Nitrogen stabilizer compositions and related methods

Abstract

The presently disclosed subject matter is directed to compositions containing antioxidants and optionally, chaotropic agents. Further described are uses of these compositions in agriculture to increase nutrient uptake and inhibit urease enzyme activity.

Description

[0001] NITROGEN STABILIZER COMPOSITIONS AND RELATED METHODS FIELD OF THE INVENTION

[0002] The presently disclosed subject matter is directed to compositions containing antioxidants and optionally chaotropic agents. Further described are uses of these compositions in agriculture to increase nutrient uptake and inhibit urease enzyme activity.

[0003] BACKGROUND

[0004] Nitrogen is an essential plant nutrient thought to be important for adequate and strong foliage. Urea provides a large nitrogen content and is the dominant nitrogen fertilizer. In the presence of soil moisture, natural or synthetic ureas are converted to ammonium ion, which is then available for plant uptake. Ammonium can be further converted by bacteria in soil to nitrate through a nitrification process. Nitrate is also available for plant uptake. However, the urea usage efficiency by plants is low. Although urea-containing fertilizers are currently being used on a scale of millions of tons per year globally and are the primary fertilizer being used, about 30% of the fertilizer being applied never reaches the intended target zone (roots).

[0005] In practice, nitrogen fertilizer is often just applied once at the beginning of the growing season. Typically, nitrogen fertilizer is formulated as dry granules, prills, or as fluids made up of urea alone or mixed with ammonium nitrate as UAN (a mixture containing urea, ammonium nitrate, and water). Urea is also present in animal manure. These forms of urea have a significant disadvantage in that they undergo rapid decomposition and generate ammonia gas when applied to soil. This is due to the presence of urease enzyme in soils, which reacts with urea to produce ammonium bicarbonate and ammonia. This general set of processes is known in the art as volatilization. Volatilization results in decreased efficiency of nitrogen fertilizer use, lower yields, plant symptoms of nitrogen deficiency, undesirable odors, and potentially harmful ammonia gas concentrations. In addition, the generated ammonia can also be converted to nitrate by bacteria in the soil, which is called nitrification. Excessive nitrate can be converted into nitric oxide or nitrous oxide by certain types of bacteria in the soil, which is called denitrification.

[0006] Urease enzyme inhibitors have been developed that are capable of delaying degradation of nitrogen fertilizer, thereby reducing losses from nitrogenous degradation products that would otherwise occur in the absence of these inhibitors. The use of urease enzyme inhibitors in combination with nitrogen fertilizers tends to increase the amount of time the nitrogen source remains in the soil and available for absorption by the plants, which then increases the effectiveness of the fertilizer, positively impacting crop yield and quality. However, problems relating to cost, safety, convenience, and stability have limited the use of these types of inhibitors. Currently, the Agrotain® line of products contain urease enzyme inhibitor N-(n-butyl)thiophosphoric triamide (NBPT) and are often used for improving nitrogen fertilizer availability and minimize ammonia volatilization. However, products such as Agrotain® exhibit various drawbacks including its chemical stability, and potential to interfere with nitrogen uptake and assimilation in target crops (Zanin L, Tomasi N, Zamboni A, Varanini Z and Pinton R (2015) The Urease Inhibitor NBPT Negatively Affects DUR3-mediated Uptake and Assimilation of Urea in Maize Roots. Front. Plant Sci. 6: 1007; Zanin L, Venuti S, Tomasi N, Zamboni A, De Brito Francisco RM, Varanini Z and Pinton R (2016) Short-Term Treatment with the Urease Inhibitor N-(n-Butyl) Thiophosphoric Triamide (NBPT) Alters Urea Assimilation and Modulates Transcriptional Profiles of Genes Involved in Primary and Secondary Metabolism in Maize Seedlings. Front. Plant Sci. 7:845). Therefore, finding urease inhibitors that are stable and safe for the environment and animals as well as non-toxic to crops would be highly desirable.

[0007] Thus, despite the continuous ongoing research efforts to improve upon existing products, there still remains a significant need in the art for developing better methods for urease inhibition and compositions that contain urease inhibitors which provide good stability while being able to efficiently control enzyme-induced urea decomposition.

[0008] SUMMARY OF THE INVENTION

[0009] The current disclosure is directed to the development of urease inhibitor compositions containing antioxidants alone or in combination with a chaotropic agent(s). Such urease inhibitor compositions as disclosed herein can help to improve nitrogen fertilizer use efficacy, particularly of solid urea-containing fertilizers.

[0010] As such, the first aspect of the current disclosure is directed to a composition comprising an antioxidant and a chaotropic agent. In some embodiments, the antioxidant is selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butyl-phenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof. In some embodiments, the chaotropic agent is selected from the group consisting of magnesium chloride, sodium perchlorate, sodium bromide, sodium trifluoroacetate, sodium thiocyanate, sodium trichloroacetate, dodine, guanidinum chloride, lithium perchlorate, lithium acetate, monoethanolamine borate, phenol, sodium dodecyl sulfate, thiourea, urea, guanidinium thiocyanate, and combinations thereof.

[0011] Another aspect of the current disclosure relates to an agricultural product comprising a granule or prill containing urea and a urease inhibitor component, wherein the urease inhibitor component is an antioxidant or a urease inhibitor composition as disclosed herein, and wherein the antioxidant selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butyl-phenol (DBP), 2,6-di-tert-butyl- p-benzoquinone (BHT-Q), and combinations thereof. In some embodiments, the urease inhibitor component is pre-infused into the granule or prill.

[0012] Another aspect of the current disclosure is directed to a method of making a granule or prill containing urea coated with a composition or formulation as disclosed herein, the method comprising obtaining a urea containing granule or prill, and spraying the surface of the urea-containing granule or prill with the disclosed composition or formulation.

[0013] Another method of making a granule or prill containing urea and the composition as disclosed herein comprises obtaining a urea melt, contacting the urea melt with the composition of any one of claims 1-16 to obtain a mixture and cooling the mixture to obtain the granule or prill.

[0014] BRIEF DESCRIPTION OF THE DRAWINGS

[0015] FIG. 1A is a graph showing an XL scatter plot of the NH3 evolution for Treatment 3 v Treatment 1 and Treatment 2.

[0016] FIG. IB is a graph showing an XL scatter plot of the NH3 evolution for Treatment 4 v Treatment 1 and Treatment 2.

[0017] FIG. 1C is a graph showing an XL scatter plot of the NH3 evolution for Treatment 5 v Treatment 1 and Treatment 2.

[0018] FIG. ID is a graph showing an XL scatter plot of the NH3 evolution for Treatment 6 v Treatment 1 and Treatment 2.

[0019] FIG. 2A is a graph showing an XL scatter plot of the NH3 evolution for Treatment 3 v Treatment 2 less Treatment 1.

[0020] FIG. 2B is a graph showing an XL scatter plot of the NH3 evolution for Treatment 4 v Treatment 2 less Treatment 1. FIG. 2C is a graph showing an XL scatter plot of the NFL evolution for Treatment 5 v Treatment 2 less Treatment 1.

[0021] FIG. 2D is a graph showing an XL scatter plot of the NFL evolution for Treatment 6 v Treatment 2 less Treatment 1.

[0022] FIG. 3A is a graph showing an XL scatter plot of the NFL evolution for Treatment 10 v Treatment 7 and Treatment 9.

[0023] FIG. 3B is a graph showing an XL scatter plot of the NFL evolution for Treatment 11 v Treatment 7 and Treatment 9.

[0024] FIG. 3C is a graph showing an XL scatter plot of the NFL evolution for Treatment 12 v Treatment 7 and Treatment 9.

[0025] FIG. 3D is a graph showing an XL scatter plot of the NFL evolution for Treatment 13 v Treatment 7 and Treatment 9.

[0026] FIG. 3E is a graph showing an XL scatter plot of the NFL evolution for Treatment 143 v Treatment 7 and Treatment 9.

[0027] FIG. 4A is a graph showing an XL scatter plot of the NFL evolution for Treatment 9 and Treatment 10 less Treatment 7.

[0028] FIG. 4B is a graph showing an XL scatter plot of the NFL evolution for Treatment 9 and Treatment 11 less Treatment 7.

[0029] FIG. 4C is a graph showing an XL scatter plot of the NFL evolution for Treatment 9 and Treatment 12 less Treatment 7.

[0030] FIG. 4D is a graph showing an XL scatter plot of the NFL evolution for Treatment 9 and Treatment 13 less Treatment 7.

[0031] FIG. 4E is a graph showing an XL scatter plot of the NFL evolution for Treatment 9 and Treatment 14 less Treatment 7.

[0032] DETAILED DESCRIPTION

[0033] 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. Tn 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.

[0034] As already mentioned above, urea (particularly solid urea) is the most widely used nitrogen fertilizer globally. The urea granule is usually produced through a granulation process or prilling process. Since most of the urea is applied to the soil early in the growing season, it is subjected to both above ground and below ground losses. The above ground loss mainly refers to the ammonia emission after urea is hydrolyzed in the soil by urease enzyme. The below ground loss mainly refers to the nitrate leaching through ground water system after ammonium goes through further nitrification processes by soil microorganisms.

[0035] In current agricultural practices, to control the hydrolysis of urea and the nitrification process, urease inhibitors and nitrification inhibitors are used as surface coating options onto the urea granule products and are applied at agricultural retailer sites when the urea granules are ready to be distributed to the field.

[0036] Only one product on the market in the United States, called SuperU by Koch, has the urease inhibitor (NBPT) pre-infused in the urea granule through the urea remelt and infusion process (US 2015 / 0101379). Since most of the urease inhibitor products are liquid products applied as surface coating on urea granules, urea pre-infused with urease inhibitors provide growers a pretreated urea option. This is a great idea because it offers convenience and cost savings to the growers. However, NBPT is costly to make and susceptible to decomposition during storage or upon heating, especially in a hygroscopic environment.

[0037] The current disclosure describes a novel, chemically stable, and environmentally friendly composition and method for pre-infused (or pretreat) urea applications. The composition generally includes an antioxidant urease inhibitor and optionally one or more chaotropic agent(s). These compositions can be formulated to be integrated into the urea manufacturing process to produce urea granules with pre-infused urease inhibitors. Furthermore, the compositions disclosed herein can also be formulated as a liquid to be used for surface-coating solid urea at the time of urea applications to agricultural fields.

[0038] The compositions and methods described advantageously herein, have been shown to provide desirable properties for the use of such urease inhibitors in agriculture, particularly when formulated together with urea-containing fertilizers. Specifically, when combining antioxidants, such as tert-butylhydroquinone (tBHQ), with chaotropic agents, beneficial properties were observed such as, but not limited to, extended thermal / chemical stability, increased shelflife, ease of handling, extended / prolonged effect of urease inhibition, as well as acceptable environmental and toxicology profiles. In addition, combining these disclosed compositions with urea-containing fertilizers afforded agricultural products with improved nitrogen utilization efficacy compared to commercially available products. Such observations were surprising and unexpected based on the current general knowledge in the art.

[0039] Thus, the compositions disclosed herein not only contribute to an increased availability of plant nutrients by inhibiting urease enzyme activity, but also extend the longevity of their performance as being efficient urease inhibitors due to their beneficial properties mentioned above.

[0040] I. Definitions

[0041] As used herein, the term “urease inhibitor” refers to a property of a compound to inhibit the activity of urease enzymes. The inhibition can be quantified as described elsewhere herein.

[0042] As used herein, the term “thermal stability” refers to the stability of a substance when exposed to a thermal stimuli over a given period of time. Examples of thermal stimuli include, but are not limited to, heat generated from an electrical source and / or heat generated from the sun.

[0043] As used herein, the term “chemical stability” refers to the resistance of a substance to structurally change when exposed to an external action such as air (which can lead to oxidation), light (e.g., sunlight), moisture / humidity (from water), heat (from the sun), and / or chemical agents. Exemplary chemical agents include, but are not limited to, any organic or inorganic substance that can degrade the structural integrity of the compound of interest (e.g., tBHQ).

[0044] As used herein, the term “antioxidant” refers to compounds that inhibit oxidation, a chemical reaction that can produce free radicals.

[0045] As used herein, the term “chaotropic agent” refers to a molecule in water solution that can disrupt the hydrogen bonding network between water molecules (i.e., exerts chaotropic activity). This has an effect on the stability of the native state of other molecules in the solution, mainly macromolecules (proteins, nucleic acids) by weakening the hydrophobic effect. For example, a chaotropic agent reduces the amount of order in the structure of a protein formed by water molecules, both in the bulk and the hydration shells around hydrophobic amino acids, and may cause its denaturation.

[0046] Thus, chaotropic agents are substances which disrupt the structure of, and denatures, macromolecules such as proteins and nucleic acids (e.g., DNA and RNA). Chaotropic solutes increase the entropy of the system by interfering with intermolecular interactions mediated by non-covalent forces such as hydrogen bonds, van der Waals forces, and hydrophobic effects. Macromolecular structure and function is dependent on the net effect of these forces (see protein folding), therefore it follows that an increase in chaotropic solutes in a biological system will denature macromolecules, reduce enzymatic activity and induce stress on a cell (i.e., a cell will have to synthesize stress protectants). Tertiary protein folding is dependent on hydrophobic forces from amino acids throughout the sequence of the protein. Chaotropic solutes decrease the net hydrophobic effect of hydrophobic regions because of a disordering of water molecules adjacent to the protein. This solubilizes the hydrophobic region in the solution, thereby denaturing the protein. This is also directly applicable to the hydrophobic region in lipid bilayers; if a critical concentration of a chaotropic solute is reached (in the hydrophobic region of the bilayer), then membrane integrity will be compromised and the cell will lyse.^

[0047] As used herein, the term “effective amount” refers to an amount of a urease inhibitor composition and / or the amount of each component in the urease inhibitor composition (i.e., tBHQ and optionally, an additive component), which is sufficient for achieving urease 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.

[0048] As used herein, the term “micronutrient” is to be understood as nutrients essential to plant growth and health that are only needed in very small quantities. A non-limiting list of micronutrients required by plants includes zinc (Zn), iron (Fe), manganese (Mn), copper (Cu), boron (B), molybdenum (Mo), and chlorine (Cl).

[0049] As used herein, the term “Size Guide Number” (SGN) refers to the diameter, expressed as millimeters x 100, of the fertilizer granules based on the median (or midpoint) within the batch. It means that half of the fertilizer granules are larger than the set SGN and half are smaller. This is determined by passing the fertilizer through various sieves and using the amounts retained by each to calculate the SGN. For example, a fertilizer of SGN 250 will have 50% of its particles retained on or around a sieve with a 2.5 millimeter opening.

[0050] As used herein, the term “median” refers to the value where half of the particle population resides above this point, and half of the particles reside below this point and are usually reported in millimeters (mm). For a particle size distribution, the median is called the dso of a particle.

[0051] As used herein, the term “uniformity index” (UI) refers to a variable that expresses relative particle size variation. UI values within the range of about 40-60 indicate that the particles are uniform in size. The larger the UI value, the more uniform in particle size variation of a product. Values outside this range indicate large variability in particle size distribution. UI is the ratio of a larger (d95) to smaller (dlO) granule for a specific granular composition multiplied by 100: formula to calculate UI is = D10 / D95 X 100, wherein DIO = particle diameter (mm) corresponding to 10% passing and D95 = particle diameter (mm) corresponding to 95% passing. For example, the meaning of a product with a UI of 50 = average small particle (.80 mm) is half the size of the average large particle (1.6 mm). A product with varying particle sizes and density can result in inconsistent distribution of product delivering inconsistent results.

[0052] As used herein, the term “mesh size” refers to the U.S. Mesh Size (or U.S. Sieve Size) that is defined as the number of openings in one square inch of a screen. For example, a 36 mesh screen will have 36 openings, while a 150 mesh screen will have 150 openings. Since the size of screen (one square inch) is constant, the higher the mesh number, the smaller the screen opening and the smaller the particle that will pass through. Generally, U.S. Mesh Size is measured using screens down to a 325 mesh (325 openings in one square inch).

[0053] Sometimes the mesh size of a product is noted with either a minus (-) or plus (+) sign. These signs indicate that the particles are either all smaller than (-) or all larger than (+) the mesh size. For example, a product identified as 100 mesh would contain only particles that passed through a 100 mesh screen. A +100 grade would contain particles that did not pass through a 100 mesh screen. When a grade of product is noted with a dash or a slash, it indicates that the product has particles contained within the two mesh sizes. For example, a 30 / 70 or 30-70 grade would only have particles that are smaller than 30 mesh and larger than 70 mesh. As used herein, the term “particle density” refers to the mass to volume ratio of particles and / or granules that is reported as lbs / ft3or kg / m3. Unlike bulk density, particle density does not include the space between individual particles, but rather a measurement of the particle density itself.

[0054] 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 nonliving 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).

[0055] 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.

[0056] 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, and rabbits, and guano from seabirds and bats. The application rates of animal manure when used as fertilizer depend highly 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.

[0057] As used herein, the term “seed” comprises seeds of all types, such as, for example, corns, seeds, fruits, tubers, seedlings, and similar forms. The seed used can be the seed of the useful plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] Additional definitions may follow below.

[0062] II. Composition The presently disclosed subject matter relates to a urease inhibitor composition comprising an antioxidant. As already mentioned above, these urease inhibitor compositions can exhibit desirable properties such as increased chemical / thermal stability, increased shelf life, reduced volatility, reduced application rate, ease of handling, extended / prolonged effect of urease inhibition, as well as excellent environmental and toxicology profdes, all of which generally contribute to an increased performance in the field.

[0063] In some embodiments, the urease inhibitor composition is in a liquid form. For example, in such embodiments, the urease inhibitor composition may further comprise an organic solvent. In such embodiments where an organic solvent is present, the antioxidant cannot be tBHQ. The amount and type or organic solvent is described in more detail below.

[0064] In some embodiments, the urease inhibitor composition is in the form of a solid. For example, in some embodiments, the urease inhibitor composition is in the form of a powder. In such embodiments, the urease inhibitor composition is selected from a coarse powder, a moderately coarse powder, a moderately fine powder, a fine powder and a very fine powder. In some embodiments, the particle size of the powder composition is from about 10 pm to about 1,700 pm, from about 10 pm to about 1,200 pm, from about 10 pm to about 1,000 pm, from about 10 pm to about 710 pm, from about 10 pm to about 355 pm, from about 10 pm to about 180 pm, from about 10 pm to about 150 pm, from about 10 pm to about 125 pm, from about 10 pm to about 90 pm, from about 10 pm to about 75 pm, from about 10 pm to about 50 pm, or from about 10 pm to about 25 pm. In some embodiments, the urease inhibitor composition is a coarse powder with an average particle size of from about 355 pm to about 1,700 pm. In some embodiments, the urease inhibitor composition is a moderately coarse powder with an average particle size (dso) of from about 355 pm to about 710 pm. In some embodiments, the urease inhibitor composition is a moderately fine powder with an average particle size (dso) of from about 180 pm to about 355 pm. In some embodiments, the urease inhibitor composition is a fine powder with an average particle size of from about 125 pm to about 180 pm. In some embodiments, the urease inhibitor composition is a very fine powder with an average particle size of less than about 125 pm.

[0065] The average particle size (dso) of the powder can vary. In some embodiments, the average particle size is less than about 1,000 pm, less than about 900 pm, less than about 800 pm, less than about 700 pm, less than about 600 pm, less than about 500 pm, less than about 400 pm, less than about 300 pm, less than about 200 pm, less than about 100 pm, or less than about 50 pm. The powder flowability of the urease inhibitor composition can vary. The flowability of a powder is characterized by its Carr-Index. In some embodiments, Carr-index of the urease inhibitor composition ranges from about 0% to about 50%, from about 0% to about 40%, from about 0% to about 37%, from about 0% to about 31%, from about 0% to about 25%, from about 0% to about 20%, from about 0% to about 15%, or from about 0% to about 10%. In some embodiments, the urease inhibitor composition as a Carr-index of from about 0% to about 10%, from about 11% to about 15%, from about 16% to about 20%, or from about 21-25%.

[0066] The bulk density of the powder urease inhibitor composition can vary. In some embodiments, the bulk density of the powder is from about 0.01 g / mL to about 2 g / mL, from about 0.1 g / mL to about 1.5 g / mL, from about 0.1 g / mL to about 1.25 g / mL, from about 0.1 g / mL to about 1.0 g / mL, from about 0.1 g / mL to about 0.7 g / mL, from about 0.1 g / mL to about 0.50 g / mL, or from about 0.1 g / mL to about 0.25 g / mL.

[0067] The moisture content of the powder urease inhibitor composition can vary. In some embodiments, the moisture content of the powder is from about 0% to about 40%, from about 0% to about 35%, from about 0% to about 30%, from about 0% to about 25%, from about 0% to about 20%, from about 0% to about 15%, from about 0% to about 10%, from about 0% to about 5%, or from about 0% to about 2.5%. In some embodiments, the moisture content of the powder is less than about 40%, less than about 30%, less than about 20%, less than about 15%, less than about 10%, less than about 8%, less than about 5%, less than about 2.5%, less than about 1%, or less than about 0.5%.

[0068] In some embodiments, the urease inhibitor composition comprises an antioxidant and a chaotropic agent. The relative amount of antioxidant and chaotropic agent present in the urease inhibitor composition can vary. In some embodiments, the amount of antioxidant and chaotropic agent present in the urease inhibitor composition ranges from about 1 : 1000 to about 1000: 1, from about 1:500 to about 500: 1, from about 1 :250 to about 250: 1, from about 1 : 150 to about 150: 1, from about 1 : 100 to about 100: 1, from about 1 :75 to about 75: 1, from about 1 :50 to about 50: 1, from about 1 :25 to about 25: 1, from about 1 :15 to about 15: 1, from about 1 :10 to about 10: 1, from about 1 :8 to about 8: 1, from about 1 :5 to about 5: 1, from about 1 :3 to about 3:1, or from about 1 :2 to about 2: 1 molar ratio of antioxidant to chaotropic agent. In some embodiments, the antioxidant and chaotropic agent are present in the urease inhibitor composition in a 1 : 1 molar ratio. The antioxidants, chaotropic agents, and / or organic solvents that can be present in the disclosed urease inhibitor composition is described in more detail below.

[0069] A. Antioxidant

[0070] The urease inhibitor compositions disclosed herein comprise an antioxidant. Exemplary antioxidants include, but are not limited to, tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butyl-phenol (DBP), 2,6-di-tert-butyl-p- benzoquinone (BHT-Q), and combinations thereof. In some embodiments, the antioxidant is tert-butylhydroquinone (tBHQ). Tert-butylhydroquinone (tBHQ, tertiary butylhydroquinone) is a synthetic aromatic organic compound and is a derivative of hydroquinone (which is a type of phenol), substituted with a / c / v-butyl group and has the following chemical structure:

[0071] TBHQ is primarily used in foods as a preservative for unsaturated vegetable oils and many edible animal fats, where it acts as an antioxidant. In addition, tBHQ has been used in other applications such as: (a) in perfumery, where it is used as a fixative to lower the evaporation rate and improve stability; (b) in industry as a stabilizer to inhibit autopolymerization of organic peroxides; (c) in fuels as an antioxidant, e.g., in biodiesel; and (d) as an additive to varnishes, lacquers, resins, and oil-field additives.

[0072] However, its effects on urease inhibition, particularly urease inhibition in soil, has not been previously disclosed. It was therefore unexpected and surprising to find that antioxidants, such as tert-butylhydroquinone, exhibit strong urease enzyme inhibitory properties when exposed to soil either alone or together with a chaotropic agent and, furthermore, in combination with fertilizer, particularly a urea-containing fertilizer.

[0073] The amount of antioxidant present in the urease inhibitor composition can vary. For example, in some embodiments, the amount of antioxidant ranges from about 0.001% to about 99%, from about 0.01% to about 90%, from about 0.1% to about 85%, from about 1% to about 80%, from about 10% to about 75%, from about 15% to about 70%, from about 20% to about 65%, from about 25% to about 60%, from about 30% to about 55%, from about 35% to about 50%, or from about 40% to about 45% by weight based on the total weight of the urease inhibitor composition. In some embodiments, the amount of antioxidant present in the urease inhibitor composition is less than about 90%, about 85%, about 80%, about 75%, about 70%, about 65%, about 50%, about 45%, about 40%, about 35%, about 30%, about 25%, about 20%, about 15%, about 10%, about 5%, or less than about 1% by weight based on the total weight of the urease inhibitor composition.

[0074] B. Chaotropic Agent

[0075] The compositions disclosed herein can also comprise a chaotropic agent. Exemplary chaotropic agents include, but are not limited to, magnesium chloride, guanidinium chloride, lithium perchlorate, lithium acetate, monoethanolamine borate, phenol, sodium dodecyl sulfate, thiourea, urea, sodium perchlorate, dodine, sodium bromide, sodium trifluoroacetate, sodium thiocyanate, sodium trichloroacetate, and combinations thereof. In some embodiments, the chaotropic agent is selected from the group consisting of magnesium chloride, guanidinium thiocyanate, guanidinium chloride, thiourea, monoethanolamine borate, and a combination thereof.

[0076] The amount of the chaotropic agent present in the urease inhibitor composition can vary. For example, in some embodiments, the amount of the chaotropic agent ranges from about 0.001% to about 99%, from about 0.01% to about 90%, from about 0.1% to about 85%, from about 1% to about 80%, from about 10% to about 75%, from about 15% to about 70%, from about 20% to about 65%, from about 25% to about 60%, from about 30% to about 55%, from about 35% to about 50%, or from about 40% to about 45% by weight based on the total weight of the urease inhibitor composition. In some embodiments, the amount of chaotropic agent present in the urease inhibitor composition is less than about 90%, about 85%, about 80%, about 75%, about 70%, about 65%, about 50%, about 45%, about 40%, about 35%, about 30%, about 25%, about 20%, about 15%, about 10%, about 5% or less than about 1% by weight based on the total weight of the urease inhibitor composition.

[0077] C. Organic Solvent

[0078] As already mentioned above, the urease inhibitor composition disclosed herein can further comprise an organic solvent. Such liquid urease inhibitor compositions must comprise a chaotropic agent when the antioxidant is tBHQ. In some embodiments, the organic solvent is one or more polar organic solvent(s). In some embodiments, the one or more polar organic solvent(s) are EPA approved. EPA-approved solvents are those that are found in the electronic code of federal regulations, for example in Title 40, Chapter I, Subchapter E, Part 180. EPA-approved solvents include, but are not limited to, the solvents listed in Table 1.

[0079] Table 1. EPA-approved solvents

[0080]

[0081]

[0082] In some embodiments, the organic solvent is selected from a sulfone, a sulfoxide, an aromatic solvent, a halogenated solvent, a glycol-based solvent, a fatty acid-based solvent, an acetate-containing solvent, a ketone-containing solvent, an ether polyol-containing solvent, an amide-containing solvent, and combinations thereof. In some embodiments, the organic solvent is environmentally friendly, such as a green solvent, a safe solvent, or a combination thereof.

[0083] In some embodiments, the one or more organic solvent(s) are all relatively free of water. In some embodiments, the organic solvent contains less than about 10% w / w, about 9% w / w, about 8% w / w, about 7% w / w, about 6% w / w, about 5% w / w, about 4% w / w, about 3% w / w, about 2% w / w, about 1% w / w, about 0.9% w / w, about 0.8% w / w, about 0.7% w / w, about 0.6% w / w, about 0.5% w / w, about 0.4% w / w, about 0.3% w / w, or less than about 0.1% w / w of water based on the total weight of the solvent. In some embodiments, the organic solvent is a liquid at 20°C.

[0084] In some embodiments, the organic solvent is a sulfone. A sulfone is a solvent that contains a sulfonyl functional group attached to two carbon atoms and is represented by the general structure R’-S(=O)2-R”, wherein both R groups contain carbon atoms. A sulfone solvent can be, but is not limited to, sulfolane, methyl sulfolane (3-methyl sulfolane), dimethyl sulfone, or a combination thereof. In some embodiments, the organic solvent is a sulfoxide. A sulfoxide solvent contains a sulfinyl (SO) functional group attached to two carbon atoms and is generally represented by R’-S(=O)-R”, wherein both R groups contain carbon atoms. A sulfoxide solvent can be, but is not limited to, dimethyl sulfoxide.

[0085] In some embodiments, the organic solvent is an ether polyol. An ether polyol contains multiple hydroxyl groups. An ether-polyol solvent can be, but is not limited to, polyethylene glycols, polypropylene glycols, polyalkylene glycols, and related compounds. In some embodiments, the polyethylene glycol has two terminal alcohols (e.g., polyethylene glycol 3350). Exemplary polyethylene glycols include, but are not limited to, diethylene glycol, triethylene glycol, or a combination thereof. Exemplary polypropylene glycols include, but are not limited to, dipropylene glycol, tripropylene glycol, or a combination thereof. In some embodiments, a polypropylene glycol has three terminal alcohols. Exemplary polypropylene glycols having three terminal alcohols, known as propoxylated glycerol, include, but are not limited to, Dow PT250 (which is a glyceryl ether polymer containing three terminal hydroxyl groups with a molecular weight of 250) and Dow PT700 (which is a glyceryl ether polymer containing three terminal hydroxyl groups with a molecular weight of 700). In some embodiments, ether polyol comprises a polyethylene or a polypropylene glycol in the molecular weight range of between about 200 and about 10,000 Da. In some embodiments, one or more of the hydroxyl groups present in the ether polyol is modified. For example, in some embodiments, one or more of the hydroxyl groups present in the ether polyol are alkylated and / or esterified. Exemplary modified ether polyols include, but are not limited to, triacetin, n-butyl ether of diethylene glycol, ethyl ether of di ethylene glycol, methyl ether of diethylene glycol, acetate of the ethyl ether of dipropylene glycol, or a combination thereof.

[0086] In some embodiments, the organic solvent is a glycol-based solvent. A glycol is an alcohol that contains two hydroxyl (-OH) groups that are attached to different carbon atoms (e.g., terminal carbon atoms). Exemplary glycol-based solvents include, but should not be limited to, ethylene glycol and / or propane 1,2,3 triol.

[0087] In some embodiments, the organic solvent is a fatty acid-based solvent. In general, a fatty acid is characterized as a compound with a carboylic acid and an aliphatic chain containing multiple carbon atoms, which can be saturated or unsaturated. In some embodiments, the fatty acid contains between 3 to about 20 carbon atoms. Example of fatty acid-based solvents include, but are not limited to, a dialkyl amide of a fatty acid (e.g., a dimethylamide). Examples of a dimethylamide of a fatty acid include, but are not limited to, a dimethyl amide of a caprylic acid, a dimethyl amide of a Cs-Cio fatty acid (Agnique AMD810), a dimethyl lactamide (Agnique AMD3L), or a combination thereof.

[0088] In some embodiments, the organic solvent is a ketone-containing solvent, which can be any solvent containing a carbonyl functional group (C=O). Examples of ketone-containing solvent include, but are not limited to, isophorone, trimethylcyclohexanone, or a combination thereof.

[0089] In some embodiments, the organic solvent is an acetate-containing solvent. Examples of acetate-containing solvents include, but are not limited to, acetate, hexyl acetate, heptyl acetate, or a combination thereof.

[0090] In some embodiments, the organic solvent is an amide-containing solvent, which can be any solvent containing and amide functionality (-NR’C(=O)R”; wherein R is an alkyl group). Examples of amide-containing solvents include, but are not limited to, N-methyl-2-pyrrolidone (NMP), N,N’ -dimethylpropyleneurea (DMPU), Rhodiasolv ADMA10 (CAS Reg. No. 14433-76- 2; N,N-dimethyloctanamide), dimethylormamide (DMF), Rhodiasolv ADMA810 (CAS Reg. No. 1118-92-9 / 14433-76-2; blend of N,N-Dimethyloctanamide and N,N-diemthyldecanamide), Rhodiasolv PolarClean (CAS Reg. No. 1174627-68-9; methyl 5 (dimethylamino)-2 methyl 5 oxopentanoate), or a combination thereof.

[0091] In some embodiments, the organic solvent is a halogenated solvent, which can be any solvent containing one or more halogens (i.e., chlorine, bromine, iodine, and fluorine). In some embodiments, the halogenated solvent is a halogenated aromatic hydrocarbon. An example of a halogenated aromatic hydrocarbon is chlorobenzene. In some embodiments, the halogenated solvent is a halogenated aliphatic hydrocarbon. An example of a halogenated aliphatic hydrocarbon is 1,1,1 -tri chloroethane.

[0092] In some embodiments, the organic solvent is an aromatic solvent. In some embodiments, the aromatic solvent is an aromatic hydrocarbon. Exemplary aromatic hydrocarbons include, but are not limited to, benzene, naphthalene, or a combination thereof. In some embodiments, the aromatic hydrocarbon is substituted. Examples of substituted aromatic hydrocarbons include, but are not limited to, alkyl-substituted benzenes and / or alkyl-substituted naphthalenes. Examples of alkyl-substituted benzenes include xylene(s), toluene, propylbenzene, or a combination thereof. In some embodiments, the organic solvent comprises xylene(s). In some embodiments, the aromatic hydrocarbon is a mixture of substituted and unsubstituted aromatic hydrocarbons, such as, but not limited to a mixture of naphthenic and alkyl substituted naphthalene.

[0093] In some embodiments, the aromatic solvent is a mixture of hydrocarbons. For example, in some embodiments, the aromatic solvent is aromatic 100, a solvent containing Naphtha (CAS Reg. No. 64742-95-6), which is a combination of hydrocarbons obtained from distillation of aromatic streams consisting predominantly of aromatic hydrocarbons Cs through Cio), or aromatic 200, a solvent containing a mixture of: aromatic hydrocarbon (C11-C14) present in 50-85% by weight; naphthalene (CAS Reg. No. 91-20-3) present in 5-20% by weight; aromatic hydrocarbon (Cio) not including naphthalene present in 5-15% by weight; and aromatic hydrocarbon (C15-C16) present in 5-15% by weight based on the total weight of the aromatic 200 composition. In some embodiments, the aromatic hydrocarbon is a mixture of aromatic 100 and aromatic 200.

[0094] In some embodiments, the organic solvent is selected from the group consisting of a sulfone, a sulfoxide, an amide-containing solvent, or a combination thereof. In some embodiments, the organic solvent is selected from the group consisting of DMSO, DMF, methylated seed oils, dimethyl sulfoxide, DMPU, NMP, or a combination thereof. In some embodiments, the organic solvent is a single solvent of the above-mentioned solvents. In some embodiments, the organic solvent comprises one or more of the above-mentioned organic solvents. The amount of organic solvent in the urease inhibitor composition can vary. For example, in some embodiments, the amount of the organic solvent ranges from about from about 0.001% to about 99%, from about 0.01% to about 90%, from about 0.1% to about 85%, from about 1% to about 80%, from about 10% to about 75%, from about 15% to about 70%, from about 20% to about 65%, from about 25% to about 60%, from about 30% to about 55%, from about 35% to about 50%, or from about 40% to about 45% by weight based on the total weight of the urease inhibitor composition. In some embodiments, the amount of organic solvent present in the urease inhibitor composition is less than about 90%, about 85%, about 80%, about 75%, about 70%, about 65%, about 50%, about 45%, about 40%, about 35%, about 30%, about 25%, about 20%, about 15%, about 10%, about 5% or less than about 1% by weight based on the total weight of the urease inhibitor composition.

[0095] III. Formulations

[0096] The disclosed urease inhibitor composition can be used in its unmodified original form (e g., neat) or can be formulated into a formulation comprising one or more auxiliaries selected from extenders, carriers, solvents, surfactants (surface-active agents), stabilizers, anti-foaming agents, anti-freezing agents, preservatives, antioxidants, viscosity modifiers, suspending agents, light absorbers, corrosion inhibitors, fragrances, pH-modifying substances, glidants, lubricants, plasticisers, complexing agents, colorants, thickeners, solid adherents, fillers, wetting agents, dispersing agents, lubricants, anticaking agents, deformers, and diluents. Such auxiliaries are known in the art and are commercially available. Their use in the formulation of the disclosed urease inhibitor compositions will be apparent to a person skilled in the art.

[0097] The amount of urease inhibitor composition present in the formulation as disclosed herein can vary. In some embodiments, the urease inhibitor composition is present in an amount ranging from about 0.1% to about 99.9%, from about 10% to about 90%, from about 20% to about 80%, from about 30% to about 70%, or from about 40% to about 60% by weight based on the total weight of the formulation. In some embodiments, the urease inhibitor composition is present in an amount ranging from about 0.1% to about 75%, from about 1% to about 70%, from about 10% to about 60%, from about 20% to about 50%, or from about 25% to about 40% by weight based on the total weight of the formulation. In some embodiments, the urease inhibitor composition is present in an amount ranging from about 10% to about 99.9%, from about 20% to about 95%, from about 30% to about 90%, from about 35% to about 80%, from about 40% to about 75%, or from about 50% to about 70% by weight based on the total weight of the formulation.

[0098] In some embodiments, the formulation contains one or more auxiliaries selected from carriers and / or solvents. Such formulations are said to be in a liquid form and do not comprise tBHQ. Exemplary carriers and / or solvent that can be used in liquid urease inhibitor formulations include, but are not limited to, water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1, 2-dichloropropane, diethanolamine, p-di ethylbenzene, di ethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, di ethylene glycol methyl ether, A,A-dimethylformamide, dimethyl sulfoxide, 1, 4-di oxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2 ethylhexanol, ethylene carbonate, 1, 1, 1 -tri chloroethane, 2-heptanone, alpha-pinene, d limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobomyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, a-linolenic acid, y- linolenic acid, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl linoleate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, A / - methyl-2-pyrrolidone and the like.

[0099] The amount of the liquid carrier(s) and / or solvent(s) present in a liquid formulation can vary. In some embodiments, the liquid carrier(s) and / or solvent(s) are present in an amount ranging from about 0.1% to about 99.9%, from about 10% to about 90%, from about 20% to about 80%, from about 30% to about 70%, or from about 40% to about 60% by weight based on the total weight of the liquid formulation. In some embodiments, the carrier(s) and / or solvent(s) are present in an amount ranging from about 0.1% to about 75%, from about 1% to about 70%, from about 10% to about 60%, from about 20% to about 50%, or from about 25% to about 40% by weight based on the total weight of the formulation. In some embodiments, the carrier(s) and / or solvent(s) are present in an amount ranging from about 10% to about 99.9%, from about 20% to about 95%, from about 30% to about 90%, from about 35% to about 80%, from about 40% to about 75%, or from about 50% to about 70% by weight based on the total weight of the formulation.

[0100] In some embodiments, the formulation contains one or more auxiliaries selected from carriers that are used in solid urease inhibitor formulations. Exemplary solid carriers include, but are not limited to, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.

[0101] The amount of the solid carrier(s) present in a solid urease inhibitor formulation can vary. In some embodiments, the solid carrier(s) are present in an amount ranging from about 0.1% to about 99.9%, from about 10% to about 90%, from about 20% to about 80%, from about 30% to about 70%, or from about 40% to about 60% by weight based on the total weight of the solid urease inhibitor formulation. In some embodiments, the solid carrier(s) are present in an amount ranging from about 0.1% to about 75%, from about 1% to about 70%, from about 10% to about 60%, from about 20% to about 50%, or from about 25% to about 40% by weight based on the total weight of the urease inhibitor formulation. In some embodiments, the solid carrier(s) are present in an amount ranging from about 10% to about 99.9%, from about 20% to about 95%, from about 30% to about 90%, from about 35% to about 80%, from about 40% to about 75%, or from about 50% to about 70% by weight based on the total weight of the urease inhibitor formulation.

[0102] In some embodiments, the formulation contains surfactants (surface-active agents). Surfactants are designed to improve the dispersing / emulsifying, absorbing, spreading, and / or sticking properties of a liquid urease inhibitor formulation such as, e.g., a spray mixture. Useful surfactants are emulsifiers and / or foam formers, dispersants, or wetting agents having ionic or nonionic properties, or mixtures of these surfactants. Non-limiting examples of these are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthal enesul phonic 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, alkylsulphates, aryl sulphonates, protein hydrolysates, lignosulphite waste liquors, and methylcellulose. The presence of a surfactant may be particularly preferred 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 urease inhibitor composition. The formulations may further 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, metal phthalocyanine dyes, and trace nutrients such as salts of sulfur, calcium, magnesium, iron, manganese, boron, copper, cobalt, molybdenum, and zinc.

[0103] The formulations may further comprise a carrier medium, or vehicle, wherein that medium or vehicle is water. Ion exchanged water (deionized water), pure water, ultrapure water, distilled water, and the like may be used as the water. In order to reduce the amount of unwanted components present in the water, the purity of water may be increased by operations such as removal of impurity ions with an ion exchange resin, removal of contaminants with a filter, and / or distillation.

[0104] Further, a skilled person in the art would also be aware of the type and combination of auxiliaries and / or carriers that would be required to optimize the urease inhibitory formulation based on the above-listed properties and additional properties apparent to a skilled person in the art.

[0105] The disclosed formulation can be in the form of a liquid or a solid. Examples of liquid and solid formulations include, but are not limited to, soluble liquids (SF), emulsifiable concentrates (EC), wettable powders (WP), dry flowable (DF) powder, flowable powder (F), water soluble powders (SP), ultra-low-volume concentrate (ULV), suspension concentrates (SC), aqueous suspensions (AS), microencapsulated suspension (ME or MT), or capsule suspension (CS). In some embodiments, the urease inhibitor composition is in the form of a soluble salt, which is water soluble and requires little to no agitation to stay in solution. These types of formulations are often referred to as solutions (S), soluble concentrates (SC), liquid (L), and water soluble concentrates (WSC). In some embodiments, these types of formulations (e.g., S) are “ready-to-use.” In some embodiments, the formulation is a tank mix formulation or a premix formulation. In some embodiments, these types of formulations (e.g., SC, WSC) are diluted with water prior to use.

[0106] In some embodiments, any of the above formulations (or urease inhibitor compositions) can be used in methods for coating a solid urea-containing fertilizer as is described in more detail below. In other embodiments, any of the above formulations (or urease inhibitor compositions) can be used in methods of making a solid urea-containing fertilizer as is described in more detail below.

[0107] IV. Agricultural Products Any of the described urease inhibitor compositions or formulations can be combined with one or more other ingredients, 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.

[0108] A. Fertilizer

[0109] In some embodiments, the described agricultural products are a combination of the described urease inhibitor compositions or formulations (generally referred to as “urease inhibitor component”) and a fertilizer. In some embodiments, the urease inhibitor component is a urease inhibitor composition comprising an antioxidant. In such embodiments, the antioxidant is selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butyl-phenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof. In some embodiments, the urease inhibitor component is a urease inhibitor composition comprising an antioxidant and a chaotropic agent. As such, the urease inhibitor component is an antioxidant or a urease inhibitor composition as described herein.

[0110] In some embodiments, the urease inhibitor component is in a liquid form. In such embodiments, liquid urease inhibitor component is free of any organic solvent when the inhibitor component is tBHQ. Thus, for embodiments wherein the inhibitor component comprises tBHQ and an organic solvent, a chaotropic agent must be present. These liquid urease inhibitor components can be combined with one or more fertilizers in liquid form. For example, in some embodiments, the described urease inhibitor component can be prepared in the form of a dispersion and / or solution in a liquid fertilizer such as UAN, Urea 20, or water. In addition, these liquid urease inhibitor components can also be applied as a surface coating to fertilizer products in solid form. For such agricultural products, the described urease inhibitor component is applied as a liquid, a dispersion, or as a powder onto the surface of a fertilizer in solid form.

[0111] For agricultural products wherein the urease inhibitor component is used as a coating, the urease inhibitor component can comprise between about 0.005% and about 15% by weight of the coated fertilizer product, about 0.01% and about 10%, about 0.05% and about 5%, about 0.05% and about 2%, or about 0.5% and about 1% by weight of the agricultural product (e.g., coated fertilizer product). In some embodiments, the described urease inhibitor component is already integrated into the fertilizer in solid form. For such agricultural products, the described urease inhibitor component is physically incorporated (e.g., pre-infused) into the fertilizer in solid form during the manufacturing process of the solid fertilizer.

[0112] For such agricultural products, wherein the urease inhibitor component is incorporated into the fertilizer product, the amount of urease inhibitor component present in the fertilizer product can vary. In some embodiments, the urease inhibitor component is present in the agricultural product (e.g., fertilizer product) in an amount of from about 0.001% to about 15% by weight, from about 0.001% to about 10%, from about 0.001% to about 5%, from about 0.01% to about 5%, from about 0.01% to about 2.5%, from about 0.1% to about 2.5%, from about 0.1% to about 2%, from about 0.1% to about 1.5%, from about 0.5% to about 1.5%, or from about 0.75% to about 1.25% based on the total weight of the agricultural product. In some embodiments, the urease inhibitor component is present in the fertilizer product in an amount of about 1% based on the total weight of the agricultural product.

[0113] The fertilizer employed for these agricultural products is not particularly limited and can be any suitable solid fertilizer for application to fields and / or crops. Such solid fertilizers can be any granular fertilizer, to which the described urease inhibitor component can be applied as a solution, liquid dispersion, or as a powder. In some embodiments, such 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. 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, a 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). For example, in some embodiments, the fertilizer is a urea-containing fertilizer in solid form. In some embodiments, the fertilizer coated with the described urease inhibitor component is a solid urea-containing fertilizer. In some embodiments, the fertilizer having the described urease inhibitor component incorporated therein is a solid urea-containing fertilizer.

[0114] In some embodiments, the solid fertilizer (e.g., urea-containing fertilizer) is in the form of granules or prills. In some embodiments, the shape of the granules or prills are round (e.g., spherical or egg-shaped) but should not be limited thereto. Additional shapes include cubic, rectangular and / or irregular.

[0115] In some embodiments, the granular / prill fertilizer (e.g., urea-containing fertilizer) contains granules / prills having an average mesh size ranging from about 1 to about 100 (e.g., 1 / 100), from about 10 to about 100 (e.g., 10 / 100), or from about 16 to about 100 (e.g., 16 / 100) U.S. mesh. In other embodiments, the granular / prill fertilizer (e.g., urea-containing fertilizer) contains granules / prills having an average mesh size ranging from about 4 to about 30 (e.g., 4 / 30), from about 5 to about 24 (e.g., 5 / 24), or from about 6 to about 16 (e.g., 6 / 16) U.S. mesh.

[0116] In some embodiments, the median particle size (dso) of the granules / prills of fertilizer (e.g., urea-containing fertilizer) ranges from about 0.1 to 3.5 mm, from about 0.5 to about 2.5 mm, from or from about 0.9 to about 1 mm (or about 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.1, 2.2., 2.3, 2.4, or 2.5 mm). In some embodiments, the median particle size (dso) of the granules / prills of the fertilizer (e.g., urea-containing fertilizer) is less than about 3.5 mm, 3.0 mm, 2.5 mm, 2.0 mm, 1.5 mm or 1.0 mm.

[0117] In some embodiments, the granular / prill fertilizer (e.g., urea-containing fertilizer) contains granules / prills 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 80 to about 250, or from about 90 to about 230 SGN.

[0118] In some embodiments, the granular / prill fertilizer (e.g., urea-containing fertilizer) contains granules / prills having a 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). In some embodiments, the granular / prill fertilizer (e.g., urea-containing fertilizer) contains granules / prills 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.

[0119] In some embodiments, the granular / prill fertilizer (e.g., urea-containing fertilizer) 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.

[0120] In some embodiments, the described urease inhibitor component can be applied with the application of a fertilizer. The urease inhibitor component can be applied prior to, subsequent to, or simultaneously with the application of fertilizers. Such liquid urease inhibitor component comprising tBHQ in combination with an organic solvent must also contain a chaotropic agent as described herein.

[0121] Urease inhibitor composition-containing fertilizer products can be applied in any manner which will benefit the crop of interest. In some embodiments, the products are applied to growth mediums in a band or row application. In some embodiment, the products are applied to or throughout the growth medium prior to seeding or transplanting the desired crop plant. In some embodiment, the products are applied to the root zone of growing plants.

[0122] 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, and peanuts; oil plants, for example, rape, mustard, and sunflowers; cucurbitaceae, for example, marrows, cucumbers, and melons; fibre plants, for example, cotton, flax, hemp, and jute; citrus fruit, for example, oranges, lemons, grapefruit and mandarins; vegetables, for example, spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, sweet potatoes, yams, and 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 oats, spring oats, fodder cereals, ray grass, cocksfoot, fescue, timothy, grass for seed, and grassland and any combination thereof.

[0123] B. Seed

[0124] Some embodiments describe agricultural seeds coated with the urease inhibitor component as disclosed herein. The urease inhibitor component can be present in the seed product at a level of from about 0.001% to about 10%, about 0.004% to about 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.

[0125] C. Other

[0126] In some embodiments, urease-inhibiting compounds, nitrification-inhibiting compounds, pesticides, herbicides, insecticides, fungicides, and / or miticides are combined with the urease inhibitor composition disclosed herein. As used herein, “pesticide” refers to any agent with pesticidal activity (e.g., herbicides, insecticides, and fungicides) and is preferably selected from the group consisting of insecticides, herbicides, and mixtures thereof, but normally excluding materials, which are asserted to have plant-fertilizing effects, 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, OH), which is hereby incorporated by reference in its entirety.

[0127] 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. Exemplary insecticides include, but are not limited to 1,2 dichloropropane, 1,3 dichloropropene, 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, esfenval erate, 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, 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, p,p’-DDT, prallethrin, precocene I, 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, 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, vamidothion, vaniliprole, XMC, xylylcarb, zeta cypermethrin and zolaprofos.

[0128] Exemplary fungicides include, but are not be limited to, acibenzolar, acylamino acid fungicides, acypetacs, aldimorph, aliphatic nitrogen fungicides, allyl alcohol, amide fungicides, ampropylfos, anilazine, anilide fungicides, antibiotic fungicides, aromatic fungicides, aureofungin, azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benzalkonium chloride, benzamacril, benzamide fungicides, benzamorf, benzanilide fungicides, benzimidazole fungicides, benzimidazole precursor fungicides, benzimidazolylcarbamate fungicides, benzohydroxamic acid, benzothiazole fungicides, bethoxazin, binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin-S, Bordeaux mixture, boric acid, boscalid, bridged diphenyl fungicides, bromuconazole, bupirimate, Burgundy mixture, buthiobate, sec-butylamine, calcium polysulfide, captafol, captan, carbamate fungicides, carbamorph, carbanilate fungicides, carbendazim, carboxin, carpropamid, carvone, Cheshunt mixture, chinomethionat, chlobenthiazone, chloraniformethan, chloranil, chlorfenazole, chlorodinitronaphthalene, chloroform, chloroneb, chloropicrin, chlorothalonil, chlorquinox, chlozolinate, ciclopirox, climbazole, clotrimazole, conazole fungicides, conazole fungicides (imidazoles), conazole fungicides (triazoles), copper(II) acetate, copper(II) carbonate, basic, copper fungicides, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper(II) sulfate, copper sulfate, basic, copper zinc chromate, cresol, cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramid, cyclic dithiocarbamate fungicides, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet, DBCP, debacarb, decafentin, dehydroacetic acid, dicarboximide fungicides, dichlofluanid, dichlone, dichlorophen, dichlorophenyl, dichlozoline, diclobutrazol, diclocymet, diclomezine, dicloran, diethofencarb, diethyl pyrocarbonate, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinitrophenol fungicides, dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon, di thiocarbamate fungicides, DNOC, dodemorph, dodicin, dodine, donatodine, drazoxolon, edifenphos, epoxi conazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, ethylene oxide, ethylmercury 2,3 dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin, ferbam, ferimzone, fluazinam, Fluconazole, fludioxonil, flumetover, flumorph, fluopicolide, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fuberidazole, furalaxyl, furametpyr, furamide fungicides, furanilide fungicides, furcarbanil, furconazole, furconazole-cis, furfural, furmecyclox, furophanate, glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiofos, hydrargaphen, hymexazol, imazalil, imibenconazole, imidazole fungicides, iminoctadine, inorganic fungicides, inorganic mercury fungicides, iodomethane, ipconazole, iprobenfos, iprodione, iprovalicarb, isopropyl alcohol, isoprothiolane, isovaledione, isopyrazam, kasugamycin, ketoconazole, kresoxim-methyl, lime sulfur (lime sulphur), mancopper, mancozeb, maneb, mebenil, mecarbinzid, mepanipyrim, mepronil, mercuric chloride (obsolete), mercuric oxide (obsolete), mercurous chloride (obsolete), metalaxyl, metalaxyl-M (a.k.a. Mefenoxam), metam, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl isothiocyanate, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, metiram, metominostrobin, metrafenone, metsulfovax, milneb, morpholine fungicides, myclobutanil, myclozolin, N-(ethylmercury)-p-toluenesulfonanilide, nabam, natamycin, nystatin, -nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone, ofurace, oprodione, organomercury fungicides, organophosphorus fungicides, organotin fungicides (obsolete), orthophenyl phenol, orysastrobin, oxadixyl, oxathiin fungicides, oxazole fungicides, oxine copper, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, pentachlorophenol, penthiopyrad, phenylmercuriurea, phenylmercury acetate, phenylmercury chloride, phenylmercury derivative of pyrocatechol, phenylmercury nitrate, phenylmercury salicylate, phenylsulfamide fungicides, phosdiphen, phosphite, phthalide, phthalimide fungicides, picoxystrobin, piperalin, polycarbamate, polymeric dithiocarbamate fungicides, polyoxins, polyoxorim, polysulfide fungicides, potassium azide, potassium polysulfide, potassium thiocyanate, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pyracarbolid, pyraclostrobin, pyrazole fungicides, pyrazophos, pyridine fungicides, pyridinitril, pyrifenox, pyrimethanil, pyrimidine fungicides, pyroquilon, pyroxychlor, pyroxyfur, pyrrole fungicides, quinacetol, quinazamid, quinconazole, quinoline fungicides, quinomethionate, quinone fungicides, quinoxaline fungicides, quinoxyfen, quintozene, rabenzazole, salicylanilide, silthiofam, silver, simeconazole, sodium azide, sodium bicarbonate[2][3], sodium orthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulfide, spiroxamine, streptomycin, strobilurin fungicides, sulfonanilide fungicides, sulfur, sulfuryl fluoride, sultropen, TCMTB, tebuconazole, tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor, thiazole fungicides, thicyofen, thifluzamide, thymol, triforine, thiocarbamate fungicides, thiochlorfenphim, thiomersal, thiophanate, thiophanate- methyl, thiophene fungicides, thioquinox, thiram, tiadinil, tioxymid, tivedo, tolclofos-methyl, tolnaftate, tolylfluanid, tolylmercury acetate, triadimefon, triadimenol, triamiphos, triarimol, triazbutil, triazine fungicides, triazole fungicides, triazoxide, tributyltin oxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, tri ti conazole, unclassified fungicides, undecylenic acid, uniconazole, uniconazole-P, urea fungicides, validamycin, valinamide fungicides, vinclozolin, voriconazole, zarilamid, zinc naphthenate, zineb, ziram, and / or zoxamide.

[0129] In some embodiments, the composition of the presently disclosed subject matter is a pesticide / urease inhibitor composition-containing product comprising a pesticide and tert-butylhydroquinone (and optionally an additive component). In some embodiments, the pesticide is an herbicide, insecticide, or a combination thereof.

[0130] The amount of urease inhibitor composition in the pesticide / urease inhibitor composition-containing product can vary. In some embodiments, the amount of urease inhibitor composition is present at a level from about 0.05% to about 10% by weight (more preferably from about 0.1% to about 4% by weight, and most preferably from about 0.2% to about 2% by weight) based upon the total weight of the pesticide / urease inhibitor composition-containing product taken as 100% by weight.

[0131] Exemplary classes of miticides include, but are not be 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, phenylsulfonamide 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, chloropropyl ate, 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- methyl, azothoate, benoxafos, bromophos, bromophos-ethyl, carbophenothion, chlorpyrifos, chlorthiophos, coumaphos, cyanthoate, demeton, demeton-O, demeton-S, dem eton -methyl, demeton-O-methyl, demeton-S-methyl, demeton S methyl sulphon, 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; phenylsulfamide 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.

[0132] 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, di chloropropene, 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.

[0133] V. Methods

[0134] In some embodiments, the urease inhibitor composition is used directly. In other embodiments, the urease inhibitor composition is formulated in ways to make its use convenient in the context of productive agriculture. For example, in some embodiments, the urease inhibitor composition is used together with a fertilizer (e.g., a urea-containing fertilizer) in agricultural products. The urease inhibitor composition used in these methods includes an antioxidant (e.g., tert-butylhydroquinone) alone or in combination with a chaotropic agent as described above. The urease inhibitor composition alone or formulated as an agricultural product (e.g., a urea-containing fertilizer) can be used in methods such as:

[0135] A. Methods of Improving Plant Growth and / or Plant Health and / or Fertilizing Soil

[0136] B. Methods of Inhibiting Urease Enzyme Activity

[0137] C. Methods for Inhibiting Ammonia Release or Evolution

[0138] D. Methods of Improving Soil Conditions E. Methods of Preparing a Urease Inhibitor Composition

[0139] F. Methods of Preparing Agricultural Products Containing a Fertilizer

[0140] A. Methods for improving plant growth comprise contacting a urease inhibitor composition as disclosed herein with soil. In some embodiments, the urease inhibitor composition is applied to the soil prior to emergence of a planted crop. In some embodiments, the urease inhibitor composition 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 urease inhibitor composition is formulated as an agricultural product together with a fertilizer (e.g., urea-containing fertilizer) and is applied in the same manner as described above for the urease inhibitor composition.

[0141] Methods for improving plant growth can also be achieved by applying a urease inhibitor composition as disclosed herein as a seed coating to a seed in the form of a liquid dispersion, which upon drying, forms a dry residue. In some embodiments, the urease inhibitor composition as disclosed herein is in a solid form (e.g., a powder), and is applied to the seed such that the powder adheres to the surface of the seed. In these embodiments, seed coating provides the antioxidant (e.g., tert-butylhydroquinone) in close proximity to the seed when planted so that the antioxidant can exert its beneficial effects in the environment where it is most needed. That is, the antioxidant (e.g., tert-butylhydroquinone) provides 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 the antioxidant (e.g., tert-butylhydroquinone) provides an enhanced opportunity for seed germination, subsequent plant growth, and an increase in plant nutrient availability.

[0142] B. Methods for inhibiting / reducing urease enzyme activity, the method comprising applying a urease inhibitor composition as disclosed herein to the soil. In some embodiments, the urease inhibitor composition is applied to the soil prior to emergence of a planted crop. In some embodiments, the urease inhibitor composition 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 urease enzyme activity is inhibited / reduced 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 about 95%.

[0143] C. Methods for inhibiting / reducing ammonia release or evolution in an affected area comprises applying a urease inhibitor composition as disclosed herein to the affected area. In some embodiments, application of the urease inhibitor to the affected area inhibits / reduces the ammonia release in the affected are 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 by at least 95%. 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 urease inhibitor may be applied directly to the manure in the collection zone. The urease inhibitor component is preferably applied at a level from about 0.005 to about 3 gallons per ton of manure, in the form of an aqueous dispersion having a pH from about 1 to about 5.

[0144] D. 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 urease inhibitor composition or an effective amount of an agricultural product as disclosed herein. The urease inhibitor composition or agricultural product as disclosed herein is generally applied at a level of from about 0.01% to about 10% by weight, about 0.1% to about 10% by weight, about 1% to about 10% by weight, or about 1% to about 5% by weight based upon the total weight of the urease inhibitor composition or agricultural product.

[0145] E. Methods of preparing a urease inhibitor composition in liquid form comprises contacting an antioxidant, a chaotropic agent, and / or one or more organic solvents as disclosed herein to form a mixture. In some embodiments, the mixture is a solution (meaning the antioxidant and chaotropic agent, if present, are fully dissolved). In some embodiments, the mixture is a dispersion (meaning the antioxidant and chaotropic agent, if present, are not fully dissolved).

[0146] Method of preparing a urease inhibitor composition in solid form, comprises grinding and / or milling the antioxidant and chaotropic agent, if present, as disclosed herein in solid form to generate a powder. In some embodiments, the antioxidant and chaotropic agent, if present, are mixed prior to the grinding and / or milling step. In such embodiments, the antioxidant and chaotropic agent, if present, are ground and / or milled simultaneously. In some embodiments, the antioxidant and chaotropic agent, if present, are ground and / or milled individually to obtain separate powders, which are then mixed together to yield the urease inhibitor composition. A skilled artisan would generally be aware of the various grinding and milling techniques. For example, in some embodiments, the method utilizes stainless steel beads as a grinding technique. The amount of antioxidant and chaotropic agent employed in these preparation methods can vary. In some embodiments, the amount of antioxidant and chaotropic agent employed in the disclosed methods ranges from about 1 : 1000 to about 1000: 1, from about 1:500 to about 500: 1, from about 1 :250 to about 250: 1, from about 1 : 150 to about 150: 1, from about 1 :100 to about 100: 1, from about 1:75 to about 75: 1, from about 1 :50 to about 50: 1, from about 1 :25 to about 25: 1, from about 1 : 15 to about 15: 1, from about 1 : 10 to about 10: 1, from about 1 :8 to about 8: 1, from about 1 :5 to about 5:1, from about 1 :3 to about 3: 1, or from about 1 :2 to about 2: 1 molar ratio of antioxidant to chaotropic agent. In some embodiments, the antioxidant and chaotropic agent are employed in a 1 : 1 molar ratio.

[0147] F. Methods of preparing agricultural products comprises contacting the described urease inhibitor composition with an agricultural product. In some embodiments, the urease inhibitor is in the form of a solution / liquid or dispersion and is sprayed onto the outer surface of an agricultural product in solid form (e.g., a fertilizer or seed). In some embodiments, the urease inhibitor composition is mixed with a urea-containing solid, liquid, or gaseous fertilizer, and especially, solid fertilizers; in the latter case, the urease inhibitor composition is applied to the surface of the (urea-containing) fertilizer as an aqueous dispersion followed by drying so that the urease inhibitor composition is present on the solid fertilizer as a dried residue. In some embodiments, the urease inhibitor composition is in a solid form, e.g., a powder. In such embodiments, the solid urease inhibitor is applied to the outer surface of the solid agricultural product such that the urease inhibitor composition adheres to its surface.

[0148] Methods of preparing agricultural products containing a fertilizer in powder form comprises grinding and / or milling the urease inhibitor composition as disclosed herein in solid form and a fertilizer (e.g., a urea-containing fertilizer) in solid form to generate a powder. In some embodiments, the described urease inhibitor composition and fertilizer are mixed prior to the grinding and / or milling step. In such embodiments, the urease inhibitor composition and fertilizer are ground and / or milled simultaneously. In some embodiments, the urease inhibitor composition and fertilizer are ground and / or milled individually to obtain separate powders, which are then mixed together to yield the agricultural product. A skilled artisan would generally be aware of the various grinding and milling techniques. For example, in some embodiments, the method utilizes stainless steel beads as a grinding technique. The amount of urease inhibition composition and fertilizer employed in these preparation methods can vary. In some embodiments, the amount of urease inhibition composition and fertilizer employed in the disclosed methods ranges from about 1 : 1000 to about 1000: 1, from about 1 :750 to about 750: 1, from about 1 :500 to about 500:1, from about 1 :250 to about 250:1, from about 1 : 150 to about 150: 1, from about 125:1 to about 1 : 125, from about 1 :100 to about 100: 1, or from about 1 : 75 to about 75: 1 weight ratio of urease inhibitory composition to fertilizer. In some embodiments, the urease inhibitory composition and fertilizer are employed in a 1 :99 molar ratio.

[0149] Methods for preparing agricultural products containing a fertilizer in the form of a granule or prill wherein the described urease inhibitor composition is incorporated within such granule or prill are also disclosed herein. In these methods, the disclosed urease inhibitor composition or formulation can be used as an additional component in the manufacturing process of such fertilizers. For example, a common fertilizer in the form of a granule or prill is a urea-containing fertilizer. Manufacturing processes of urea-containing granule or prills are generally known in the art and generally employ a urea melt or an aqueous urea solution.

[0150] The source of urea to prepare the urea melt or aqueous urea solution can include any suitable urea source. In some embodiments, the urea source is urea which has been synthesized and still molten (not cooled and re-melted). In some embodiments, the urea source is a solid form of urea, including, but not limited to, granulated or prilled urea, that is, re-melted and dehydrated. In some embodiments, the urea is produced from ammonia and carbon dioxide, for example, in an industrial urea production plant. One of skill in the art will appreciate other urea sources for the inventive methods.

[0151] The amount of the urea in the urea-containing granular fertilizer can range from about 1% to about 99% by weight of the total weight of the agricultural product (urease inhibitor pre-infused urea-containing granule). The amount of the urea present in the agricultural product can be about 1% to about 99% by weight, from about 10% to about 99% by weight, from about 20% to about 99% by weight, from about 30% to about 99% by weight, from about 40% to about 99% by weight, from about 50% to about 99% by weight, from about 60% to about 99% by weight, from about 70% to about 99% by weight, from about 80% to about 99% by weight, or from about 90% to about 99% by weight based on the total weight of the agricultural product. In some embodiments, the amount of urea is at least about 60 wt. %, about 70 wt. %, about 80 wt. %, about 90 wt. %, about 91 wt. %, about 92 wt. %, about 93 wt. %, about 94 wt. %, about 95 wt. %, about 96 wt. %, about 97 wt. %, about 98 wt. %, or about 99 wt. % based on the total weight of the agricultural product.

[0152] In some embodiments, the urea melt can initially contain up to about 70 wt. %, about 75 wt. %, about 80 wt. %, about 85 wt. %, about 80 wt. % urea in water, either from the source of the urea used or from the addition of UF85 and the like. Such an aqueous urea melt can be concentrated further by vacuum concentration, or evaporation at atmospheric pressure to afford a concentrated urea melt. In some embodiments, the resulting urea melt comprises a concentration of water that is reduced to less than about 9%, 8%, 7%, 6%, 5.5%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%, or less than 1% (e.g., about 0.5, 0.4, 0.3, 0.2, or 0.1%) based on the total weight of the urea melt.

[0153] In some embodiments, the disclosed methods provide agricultural products wherein the concentration of water is at most about 1 weight percent based on the total weight of the agricultural product.

[0154] Thus, in some embodiments, the methods for preparing agricultural products such as a urea-containing fertilizer in the form of a granule or prill wherein the described urease inhibitor composition is incorporated therein comprises obtaining a urea melt, contacting the urea melt with the urease inhibitor composition or formulation disclosed herein thereby producing a urea melt-urease inhibitor mixture, and forming the urea melt-urease inhibitor mixture into granules and / or prills.

[0155] In some embodiments, the contacting step of the method comprises mixing of the urease inhibitor with the urea melt. Sufficient mixing of both components should be provided in order to facilitate homogenous distribution of the urease inhibitor composition or formulation throughout the urea melt. The homogeneous distribution of urease inhibitor in the granular fertilizer compositions of this invention enhances the performance of these compositions in terms of their ability to promote plant growth and inhibit urease enzyme activity. Thus, in some embodiments, the urease inhibitor composition is added to the urea melt (or vice versa) before the forming step, which takes place either in a granulator or prilling tower.

[0156] In order to ensure a homogenous distribution of the urease inhibitor composition in the urea melt-urease inhibitor mixture produced in the contacting step, adequate time must be provided to allow dissolution of both components (i.e., urea melt and urease inhibitor composition). Thus, in some embodiments, a convenient point for the addition of urease inhibitor composition or formulation disclosed herein to the urea melt in a urea production plant would be before or between the evaporation steps used to reduce the water content of the urea melt. In some embodiments, the urease inhibitor of formulation disclosed herein is introduced into the urea melt just before the granulation or prilling step with only sufficient retention time in the melt to allow for distribution of the urease inhibitor in the melt.

[0157] In some embodiments, the retention time of the urea melt between the point of urease inhibitor addition and the granulation step is less than 5 minutes or even less than 1 minute. In some embodiments, the retention time is as little as about 50, or 40, or 30, or 29, or 28, or 27, or 26, or 25, or 24, or 23, or 22, or 21, or 20, or 19, or 18, or 17, or 16, or 15, or 14, or 13, or 12, or 11, or 10, or 9, or 8, or 7, or 6, or 5, or 4, or 3, or 2, or 1 seconds. Longer retention times may result in partial decomposition of the urease inhibitor, higher concentrations of biuret, and / or reduced effectiveness of the agricultural product.

[0158] In some embodiments, the urease inhibitor composition or formulation is added to the urea melt at varying flow rates. In some embodiments, the urease inhibitor composition or formulation is added at a flow rate from about 5 Ibs / hr to about 2500 Ibs / hr, from about 10 Ibs / hr to about 2500 Ibs / hr, from about 20 Ibs / hr to about 220 Ibs / hr, from about 50 Ibs / hr to about 200 Ibs / hr, or from about 75 Ibs / hr to about 150 Ibs / hr.

[0159] In some embodiments, the urease inhibitor composition or formulation disclosed herein is contacted with the urea melt prior to the evaporation of excess water present in the urease inhibitor-urea melt composition.

[0160] When forming the granules or prills, the urease inhibitor-urea melt composition is cooled down in a granulator or prilling tower. In general, the granulation process is carried out in the granulator and requires that a rotating high-velocity air stream is established in the central agglomeration tube. Particles are picked up at the base of the tube and accelerated by the air stream. The particles come into contact with fluid droplets produced from the spray nozzle at the base of the tube. Due to the relative velocity of particles, air and fluid droplets are high so wetting is efficient and drying begins almost immediately. During granulation, the urease inhibitor-urea melt composition is sprayed onto the circulating recycled prills (or seed particles, such as solid urea or solid urease inhibitor) while air passes through the granulator and solidifies the urease inhibitor-urea melt composition deposited on the seed material. In some cases, urease inhibitor- urea melt composition is conditioned prior to spraying. This can enhance the storage and handling characteristics of the granular agricultural product. There are two types of granulators: drum granulators and pan granulators. In drum granulation, solids are built up in layers on seed granules placed in a rotating drum granulator / cooler approximately 4.3 meters (14 feet) in diameter. Pan granulators also form the product in a layering process, and are a type of agitation (tumble- growth / non-pressure / wet granulation) agglomeration equipment used throughout various industries to pelletize fines into rounded granules.

[0161] During the prilling process in the prilling tower, the concentrated urease inhibitor-urea melt composition is fed to a perforated rotating bucket / shower-type spray head located at the top of the prilling tower. The bucket is rotated at high speed and sprays urease inhibitor-urea melt composition in the form of droplets. Liquid droplets are solidified and cooled on free-fall through the tower against a forced or natural up-draft of ambient air. The product is removed from the tower base to a conveyor belt. Cooling to ambient temperature and screening may be used before the product is transferred to storage. There are two different types of prill towers: fluidized bed and nonfluidized bed. The major difference is that a separate solids cooling operation may be required to produce agri cultural -grade prills in a nonfluidized bed prill tower.

[0162] The disclosed methods herein are not limited to the above described methods for the preparation of solid fertilizer granules or prills and a skilled artisan would generally be familiar with any variations of the above-disclosed methods, wherein the disclosed urease inhibitor composition or formulation can be used as an additive to prepare the disclosed urea-containing granules or prills pre-infused with the urease inhibitor composition disclosed herein.

[0163] In other words, it is to be understood that this disclosure is not limited to particular embodiments described, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

[0164] As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order that is logically possible.

[0165] It is to be understood that, unless otherwise indicated, the present disclosure is not limited to particular materials, reagents, reaction materials, manufacturing processes, or the like, as such can vary. It is also to be understood that the terminology used herein is for purposes of describing particular embodiments only, and is not intended to be limiting. It is also possible in the present disclosure that steps can be executed in different sequence where this is logically possible.

[0166] Particular embodiments of the subject matter described herein include:

[0167] 1. A composition comprising: an antioxidant; and a chaotropic agent.

[0168] 2. The composition of embodiment 1, wherein the chaotropic agent is selected from the group consisting of magnesium chloride, sodium perchlorate, sodium bromide, sodium trifluoroacetate, sodium thiocyanate, sodium tri chloroacetate, dodine, guanidinium chloride, guanidinium thiocyanate, lithium perchlorate, lithium acetate, monoethanolamine borate, phenol, sodium dodecyl sulfate, thiourea, urea, , and combinations thereof.

[0169] 3. The composition of embodiment 1 or embodiment 2, wherein the chaotropic agent is selected from the group consisting of magnesium chloride, monoethanolamine borate, thiourea, and guanidinum chloride.

[0170] 4. The composition of any one of the preceding embodiment, wherein the antioxidant and chaotropic agent are present in a molar ratio of from about 1 :2 to about 2:1.

[0171] 5. A composition comprising an antioxidant selected from the group consisting of tert-butylhydroquinone (tBHQ), p- hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butyl-phenol (DBP), 2,6-di-tert-butyl- p-benzoquinone (BHT-Q), and combinations thereof, wherein the composition inhibits urease enzyme activity. 6. The composition of any one of embodiments 1-4, wherein the antioxidant is selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butyl-phenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof.

[0172] 7. The composition of any one of the preceding embodiments, wherein the antioxidant is tert- butylhydroquinone (tBHQ).

[0173] 8. The composition of any one of the preceding embodiments, wherein the composition is in a solid form.

[0174] 9. The composition of embodiment 8, wherein the composition is in the form of a powder.

[0175] 10. The composition of any one of embodiment 1-7, wherein the composition is in a liquid form.

[0176] 11. The composition of embodiment 10, wherein the composition further comprises an organic solvent.

[0177] 12. The composition of embodiment 11, wherein the organic solvent is selected from the group consisting of dimethyl sulfoxide, sulfolane, DMF, DMPU, NMP, and a combination thereof.

[0178] 13. The composition of any one of the preceding embodiments, wherein the composition is used in a method or process for preparing urea-containing powders, granules, prills, or liquid formulations.

[0179] 14. The composition of any one of the preceding embodiments, wherein the composition inhibits urease enzyme activity.

[0180] 15. An agricultural product comprising: a granule or prill containing urea; and a urease inhibitor component, wherein the urease inhibitor component is an antioxidant or a composition of any one of embodiments 1-4 and 6-14, and wherein the antioxidant selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butyl-phenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof.

[0181] 16. The agricultural product of embodiment 15, wherein the urease inhibitor component is in a liquid form.

[0182] 17. The agricultural product of embodiment 16, wherein the urease inhibitor component is free of any organic solvent when the inhibitor component is tBHQ.

[0183] 18. The agricultural product of any one of embodiments 15-17, wherein the urease inhibitor component is sprayed onto the surface of the granule or prill.

[0184] 19. The agricultural product of embodiment 15, wherein the urease inhibitor component is in a solid form and adheres onto the surface of the granule or prill.

[0185] 20. The agricultural product of any one of the preceding embodiments, wherein the urease inhibitor component is present in an amount of from about 0.001% to about 10% by weight, based on the total weight of the agricultural product.

[0186] 21. The agricultural product of embodiment 15, wherein the urease inhibitor component is preinfused into the granule or prill.

[0187] 22. The agricultural product of embodiment 21 , wherein the weight ratio of urea to urease inhibitor component present in the granule or prill is from about 1 : 10 to about 10: 1.

[0188] 23. A method of making a composition of any one of embodiments 1-4 and 6-14, the method comprising: contacting the antioxidant with the chaotropic agent.

[0189] 24. The method of embodiment 23, wherein the contacting step comprises milling, grinding, or a combination thereof.

[0190] 25. The method of embodiment 23, wherein the contacting step comprises a solvent. 26. A method of making a granule or prill containing urea coated with a composition or formulation of any one of the preceding embodiments, the method comprising: obtaining a urea containing granule or prill; and spraying the surface of the urea-containing granule or prill with the composition or formulation of any one of the preceding embodiments.

[0191] 27. A method of making a granule or prill containing urea and the composition of any one of embodiments 1-16, the method comprising: obtaining a urea melt; contacting the urea melt with the composition of any one of embodiments 1-16 to obtain a mixture; and cooling the mixture to obtain the granule or prill.

[0192] 28. The method of embodiment 27, wherein the method comprises a prilling tower.

[0193] 29. The method of embodiment 27, wherein the method comprises a granulator.

[0194] 30. A method of improving plant growth and / or health comprising applying a composition or agricultural product according to any one of the preceding embodiments to the soil.

[0195] 31. The method of embodiment 30, wherein the composition of any one of embodiments 1-16 or agricultural product of any one of embodiments 17-23 is applied to the soil prior to emergence of a crop plant.

[0196] 32. The method of embodiment 31, wherein the composition or agricultural product is applied to the soil adjacent to a crop plant, at the base of the crop plant, or in the root zone of the crop plant.

[0197] 33. The method of embodiment 31 or embodiment 32, wherein the crop plant is selected from the group consisting of: cereal, wheat, barley, oat, triticale, rye, rice, maize, soya beans, potato, vegetable, peanuts, cotton, oilseed grape and fruit plant.

[0198] 34. The method of embodiment 30, wherein the applying step comprises contacting at a rate of about 5 lbs to about 30 lbs per acre of the composition or agricultural product. 35. The method of embodiment 30, wherein the composition or agricultural product is used in an amount ranging from about 25 to about 300 kg / ha.

[0199] 36. A method of reducing atmospheric ammonia and / or nitrification comprising applying a composition of any one of the preceding embodiments to an area subject to evolution of ammonia and / or nitrification.

[0200] 37. A method of inhibiting a soil condition selected from the group consisting of nitrification processes, urease activities, and combinations thereof, wherein said method comprises applying an effective amount of a composition or an agricultural product of any one of the preceding embodiments to the soil.

[0201] EXAMPLES

[0202] It should be understood that the following examples are provided by way of illustration only and nothing therein should be taken as a limiting.

[0203] Example 1: Screening of Urease Inhibitor Compositions

[0204] Evaluation of antioxidants in combination with a chaotropic agent was tested. The test samples were as follows:

[0205] Treatment 2 - MgCb and tBHQ at 1 : 1 molar ratio; both chemicals were in powder forms and were milled together by grinding using stainless steel beads.

[0206] Treatment 3 - MEA borate and tBHQ at 1 : 1 molar ratio; tBHQ powder was stirred into MEA borate liquid at 1 : 1 molar ratio and then ground with stainless steel beads.

[0207] Treatment 4- Guanidinium chloride and tBHQ at 1 : 1 molar ratio; both chemicals were in powder forms and were milled together by grinding using stainless steel beads.

[0208] Treatment 5- Thiourea and tBHQ; both chemicals were in powder forms and were milled together by grinding using stainless steel beads.

[0209] Each of the above samples was incorporated into urea by grinding the urea granule with the above Treatment sample together at a weight percent loading of 1% Treatment sample to urea. The end product was in powder form with 99% urea and 1% of each Treatment candidate sample. The pre-incorporated urea powder was then used for the Draeger tube tests, and the results are given below.

[0210] Treatment 2 was used as positive control. It is the commercial Agrotain product from Koch and it contains NBPT as urease inhibitor. Each sample was replicated in 5 repeats. Treatment 1 was negative control or bare soil with no treatment applied. The numbers in the above table were equivalent NH3 emissions captured at the specific time of the test. The unit of measure is ppm. All four milled samples presented in this disclosure outperformed the industry standard. Graphic depictions of these results are given in FIGs. 1 A- ID. Results for the various Treatments minus Treatment 1 are found in FIGs. 2A-D (i.e.,.the soil control values were subtracted from the commercial control (Agrotain) and from the various treatments and the differences were plotted).

[0211] Example 2: Screening of Urease Inhibitor-Urea Compositions

[0212] Evaluation of antioxidant tBHQ in combination with urea was tested. The test samples were as follows:

[0213] 1) Treatment 7 is untreated control (no urea) 2) Treatment 8 is milled urea

[0214] 3) Treatment 9 is Agrotain control (Agrotain is a Koch product which is an industry-recognized NBPT-containing urease inhibitor product) 4) Treatment 10 is tBHQ (in DMSO-Xylenes; internal control)

[0215] 5) Treatment 11 - 0.5% milled urea-tBHQ

[0216] 6) Treatment 12 - 1% milled urea-tBHQ

[0217] 7) Treatment 13 - 1.5% milled urea-tBHQ 8) Treatment 14 - 5% milled urea-tBHQ

[0218] Each of the above samples was incorporated into urea by grinding the urea granule with the above Treatment sample together at a weight percent loading of the Treatment sample as indicated above to the urea. The end products were mixtures in powder form. The preincorporated urea powder was then used for the Draeger tube tests and the results are shown in FIGs. 3A-3E.

[0219] Graphic depictions of these results are given in FIGs. 3A-3E. Results for the various Treatments minus Treatment 7 are found in FIGs. 4A-4E. Example 3: Draeger test tube protocol

[0220] A Draeger tube protocol was developed and used soils from NCSU Ag research facility at Oxford, North Carolina. Samples were prepared by co-dissolution in the appropriate solvent by rolling on a sample roller for 2-4 hours at ambient temperature and allowed to stand over the weekend to make sure there was no haziness and / or precipitate that developed. Typical sample size was 4-4.5 g in a 12 mL cylindrical glass vial. These clear (sometimes colored as light peach) solutions were applied on urea prills at 3 qts / ton (L, for low rate) and 6 qts / ton (H, for high rate). Readings were plotted as a graph where time is the independent variable and NFfc recorded (on a linear Draeger scale) on the y-axis to generate, in general, “S” shaped outputs. Samples were stored at ambient temperature for 6 months (or 12 months) to see any development of precipitates, thickening or haziness.

Claims

That which is claimed is:

1. A composition comprising: an antioxidant; and a chaotropic agent.

2. The composition of claim 1, wherein the chaotropic agent is selected from the group consisting of magnesium chloride, sodium perchlorate, sodium bromide, sodium trifluoroacetate, sodium thiocyanate, sodium tri chloroacetate, dodine, guanidinium chloride, guanidinium thiocyanate, lithium perchlorate, lithium acetate, monoethanolamine borate, phenol, sodium dodecyl sulfate, thiourea, urea, , and combinations thereof.

3. The composition of claim 1, wherein the chaotropic agent is selected from the group consisting of magnesium chloride, monoethanolamine borate, thiourea, and guanidinum chloride.

4. The composition of claim 1 or claim 2, wherein the antioxidant and chaotropic agent are present in a molar ratio of from about 1 :2 to about 2: 1.

5. A composition comprising an antioxidant selected from the group consisting of tert-butylhydroquinone (tBHQ), p- hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butyl-phenol (DBP), 2,6-di-tert-butyl- p-benzoquinone (BHT-Q), and combinations thereof, wherein the composition inhibits urease enzyme activity.

6. The composition of claim 1 or claim 2, wherein the antioxidant is selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butyl-phenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof.

7. The composition of claim 1, 2 or 5, wherein the antioxidant is tert-butylhydroquinone (tBHQ).

8. The composition of claim 1 or 5, wherein the composition is in a solid form.

9. The composition of claim 8, wherein the composition is in the form of a powder.

10. The composition of claim 1 or claims 5, wherein the composition is in a liquid form.

11. The composition of claim 10, wherein the composition further comprises an organic solvent.

12. The composition of claim 11, wherein the organic solvent is selected from the group consisting of dimethyl sulfoxide, sulfolane, DMF, DMPU, NMP, and a combination thereof.

13. The composition of claim 1 or claim 5, wherein the composition is used in a method or process for preparing urea-containing powders, granules, prills, or liquid formulations.

14. The composition of claim 1 or claim 5, wherein the composition inhibits urease enzyme activity.

15. An agricultural product comprising: a granule or prill containing urea; and a urease inhibitor component, wherein the urease inhibitor component is an antioxidant or a composition of claim 1, and wherein the antioxidant is selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butyl-phenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof.

16. The agricultural product of claim 15, wherein the urease inhibitor component is in a liquid form.

17. The agricultural product of claim 16, wherein the urease inhibitor component is free of any organic solvent when the inhibitor component is tBHQ.

18. The agricultural product of claims 15, 16 or 17, wherein the urease inhibitor component is sprayed onto the surface of the granule or prill.

19. The agricultural product of claim 15, wherein the urease inhibitor component is in a solid form and adheres onto the surface of the granule or prill.

20. The agricultural product of claim 15, wherein the urease inhibitor component is present in an amount of from about 0.001% to about 10% by weight, based on the total weight of the agricultural product.

21. The agricultural product of claim 15, wherein the urease inhibitor component is pre-infused into the granule or prill.

22. The agricultural product of claim 21, wherein the weight ratio of urea to urease inhibitor component present in the granule or prill is from about 1 : 10 to about 10: 1.

23. A method of making a composition of claim 1, the method comprising: contacting the antioxidant with the chaotropic agent.

24. The method of claim 23, wherein the contacting step comprises milling, grinding, or a combination thereof.

25. The method of claim 23, wherein the contacting step comprises a solvent.

26. A method of making a granule or prill containing urea coated with a composition of claim 1 or claim 5, the method comprising: obtaining a urea containing granule or prill; and spraying the surface of the urea-containing granule or prill with the composition of claim 1 of claim 5.

27. A method of making a granule or prill containing urea and the composition of claim 1 or claim 5, the method comprising: obtaining a urea melt; contacting the urea melt with the composition of claim 1 or claim 5 to obtain a mixture; and cooling the mixture to obtain the granule or prill.

28. The method of claim 27, wherein the method comprises a prilling tower.

29. The method of claim 27, wherein the method comprises a granulator.

30. A method of improving plant growth and / or health comprising applying a composition of claim 1 or claim 5 to the soil.

31. The method of claim 30, wherein the composition is applied to the soil prior to emergence of a crop plant.

32. The method of claim 31, wherein the composition is applied to the soil adjacent to a crop plant, at the base of the crop plant, or in the root zone of the crop plant.

33. The method of claim 31 or claim 32, wherein the crop plant is selected from the group consisting of: cereal, wheat, barley, oat, triticale, rye, rice, maize, soya beans, potato, vegetable, peanuts, cotton, oilseed grape and fruit plant.

34. The method of claim 30, wherein the applying step comprises contacting at a rate of about5 lbs to about 30 lbs per acre of the composition.

35. The method of claim 30, wherein the composition is used in an amount ranging from about 25 to about 300 kg / ha.

36. A method of reducing atmospheric ammonia and / or nitrification comprising applying a composition of claim 1 or claim 5 to an area subject to evolution of ammonia and / or nitrification.

37. A method of inhibiting a soil condition selected from the group consisting of nitrification processes, urease activities, and combinations thereof, wherein said method comprises applying an effective amount of a composition of claim 1 or claim 5 to the soil.

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