenoxystrobin, pyriminostrobin; sulfite ester acaricides - aramite, propargite; tetronic acid acaricides - spirodiclofen; tetrazine acaricides, clofentezine, diflovidazin; thiazolidine acaricides - flubenzimine, hexythiazox; thiocarbamate acaricides - fenothiocarb; thiourea acaricides - chloromethiuron, diafenthiuron; unclassified acaricides - acequinocyl, acynonapyr, amidoflumet, arsenous, oxide, clenpirin, closantel, crotamiton, cycloprate, cymiazole, disulfiram, etoxazole, fenazaflor, fenazaquin, fluenetil, mesulfen, MNAF, nifluridide, nikkomycins, pyridaben, sulfiram, sulfluramid, sulfur, thuringiensin, triarathene.

[0117] In some embodiments, a miticide can also be selected from abamectin, acephate, acequinocyl, acetamiprid, aldicarb, allethrin, aluminum phosphide, aminocarb, amitraz, azadiractin, azinphos-ethyl, azinphos-m ethyl, Bacillus thuringiensis, bendiocarb, beta-cyfluthrin, bifenazate, bifenthrin, bornyl, buprofezin, calcium cyanide, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, chlorfenvinphos, chlorobenzilate, chloropicrin, chlorpyrifos, clofentezine, chlorfenapyr, clothianidin, coumaphos, crotoxyphos, crotoxyphos + dichlorvos, cryolite, cyfluthrin, cyromazine, cypermethrin, deet, deltamethrin, demeton, diazinon, dichlofenthion, dichloropropene, dichlorvos, dicofol, dicrotophos, dieldrin, dienochlor, diflubenzuron, dikar (fungicide + miticide), dimethoate, dinocap, dinotefuran, dioxathion, disulfoton, emamectin benzoate, endosulfan, endrin, esfenvalerate, ethion, ethoprop, ethylene dibromide, ethylene dichloride, etoxazole, famphur, fenitrothion, fenoxycarb, fenpropathrin, fenpyroximate, fensulfothion, fenthion, fenvalerate, flonicamid, flucythrinate, fluvalinate, fonofos, formetanate hydrochloride, gamma-cyhalothrin, halofenozide, hexakis, hexythiazox, hydramethylnon, hydrated lime, indoxacarb, imidacloprid, kerosene, kinoprene, lambda-cyhalothrin, lead arsenate, lindane, malathion, mephosfolan, metaldehyde, metam-sodium, methamidophos, methidathion, methiocarb, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl bromide, methyl parathion, mevinphos, mexacarbate, Milky Disease Spores, naled, naphthalene, nicotine sulfate, novaluron, oxamyl, oxydemeton- methyl, oxythioquinox, para-dichlorobenzene, parathion, PCP, permethrin, petroleum oils, phorate, phosalone, phosfolan, phosmet, phosphamidon, phoxim, piperonyl butoxide, pirimicarb, pirimiphos-methyl, profenofos, propargite, propetamphos, propoxur, pymetrozine, pyrethroids - synthetic: see allethrin, permethrin, fenvalerate, resmethrin, pyrethrum, pyridaben, pyriproxyfen, resmethrin, rotenone, s-methoprene, soap, pesticidal, sodium fluoride, spinosad, spiromesifen, sulfotep, sulprofos, temephos, terbufos, tetrachlorvinphos, tetrachlorvinphos + dichlorvos, tetradifon, thiamethoxam, thiodicarb, toxaphene, tralomethrin, trimethacarb, and tebufenozide.

[0118] In some embodiments, nitrification inhibiting compounds selected from the group consisting of nitrapyrin, pronitradine, and 3,4-dimethylpyrazole-phosphate are combined with one or more of the described compositions or formulations of the invention.

[0119] V. Methods

[0120] In some embodiments, the non-aqueous nitrification inhibitor composition disclosed herein are used directly. In other embodiments, the non-aqueous nitrification inhibitor compositions disclosed herein are formulated in ways to make their use convenient in the context of productive agriculture. The non-aqueous nitrification inhibitor compositions used in these methods include the compositions as described above. Such non-aqueous nitrification inhibitor compositions can be used in methods such as:

[0121] A. Methods of Improving Plant Growth and / or Fertilizing Soil

[0122] B. Methods of Inhibiting Nitrification or Ammonia Release or Evolution

[0123] C. Methods of Improving Soil Conditions

[0124] D. Methods for Reducing Nitrogen (N) Leaching and / or Dentrifi cation

[0125] A. Methods for fertilizing soil and / or improving plant / crop growth and / or health comprise contacting a non-aqueous nitrification inhibitor composition or an agricultural formulation thereof containing thiram and DCD as active agents as disclosed herein with soil. In some embodiments, the non-aqueous nitrification inhibitor composition or an agricultural formulation thereof is applied to the soil prior to emergence of a planted crop. In some embodiments, the non-aqueous nitrification inhibitor composition or an agricultural formulation thereof is applied to the soil post emergence of a planted crop. In some embodiments, the non-aqueous nitrification inhibitor composition or an agricultural formulation thereof is applied to the soil adjacent to the plant and / or at the base of the plant and / or in the root zone of the plant. In some embodiments, the methods disclosed herein increase plant health and / or crop yield of plants and / or crops by at least about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or at least by 95% compared to plants and / or crops which are untreated. Methods for improving plant growth can also be achieved by applying a non-aqueous nitrification inhibitor composition or an agricultural formulation thereof containing thiram and DCD as active agents as described herein as a seed coating to a seed in the form of a liquid dispersion which upon drying forms a dry residue. In these embodiments, seed coating provides the non-aqueous nitrification inhibitor composition or an agricultural formulation thereof in close proximity to the seed when planted so that the thiram and DCD can exert their beneficial effects in the environment where they are most needed. That is, thiram and DCD provide an environment conducive to enhanced plant growth in the area where the effects can be localized around the desired plant. In the case of seeds, the coating containing thiram and DCD provides an enhanced opportunity for seed germination, subsequent plant growth, and an increase in plant nutrient availability.

[0126] B. Methods for inhibiting / reducing nitrification or ammonia release or evolution in an affected area comprises applying a non-aqueous nitrification inhibitor composition or agricultural formulation containing thiram and DCD as active agents as described herein to the affected area. The affected area may be soil adjacent to a plant, a field, a pasture, a livestock or poultry confinement facility, pet litter, a manure collection zone, upright walls forming an enclosure, or a roof substantially covering the area, and in such cases the composition may be applied directly to the manure in the collection zone. The non-aqueous nitrification inhibitor composition is preferably applied at a level from about 0.005-3 gallons per ton of manure, in the form of an aqueous dispersion having a pH from about 1-5.

[0127] Nitrification in nature is a two-step oxidation process of ammonium (NHC) or ammonia (NH3) to nitrate (NO3 ) catalyzed by two ubiquitous bacterial groups. The first reaction is oxidation of ammonium to nitrite by ammonia-oxidizing bacteria (AOB) represented by the “Nitrosomonas” genus. The second reaction is oxidation of nitrite (NO2 ) to nitrate by nitrite-oxidizing bacteria (NOB), represented by the “Nitrobacter” genus. In some embodiments, the non-aqueous nitrification inhibitor composition and / or agricultural composition of the invention inhibits nitrification by inhibiting an ammonia-oxidizing bacteria (AOB). In some embodiments, the nonaqueous nitrification inhibitor composition and / or agricultural composition inhibits a bacteria of the Nitrosomonas genus. In some embodiments, the composition and / or agricultural composition inhibits Nitrosomonas europaea. In some embodiments, the nitrification (and / or ammonia-oxidizing bacteria (AOB)) is inhibited from about 10% to about 99%, from about 25% to about 85%, from about 50% to about 75% (or by at least about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, or by at least 98%).

[0128] In some embodiments, the nitrification (and / or ammonia-oxidizing bacteria (AOB)) is inhibited by from about 10% to about 85%, from about 25% to about 75%, from about 50% to about 75% more (or by at least about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, or by at least 85% more) compared to a DCD-containing composition with no thiram. Not to be bound by theory, but it is believed that combining thiram with DCD as disclosed herein produces a synergistic effect for the inhibition of nitrification. Therefore, in some embodiments, the oxygen consumption of the ammonia oxidizing bacteria in the presence of the disclosed non-aqueous nitrification inhibitor composition is reduced by about 1% to about 90%, by about 10% to about 90%, by about 20% to about 90%, by about 30% to about 90%, by about 40% to about 95%, by about 50% to about 90%, by about 55% to about 85%, by about 60% to about 80%, or by about 65% to about 80% (or by at least about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, or at least by about 90%).

[0129] Thus, in some embodiments, the nitrification (and / or ammonia-oxidizing bacteria (AOB)) is inhibited when an effective amount of the non-aqueous nitrification inhibitor composition of the invention comprises a synergistically effective amount of thiram and DCD such that nitrification is inhibited by from about 10% to about 80% compared to the sum of the individual nitrification inhibition of thiram or DCD by itself.

[0130] C. Methods for improving soil conditions selected from the group consisting of nitrification processes, urease activities, and combinations thereof, comprising the step of applying to soil an effective amount of a described non-aqueous nitrification inhibitor composition or agricultural formulation containing thiram and DCD as active agents as disclosed herein. In some embodiments, the composition is mixed with an ammoniacal solid, liquid, or gaseous fertilizer, and especially solid fertilizers; in the latter case, the composition is applied to the surface of the fertilizer as an aqueous dispersion followed by drying, so that the composition is present on the solid fertilizer as a dried residue. The composition is generally applied at a level of from about 0.01-10% by weight, based upon the total weight of the composition / fertilizer product taken as 100% by weight. Where the fertilizer is an aqueous liquid fertilizer, the composition is added thereto with mixing.

[0131] D. Methods for reducing Nitrogen (N) leaching and / or dentrification from the soil comprise contacting a non-aqueous nitrification inhibitor composition or an agricultural formulation thereof containing thiram and DCD as active agents as disclosed herein with soil. In some embodiments, the non-aqueous nitrification inhibitor composition or an agricultural formulation thereof is applied to the soil prior to emergence of a planted crop. In some embodiments, the non-aqueous nitrification inhibitor composition or an agricultural formulation thereof is applied to the soil post emergence of a planted crop. In some embodiments, the non-aqueous nitrification inhibitor composition or an agricultural formulation thereof is applied to the soil adjacent to the plant and / or at the base of the plant and / or in the root zone of the plant. In some embodiments, the methods disclosed herein reduce leaching and / or dentrification of Nitrogen (N) within the soil by at least about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or at least by 95% compared to soil that is untreated.

[0132] In some embodiments, the methods A, B, and D described herein involve treatment of the soil with the compositions or formulations directly or by action on their surroundings, by any customary treatment methods, for example, by side-dressing, placing, dropping, spreading, spraying, broadcasting, deep or sub-surface placement, localized placement, contact, band, hill, and row placement, knife-in, etc., and any other method. The soil may be in the area near or adjacent, i.e., vicinity, to a plant of interest, such as a crop plant.

[0133] In some embodiments, the methods A, B, C and D above comprise contacting a desired area with the disclosed non-aqueous nitrification inhibitor composition at a rate of about 100 g to about 120 g per acre of DCD. The nitrification inhibitor DCD can, in some embodiments, be in solution at an amount of about 0.5 lbs to about 4 lbs per U.S. gallon, or from about 1 lb to about 3 lbs / per U.S. gallon, or about 2 lbs per U.S. gallon. In some embodiments, the method includes contacting the desired area at a rate of about 0.5 to about 4 qt / A, or about 1 to about 2 qt / A. In some embodiments, exemplary plant / crop of methods A, B, and / or D include cereals (wheat, barley, oats, triticale, rye, and rice), maize, soya beans, potatoes, vegetables, peanuts, cotton, oilseed rape, tree nuts, turf, ornamentals, and / or fruit plants.

[0134] V. Articles of Manufacture

[0135] In another aspect, described herein are articles of manufacture, for example, a “kit,” containing the thiram and DCD. The kit comprises a container comprising thiram. The kit can further comprise a separate container comprising DCD. The kit advantageously can contain premeasured amounts, for example, in amounts set forth elsewhere herein, of each of the components such that, for example, a tank-mix can be easily prepared by the end-user by combining the contents of the kit in a solvent, such as water. The kit may further comprise a label or package insert, on or associated with the container. The term “package insert” is used to refer to instructions customarily included in agricultural packages, and can contain usage, application rates, and warnings concerning the use of the components. Suitable containers for inclusion in the kit include, for example, bottles, vials, syringes, blister pack, etc. The container may be formed from a variety of materials such as glass or plastic.

[0136] EXAMPLES

[0137] EXAMPLE 1: Preparation of a non-aqueous suspension concentrate composition (1)

[0138] A non-aqueous suspension concentrate composition is prepared by the following procedure. To 486.0 g of lubricating oils (petroleum), Cl 5-30, hydrotreated neutral oil-based add 15.0 g of Bentone 34, 235.0 g of water, 20.0 g of Igepal CO 430, 20.0 g of Genamin C100, 20.0 g of Rheosperse 3840, 104.0 g Thiram, and 100.0 g of Dicyandiamide powder. All percentages are weight present and based on the total weight of the formulation. Composition is mixed at room temperature and analyzed by HPLC for active concentration. See table below.

[0139] EXAMPLE 2: Preparation of a non-aqueous suspension concentrate composition (2)

[0140] The non-aqueous suspension concentrate composition is prepared by the following procedure. To 486.0 g of isoparaffinic hydrocarbon Exxsol D60 add 13.6 g of Bentone 34, 268.0 g of water, 23.7 g of Igepal CO 430, 23.7 g of Genamin C100, 15.0 g of Rheosperse 3840, 104.0 g Thiram, and 100.0 g of Dicyandiamide powder. All percentages are weight present and based on the total weight of the formulation. Composition is mixed at room temperature and analyzed by HPLC for active concentration.

Claims

THAT WHICH IS CLAIMED IS:

1. A non-aqueous nitrification inhibitor composition comprising: thiram; dicyandiamide (DCD); a stabilizer present in an amount of from about 1% to about 3% by weight; an emulsifier present in an amount of from about 1% to about 4% by weight; a surfactant present in an amount of from about 1% to about 3% by weight; a dispersant or wetting agent present in an amount of from about 1.5% to about 2.5% by weight, wherein thiram and DCD are present in a combined amount of from about 0.1 % to about 20 % by weight and all weights are based on the composition being 100%.

2. The composition of claim 1, wherein the non-aqueous nitrification inhibitor composition is in the form of a suspension concentrate.

3. The composition of claim 2, wherein thiram and DCD are in solid or solidified form dispersed throughout the concentrate.

4. The composition of claim 1, wherein thiram and DCD are present in synergistically effective amounts.

5. The composition of claim 1, wherein thiram and DCD are present in the composition at a weight ratio of from about 1 : 10 to about 10: 1 of thiram:DCD.

6. The composition of claim 1, wherein thiram is present in an amount of from about 5% to about 50% by weight based on the total weight of the composition.

7. The composition of claim 1, wherein DCD is present in an amount of from about 1% to about 15% by weight based on the total weight of the composition8. The composition of claim 1, wherein the amount of thiram is greater than the amount of DCD present in the composition.

9. The composition of claim 1, wherein the surfactant is a non-ionic surfactant selected from the group consisting of fatty alcohol ethoxylate, alkyl phenol ethoxylate and fatty acid alkoxylate.

10. The composition of claim 9, wherein the non-ionic surfactant is a fatty alcohol ethoxylate.

11. The composition of claim 10, wherein the fatty alcohol ethoxylate is Genamin C100.

12. The composition of claim 1, wherein the emulsifier is Igepal CO430.

13. The composition of claim 1, wherein the dispersant or wetting agent is Rheosperse.

14. The composition of claim 1, wherein the stabilizer is Bentone.

15. The composition of claim 3, wherein the solid of solidified from of DCD and thiram are granules.

16. The composition of claim 15, wherein the granules have a mean particle size (d50) between 0.01 mm and 0.1 mm.

17. The composition of claim 15, wherein the granules have a particle size ranging from about 150 to about 230 SGN.

18. The composition of claim 15, wherein the granules have a mesh size ranging from about 140 to about 635 US mesh.

19. The composition of claim 14, wherein the stabilizer is present in an amount of from about 1.3 % to about 1.7 % by weight, based on the total weight of the composition.

20. The composition of claim 12, wherein the emulsifier is present in an amount of from about 1.8 % to about 2.2% by weight, based on the total weight of the composition.

21. The composition of claim 9, wherein the surfactant is present in an amount of from about 1.8 % to about 2.2% by weight, based on the total weight of the composition.

22. An agricultural composition comprising the non-aqueous suspension concentrate composition of claim 1 and an agricultural product, wherein the agricultural product is selected from the group consisting of a fertilizer, agriculturally active compounds, seed, urease inhibitors, pesticides, herbicides, insecticides, nitrification inhibitors, and a combination thereof..

23. The agricultural composition of claim 22, wherein the agricultural product is a fertilizer.

24. The agricultural composition of claim 23, wherein the fertilizer is a liquid.

25. The agricultural composition of claim 24, wherein the liquid fertilizer contains UAN-32.

26. The agricultural composition of claim 22, wherein the agricultural product and the non-aqueous suspension concentrate composition are present in a ratio of about 1 : 1 by weight.

27. A method of fertilizing soil and / or improving plant / crop growth and / or health comprising applying a non-aqueous suspension concentrate composition of claim 1 or an agricultural composition of claim 22 to the soil.

28. The method of claim 27, wherein the non-aqueous suspension concentrate composition or agricultural composition is applied to the soil prior to emergence of a planted crop.

29. The method of claim 27, wherein the non-aqueous suspension concentrate composition or agricultural composition is applied to the soil adjacent to a plant, at the base of the plant, or in the root zone of the plant.

30. The method of claim 27, wherein the plant / crop is selected from the group consisting of: cereal, wheat, barley, oat, triticale, rye, rice, maize, soyabeans, potato, vegetable, peanuts, cotton, oilseed, grape, tree nuts, turf, ornamentals, and fruit plant.

31. The method of claim 30, wherein an effective amount of the composition comprises a synergistically effective amount of thiram and DCD such that nitrification is reduced by at least10% more compared to the sum of the individual nitrification inhibition of thiram and DCD by itself.

Images