Compositions for enhancing nitrogen fertilizers by incorporating antioxidant moieties and methods of use thereof

Abstract

The present invention relates to urease inhibitor compositions containing a tert-butylhydroquinone and optionally an additive component for enhancing the inhibitory properties of the tert-butylhydroquinone. The use of the composition in agriculture to increase nutrient uptake and inhibit urease activity is also described.

Description

Technical Field

[0001] The presently disclosed subject matter relates to compositions containing tert-butylhydroquinone. Further described is the use of the compositions in agriculture to enhance nutrient uptake and inhibit urease activity. Background Art

[0002] Nitrogen is an essential plant nutrient and is considered crucial for lush and strong foliage. Urea provides a high nitrogen content and is the primary nitrogen fertilizer. In the presence of soil moisture, natural or synthetic urea is converted to ammonium ions, which are then available for plant uptake. Ammonium can be further converted to nitrate by bacteria in the soil via the nitrification process. Nitrate is also available for plant uptake. However, the efficiency of plant use of urea is low. Although millions of tons of urea-containing fertilizers are currently used globally each year and are the predominantly used fertilizers, approximately 30% of the applied fertilizers never reach the intended target area (the roots).

[0003] In practice, nitrogen fertilizers are often applied only once at the start of the growing season. Typically, nitrogen fertilizers are formulated as dry granules, pellets, or fluids made from urea alone or in combination 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 the significant drawback that they undergo rapid decomposition upon application to the soil and produce ammonia gas. This is due to the presence of urease in the soil, which reacts with urea to produce ammonium bicarbonate and ammonia. This series of processes is known in the art as volatilization. Volatilization results in reduced nitrogen fertilizer use efficiency, reduced yields, nitrogen deficiency symptoms in plants, the production of unpleasant odors, and potentially harmful ammonia concentrations. In addition, the ammonia produced can be converted to nitrate by bacteria in the soil, which is called nitrification. Excess nitrate can be converted to nitric oxide or nitrous oxide by certain types of bacteria in the soil, which is called denitrification.

[0004] Urease inhibitors that are able to delay the degradation of nitrogen fertilizers have been developed, thereby reducing the loss of nitrogen-containing degradation products that would otherwise occur in the absence of these inhibitors. Urease inhibitors, when used in combination with nitrogen fertilizers, tend to increase the amount of time the nitrogen source remains in the soil and is available for plant uptake, thus increasing the effectiveness of the fertilizer and having a positive impact on crop yield and quality. However, issues related to cost, safety, convenience, and stability limit the use of these types of inhibitors. Currently, product lines contain the urease inhibitor N-(n-butyl) thiophosphoric triamide (NBPT) and are commonly used to improve nitrogen fertilizer availability and minimize ammonia volatilization. However, for example Products such as these also exhibit various drawbacks, including their chemical stability and potential interference 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). Thus, there is a great need to discover urease inhibitors that are stable and safe for the environment and animals and non-toxic to crops.

[0005] Accordingly, despite continued efforts to conduct research to improve existing products, there is still a great need in the art to develop preferred methods of inhibiting urease and compositions containing urease inhibitors that provide good stability while being able to effectively control enzyme-induced urea decomposition. SUMMARY OF THE INVENTION

[0006] In one aspect, the subject matter described herein relates to a method of inhibiting urease activity, which comprises applying a urease inhibitor composition to the soil, wherein the urease inhibitor composition contains tert-butylhydroquinone and an organic solvent.

[0007] In one aspect, the subject matter described herein relates to a method of fertilizing the soil and / or improving plant growth and / or health, which comprises contacting a urease inhibitor composition with the soil, wherein the urease inhibitor composition contains tert-butylhydroquinone and an organic solvent. In another aspect, the organic solvent is selected from aromatic solvents, sulfoxides, green solvents, safe solvents, or combinations thereof.

[0008] In one aspect, the subject matter described herein relates to an agricultural composition comprising a urease inhibitor composition containing tert-butylhydroquinone and an organic solvent; and a solid urea-containing fertilizer, wherein the surface of the urea-containing fertilizer is coated with the urease inhibitor composition.

[0009] In one aspect, the subject matter described herein relates to an agricultural composition comprising a urease inhibitor composition; and a solid urea-containing fertilizer, wherein the urease inhibitor composition comprises tert-butylhydroquinone; and an organic solvent, and wherein the surface of the urea-containing fertilizer is coated with the urease inhibitor composition.

[0010] In one aspect, the subject matter described herein relates to a method of preparing the disclosed agricultural composition, the method comprising applying a urease inhibitor composition in liquid or dispersion form to the surface of a solid urea-containing fertilizer, thereby coating the solid urea-containing fertilizer, wherein the urease inhibitor composition comprises tert-butylhydroquinone and an organic solvent.

[0011] In one aspect, the subject matter described herein relates to a urease inhibitor composition comprising: tert-butylhydroquinone; an additive selected from additives containing an α,β-unsaturated carbonyl system, acid-containing additives, ester-containing additives, aromatic additives, ethylene glycol-containing additives; and an organic solvent, wherein the tert-butylhydroquinone and the additive components are present in synergistic amounts. Description of the Drawings

[0012] Figure 1 Bar graph showing N-NH4 - , N-NO3 - and total inorganic N (N-NH4 + + N-NO3 - ) concentrations at the end of the experiment. Lowercase letters within the bars indicate significant N-NH4 + differences between treatments (p < 0.005), while letters outside the bars indicate significant N-NO3 - differences. Uppercase letters at the top of the bars indicate significant differences in total inorganic N between treatments; and

[0013] Figure 2 Bar graph showing soil pH at the end of the experiment. Lowercase letters indicate significant differences between treatments (p < 0.005); and Detailed Description

[0014] The presently disclosed subject matter will now be described more fully hereinafter. However, many modifications and other embodiments of the presently disclosed subject matter will come to mind to those skilled in the art in light of the foregoing description. Thus, it is to be understood that the presently disclosed subject matter is not limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. In other words, the subject matter described herein covers all alternatives, modifications, and equivalents. If one or more of the incorporated documents, patents, and similar materials are different from or contradict this application, including but not limited to the defined terms, term usage, the described technologies, etc., this application shall prevail. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety.

[0015] As described above, urea is one of the main nitrogen fertilizers widely used in agricultural production. It is believed that if not applied correctly, up to 40% of the nitrogen applied as urea can be lost because, after field application, it can react with water via urease to form ammonium carbonate. Ammonium carbonate is unstable and decomposes into carbon dioxide and ammonia, which can volatilize and be lost to the air. The losses can be substantial and depend on various factors such as soil pH, soil temperature, soil moisture, the cation exchange capacity of the soil, and the soil organic matter content.

[0016] Many methods for controlling the volatile nitrogen loss of urea have been developed or proposed, including the application of metal salts of copper and zinc, boron compounds, organic urease inhibitors, acid coatings, polymer coatings, and the reaction of urea with aldehydes to form reaction adducts. For example, N-(butyl) thiophosphoric triamide (NBPT) is one of the most well-known urease inhibitors in the agricultural field worldwide and is the active ingredient of a product series. However, the compound itself is thermally unstable and decomposes upon contact with water and acid. Once decomposed, it cannot effectively exert the required inhibitory effect on urease. Therefore, it would be of great value to discover and / or develop new classes of urease inhibitors, compositions, and / or formulations that exhibit improved chemical / thermal stability, are less prone to decomposition, and are more environmentally friendly.

[0017] Advantageously, the compositions and methods described herein have been shown to provide the desired properties for using such urease inhibitors in the agricultural field, particularly when formulated with certain additive components. Specifically, beneficial properties such as (but not limited to) extended thermal / chemical stability, increased shelf life, reduced application rates, ease of handling, extended urease inhibition effect, and acceptable environmental and toxicological profiles have been observed when the urease inhibitor tert-butylhydroquinone (tBHQ) is combined with the additive components. The additive components disclosed herein have a wider variety of different chemical structure classes, and the beneficial properties observed can be seen when both reagents (i.e., tBHQ and the additive component) are present. In some embodiments, the reagents are present in synergistically effective amounts.

[0018] Accordingly, the compositions disclosed herein not only contribute to increasing the availability of plant nutrients by inhibiting urease activity, but also extend the lifespan of their performance as effective urease inhibitors due to their aforementioned beneficial properties.

[0019] I. Definitions

[0020] As used herein, the term "aromatic ring system" refers to a ring system containing at least one heteroaryl ring and / or at least one aryl ring.

[0021] As used herein, the term "heteroaryl" refers to a group containing at least a five- or six-membered unsaturated and conjugated aromatic ring, said ring containing at least two ring carbon atoms and one to four ring heteroatoms selected from nitrogen, oxygen, and / or sulfur. Such heteroaryl is often alternatively referred to as "heteroaromatic" by those skilled in the art. In some embodiments, the heteroaryl has two to twelve carbon atoms, or four to five carbon atoms in the heteroaryl ring. Examples include but are not limited to pyridyl, pyrimidinyl, pyrazinyl, pyrrolyl, furyl, tetrazolyl, isoxazolyl, oxadiazolyl, benzothienyl, benzofuranyl, quinolinyl, isoquinolinyl, etc.

[0022] As used herein, the term "aryl" refers to a group containing at least one unsaturated and conjugated six-membered ring similar to a benzene ring. An aryl having such an unsaturated and conjugated ring is also referred to as an "aromatic" group by those skilled in the art. Preferably, the aryl has 6 to 12 ring carbons. Aryl includes but is not limited to aromatic groups containing phenyl and naphthyl ring groups.

[0023] As used herein, the term "substituted" refers to a moiety (e.g., heteroaryl, aryl, alkyl, and / or alkenyl) where the moiety is bonded to one or more additional organic or inorganic substituents. In some embodiments, the substituted moiety comprises 1, 2, 3, 4, or 5 additional substituents or groups. Suitable organic and inorganic substituents include (but are not limited to) hydroxy, cycloalkyl, aryl, substituted aryl, heteroaryl, heterocycle, substituted heterocycle, amino, mono-substituted amino, di-substituted amino, acyloxy, nitro, cyano, carboxy, alkoxycarbonyl, alkylformamide, substituted alkylformamide, dialkylformamide, substituted dialkylformamide, alkylsulfonyl, alkylsulfinyl, thioalkyl, alkoxy, substituted alkoxy, or haloalkoxy, where the terms are defined herein. Unless otherwise specified herein, organic substituents can contain from 1 to 4 or 5 to 8 carbon atoms. When a substituted moiety is bonded thereto by more than one substituent, then the substituents can be the same or different.

[0024] As used herein, the term "unsubstituted" refers to a moiety (e.g., heteroaryl, aryl, alkenyl, and / or alkyl) as described above that is not bonded to one or more additional organic or inorganic substituents, meaning that such moieties are substituted only with hydrogen.

[0025] As used herein, the terms "halo", "halogen", or "halide" refer to a fluorine, chlorine, bromine, or iodine atom or ion.

[0026] As used herein, the term "alkoxy" or "alkoxide" refers to an alkyl group bonded via a single terminal ether bond; i.e., an "alkoxy" group can be defined as -OR, where R is an alkyl group as defined above. Examples include but are not limited to methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, isobutoxy, and the like.

[0027] As used herein, the term "substituted alkoxy" refers to an alkoxy group as defined above that has one, two, or more than two additional organic or inorganic substituents bonded to the alkyl group. Suitable organic and inorganic substituents include but are not limited to hydroxy, cycloalkyl, amino, mono-substituted amino, di-substituted amino, acyloxy, nitro, cyano, carboxy, alkoxycarbonyl, alkylformamide, substituted alkylformamide, dialkylformamide, substituted dialkylformamide, alkylsulfonyl, alkylsulfinyl, thioalkyl, thiohaloalkyl, alkoxy, substituted alkoxy, or haloalkoxy. When the alkyl group of the alkoxy is bonded thereto by more than one substituent, then the substituents can be the same or different.

[0028] As used herein, the term "amino" refers to a substituted or unsubstituted trivalent nitrogen radical or group structurally related to ammonia (NH3) by replacing one or more hydrogen atoms of ammonia with substituents.

[0029] As used herein, the term "monosubstituted amino" refers to an amino group substituted by a group selected from alkyl, substituted alkyl, or aralkyl, where the term has the same definition as seen herein.

[0030] As used herein, the term "disubstituted amino" refers to an amino group substituted by two groups, which may be the same or different, selected from aryl, substituted aryl, alkyl, substituted alkyl, or aralkyl, where the term has the same definition as disclosed herein. Examples include, but are not limited to, dimethylamino, methylethylamino, diethylamino, etc. The two substituents present may be the same or different.

[0031] As used herein, the term "haloalkyl" refers to an alkyl group as defined above, which is substituted by one or more halogen atoms (such as fluorine, chlorine, bromine, or iodine, preferably fluorine). Examples include, but are not limited to, trifluoromethyl, pentafluoroethyl, etc.

[0032] As used herein, the term "haloalkoxy" refers to a haloalkyl group as defined above, which is directly bonded to oxygen to form trifluoromethoxy, pentafluoroethoxy, etc.

[0033] As used herein, the term "acyl" refers to a group containing a carbonyl (-C(O)-R group), where the R group is hydrogen or has 1 to 8 carbons. Examples include, but are not limited to, formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, heptanoyl, benzoyl, etc.

[0034] As used herein, the term "acyloxy" refers to a group containing a carboxy (-O-C(O)-R) group, where the R group contains hydrogen or 1 to 8 carbons. Examples include, but are not limited to, acetoxy, propionyloxy, butyryloxy, isobutyryloxy, benzoyloxy, etc.

[0035] As used herein, the term "alkyl" refers to a saturated hydrocarbon group containing 1 to 12 carbons, 1 to 8 carbons, 1 to 6 carbons, 1 to 4 carbons, or 5 to 8 carbons. In some cases, alkyl refers to a saturated hydrocarbon group containing more than 8 carbons. An alkyl group is structurally similar to an acyclic alkane compound, which is modified by removing one hydrogen from the acyclic alkane and substituting it with a non-hydrogen group or radical. The alkyl group may be branched or unbranched. A lower alkyl group has 1 to 4 carbon atoms. A higher alkyl group has 5 to 8 carbon atoms. Examples of alkyl, lower alkyl, and higher alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, n-pentyl, n-hexyl, isooctyl, etc.

[0036] As used herein, the term "alkenyl" refers to an unsaturated hydrocarbon group having 2 to 8, 2 to 6, 2 to 4, or 5 to 8 carbons and at least one carbon-carbon double bond. In some cases, alkenyl refers to an unsaturated hydrocarbon group having greater than 8 carbons. The unsaturated hydrocarbon group is similar to the alkyl group as defined above and further comprises at least one carbon-carbon double bond. Examples include but are not limited to vinyl, allyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 5-heptenyl, 6-heptenyl, and the like. The term "alkenyl" includes dienes and trienes having straight and branched chains.

[0037] As used herein, the term "stereoisomer" refers to isomers having the same composition (i.e., the same parts) but differing in the orientation of those parts in space. There are two types of stereoisomers: enantiomers and diastereomers.

[0038] As used herein, the term "enantiomeric excess" (ee) is a measure of the purity of a chiral substance and is used to describe the extent to which the amount of one enantiomer in a sample is greater than the amount of the other enantiomer. The ee of a racemic mixture is 0%, while the ee of a single, completely pure enantiomer is 100%.

[0039] As used herein, the term "diastereomeric excess" (de) is a measure of the purity of a chiral substance and is used to describe the extent to which the amount of one diastereomer in a sample is greater than the amount of the other diastereomer. The de of a racemic mixture is 0%, while the de of a single, completely pure diastereomer is 100%.

[0040] As used herein, the term "urease inhibitor" refers to the property of a compound to inhibit the activity of urease. Inhibition can be quantified as described elsewhere herein.

[0041] As used herein, the term "thermal stability" refers to the stability of a substance when exposed to thermal stimuli over a given period of time. Examples of thermal stimuli include but are not limited to heat generated from a power source and / or heat generated from the sun.

[0042] As used herein, the term "chemical stability" refers to the resistance of a substance to structural changes when exposed to external agents such as air (which can cause oxidation), light (such as sunlight), moisture / water vapor (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).

[0043] As used herein, the term "effective amount" refers to the amount of the urease inhibitor composition and / or the amount of each component in the urease inhibitor composition (i.e., tBHQ and optional additive components) that is sufficient to achieve urease inhibition as described below. More exemplary information regarding the amounts to be used, the mode of application, and suitable ratios is given below. Those skilled in the art are well aware of the fact that such amounts can vary widely and depend on various factors such as weather, target species, location, application pattern, soil type, cultivated plants or substances to be treated, and climatic conditions.

[0044] As used herein, the term "green solvent" should be understood to mean an environmentally friendly solvent or bio-solvent derived from the processing of agricultural crops. Examples of green solvents include ionic liquids, supercritical fluids, water, and supercritical water. These solvents are more eco-friendly, less toxic, and less hazardous compared to traditional organic compounds.

[0045] As used herein, the term "safe solvent" should be understood to mean a solvent that is considered safe for the environment and includes solvents such as water, ethanol, 1-propanol, acetone, acetonitrile, 2-propanol, and methanol.

[0046] As used herein, the term "synergistically effective" refers to an effect obtained from two different chemical substances (e.g., tBHQ and an additive component) that is greater than the sum of their individual effects at the same dose.

[0047] The term "synergistic effect" means that the improvement in plant growth and development is related to at least one effect, the degree of which is greater than the additive effect. The additive effect is the expected effect resulting from the individual action of each active compound. The degree of the synergistic effect is significantly higher than the additive effect. The expected activity of a given combination of two active compounds can be calculated as follows (see Colby, S.R., "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds 15, pages 20 - 22, 1967). The synergistic effect of the combination of active ingredients used in the examples allows the total application rate of the substance to be reduced to achieve the same effect.

[0048] As used herein, the term "micronutrient" is understood to mean a nutrient that is essential for plant growth and health and is required in only very small amounts. 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 guidance number" (SGN) refers to the diameter of a fertilizer particle (expressed as millimeters × 100) based on the median (or midpoint) within a batch. It means that half of the fertilizer particles are larger than the set SGN and half are smaller. It is determined by passing the fertilizer through various sieves and calculating the SGN using the amount retained on each sieve. For example, a fertilizer with an SGN of 250 will have 50% of its particles retained on or around a sieve with an opening of 2.5 millimeters.

[0050] As used herein, the term "median" refers to the value at which half of the particle population is above the point and half is below the point, and is typically reported in millimeters (mm). For a particle size distribution, the median is referred to as the D50 of the particles.

[0051] As used herein, the term "uniformity index" (UI) refers to a variable that represents the relative particle size variation. A UI value in the range of approximately 40 to 60 indicates uniform particle size. The larger the UI value, the more uniform the particle size variation of the product. Values outside this range indicate a greater variability in the particle size distribution. UI is the ratio of the larger (d95) particles to the smaller (d10) particles in a specific particle composition multiplied by 100: The formula for calculating UI is = D10 / D95 × 100, where D10 = particle size (mm) corresponding to 10% passing, and D95 = particle size (mm) corresponding to 95% passing. For example, a product with a UI of 50 means that the average small particles (0.80 mm) are half the size of the average large particles (1.6 mm). Products with different particle sizes and densities can cause inconsistent distributions of the product, resulting in inconsistent results.

[0052] As used herein, the term "sieve opening size" refers to the U.S. sieve opening size (or U.S. sieve size), which is defined as the number of openings in a sieve per square inch. For example, a 36-mesh sieve will have 36 openings, while a 150-mesh sieve will have 150 openings. Since the size of the sieve (per square inch) is constant, the higher the number of sieve openings, the smaller the sieve opening, and the fewer particles will pass through. Generally, U.S. sieve opening sizes are measured using sieves with a minimum of 325 mesh (325 openings per square inch).

[0053] Sometimes, the sieve opening size of a product is labeled with a minus (-) or plus (+) sign. These signs indicate that the particles are all smaller (-) or all larger (+) than the sieve opening size. For example, a product identified as -100 mesh will only contain particles that pass through a 100-mesh sieve. A +100 grade product will contain particles that do not pass through a 100-mesh sieve. When a product grade is labeled with a dash or a slash, it indicates that the particles in the product are within two sieve opening size ranges. For example, a 30 / 70 or 30 to 70 grade will only have particles smaller than 30 mesh and larger than 70 mesh.

[0054] As used herein, the term "particle density" refers to the mass-to-volume ratio of particles and / or granules reported as lbs / ft 3 or kg / m 3 . Different from bulk density, particle density does not include the space between individual particles, but rather is a measurement of the particle density itself.

[0055] As used herein, the term "soil" shall be understood as a natural body that contains living matter (such as microorganisms (e.g., bacteria and fungi), animals, and plants) and inanimate matter (such as minerals and organic matter (e.g., organic compounds in varying degrees of decomposition), liquids, and gases) present on the land surface, and is characterized in that the soil layer is distinguishable from the initial material as a result of various physical, chemical, biological, and anthropogenic processes. From an agricultural perspective, soil is mainly regarded as a substrate for plants and the main nutrient base (plant habitat).

[0056] As used herein, the term "fertilizer" shall be understood as a compound applied to promote the growth of plants and fruits. Fertilizers are typically applied via the soil (for uptake by plant roots) or by foliar application (for uptake by leaves). The term "fertilizer" can be further divided into two main categories: a) organic fertilizers (composed of decomposed plant / animal matter) and b) inorganic fertilizers (composed of chemicals and minerals). Organic fertilizers include manure, slurry, vermicompost, peat, seaweed, sewage sludge, and guano. Green manure crops are also grown regularly to add nutrients (especially nitrogen) to the soil. Manufactured organic fertilizers include compost, blood meal, bone meal, and seaweed extracts. Other examples are enzyme-digested proteins, fish meal, and feather meal. Decayed crop residues from previous years are another source of fertility. Additionally, naturally occurring minerals such as rock phosphate, potassium sulfate, and limestone are also regarded as inorganic fertilizers. Inorganic fertilizers are usually manufactured via chemical processes (such as the Haber - Bosch process), also using naturally occurring mineral deposits and chemically altering them (such as concentrated triple superphosphate). Naturally occurring inorganic fertilizers include Chilean sodium nitrate, rock phosphate, and limestone.

[0057] As used herein, the term "manure" is organic matter used as an organic fertilizer in agriculture. Depending on its structure, manure can be classified into liquid manure, semi-liquid manure, stable or solid manure, and straw manure. Depending on its source, manure can be classified into manure derived from animals or plants. Common forms of animal manure include feces, urine, farm slurry (liquid manure), or farmyard manure (FYM), however FYM also contains a certain amount of plant material (typically straw), which may have been used as bedding for animals. Manure that can be used comes from the following animals, including horses, cattle, pigs, sheep, chickens, turkeys, rabbits, and guano from seabirds and bats. When used as a fertilizer, the application rate of animal manure highly depends on the source (animal type). Plant manure can be derived from any type of plant, however these plants can also be specifically grown for plowing into the soil (e.g., legumes), thereby improving the structure and fertility of the soil. In addition, the plant material used as manure can include the contents of the rumen of slaughtered ruminants, spent hops (residue from brewing beer), or seaweed.

[0058] As used herein, the term "seed" includes all types of seeds, such as corn, seeds, fruits, tubers, seedlings, and similar forms. The seeds used can be the seeds of the applicable plants mentioned above, and can also be the seeds of genetically modified plants or plants obtained by conventional breeding methods.

[0059] Throughout this specification and the claims, the words "comprise", "comprises", and "comprising" are used in a non-exclusive sense, unless the context otherwise requires and are synonymous with "include", "contain", or "characterized by", which means that it is open-ended and does not exclude additional unrecited elements or method steps.

[0060] As used herein, the term "about" when referring to a value means to cover variations of ±5% in some embodiments, ±2% in some embodiments, ±1% in some embodiments, ±0.5% in some embodiments, and ±0.1% in some embodiments relative to the specified amount, as such variations are suitable for carrying out the disclosed methods or using the disclosed compositions.

[0061] When a range of values is provided, it is to be understood that unless the context clearly indicates otherwise, each intermediate value (to one tenth of the unit of the lower limit) between the upper and lower limits of the stated range and any other stated value or intermediate value within that specified range is covered. Also covered are the upper and lower limits of these smaller ranges that can independently be included within a smaller range, subject to any specific exclusions within the specified range. Where the specified range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

[0062] Additional definitions may follow below.

[0063] II. Composition

[0064] The presently disclosed subject matter relates to a urease inhibitor composition that includes tert-butylhydroquinone (tBHQ) and an organic solvent. As mentioned above, these urease inhibitor compositions can exhibit desirable properties such as increased chemical / thermal stability, increased shelf life, reduced volatility, reduced application rates, ease of handling, an extended / prolonged effect of urease inhibition, and excellent environmental and toxicological characteristics, all of which generally contribute to improved performance in the art.

[0065] In some embodiments, the urease inhibitor composition further includes an additive component. The function of the additive component is to facilitate the beneficial properties of tBHQ when formulated alone or in combination with an agricultural product (i.e., a fertilizer). In some embodiments, the additive component and the organic solvent can be the same. In some embodiments, the organic solvent and the additive component are different.

[0066] The amount of tert-butylhydroquinone present in the urease inhibitor composition can vary. For example, in some embodiments, based on the total weight of the urease inhibitor composition, the amount of tert-butylhydroquinone is in the range of from about 0.001 wt% to about 70 wt%, from about 0.01 wt% to about 65 wt%, from about 0.1 wt% to about 65 wt%, from about 1 wt% to about 65 wt%, from about 1 wt% to about 60 wt%, from about 1 wt% to about 50 wt%, from about 5 wt% to about 45 wt%, from about 10 wt% to about 40%, from about 15 wt% to about 35%, from about 20 wt% to about 30% or from about 25 wt% to about 30%. In some embodiments, based on the total weight of the urease inhibitor composition, the amount of tert-butylhydroquinone present in the urease inhibitor composition is less than about 70 wt%, about 65 wt%, about 50 wt%, about 45 wt%, about 40 wt%, about 35 wt%, about 30 wt%, about 25 wt%, about 20 wt%, about 15 wt%, about 10 wt%, about 5 wt% or less than about 1 wt%.

[0067] The amount of the additive component in the urease inhibitor composition can vary. For example, in some embodiments, based on the total weight of the urease inhibitor composition, the amount of the additive component is in the range of about 0.001 wt% to about 60 wt%, about 0.01 wt% to about 60 wt%, about 0.1 wt% to about 60 wt%, about 1 wt% to about 60 wt%, about 2 wt% to about 55 wt%, about 5 wt% to about 50 wt%, about 10 wt% to about 45%, about 15 wt% to about 40%, about 20 wt% to about 35%, about 20 wt% to about 30% or about 20 wt% to about 25%. In some embodiments, based on the total weight of the urease inhibitor composition, the amount of the additive component present in the urease inhibitor composition is less than about 60 wt%, about 55 wt%, about 50 wt%, about 45 wt%, about 40 wt%, about 35 wt%, about 30 wt%, about 25 wt%, about 20 wt%, about 15 wt%, about 10 wt%, about 5 wt% or less than about 1 wt%.

[0068] In some embodiments, the relative amounts of tert-butylhydroquinone and the additive component present in the urease inhibitor composition can vary. In some embodiments, the amounts of tert-butylhydroquinone and the additive component present in the urease inhibitor composition are in the range of about 1:1000 to about 1000:1, about 1:500 to about 500:1, about 1:250 to about 250:1, about 1:150 to about 150:1, about 1:100 to about 100:1, about 1:75 to about 75:1, about 1:50 to about 50:1, about 1:25 to about 25:1, about 1:15 to about 15:1, about 1:10 to about 10:1, about 1:5 to about 5:1 or about 1:2 to about 2:1 weight ratio of tert-butylhydroquinone to the additive component. In some embodiments, tert-butylhydroquinone and the additive component are present in the urease inhibitor composition in a synergistically effective amount.

[0069] Tert-butylhydroquinone, the additive component and the organic solvent are discussed in more detail below.

[0070] A. Tert-butylhydroquinone

[0071] Tert-butylhydroquinone (tBHQ, tertiary butylhydroquinone) is a synthetic aromatic organic compound. It is a derivative of hydroquinone (which is of the type of phenol), substituted by tert-butyl groups, and has the following chemical structure:

[0072]

[0073] TBHQ is mainly used as a preservative for unsaturated vegetable oils and many edible animal fats in foods, where it acts as an antioxidant. In addition, tBHQ can be used in other applications, such as: (a) as a fixative in perfumes to reduce the evaporation rate and improve stability; (b) as a stabilizer in industry to inhibit the self-polymerization of organic peroxides; (c) as an antioxidant in fuels, such as biodiesel; and (d) as an additive in varnishes, paints, resins, and oilfield additives.

[0074] However, its effect on urease inhibition, especially urease inhibition in soil, has not been previously disclosed. Therefore, when tert-butylhydroquinone is exposed to soil alone or in combination with fertilizers (especially urea-containing fertilizers), it exhibits extremely strong inhibitory properties against urease, and this finding is both unexpected and surprising. Additional studies have shown that its strong urease inhibitory properties are largely due to the tert-butyl alkyl substituent present in the compound, as unsubstituted hydroquinone exhibits significantly weaker urease inhibitory properties.

[0075] B. Additive Components

[0076] The additive components disclosed herein are compounds that further promote and / or enhance the urease inhibitory properties of tBHQ when added to a urease inhibitor composition. In some embodiments, the additive components have a synergistic effect on the enzyme inhibitory properties of tBHQ.

[0077] In some embodiments, such additive components are selected from compound classes such as additives containing an α,β-unsaturated carbonyl system, acid-containing additives, ester-containing additives, aromatic additives, ethylene glycol-containing additives, or combinations thereof. Without being bound by theory, it is believed that such compounds can participate in hydrogen bonding with tert-butylhydroquinone and can thus be suitable co-solvents in the disclosed urease inhibitory compositions.

[0078] In some embodiments, the additive component comprises an additive containing an α,β-unsaturated carbonyl system. In some embodiments, the additive containing an α,β-unsaturated carbonyl system is derived from acyclic monoterpenes and / or contains one or more isoprene units. In some embodiments, the additive containing an α,β-unsaturated carbonyl system contains an aromatic ring system. Exemplary additives containing an α,β-unsaturated carbonyl system include (but are not limited to) citral (3,7-dimethyl-2,6-octadienal), mesityl oxide, α-amylcinnamaldehyde, coumarin (2H-chromen-2-one), or combinations thereof. In some embodiments, the additive component is mesityl oxide.

[0079] In some embodiments, the additive component comprises an additive containing an aromatic ring system, which can be any compound containing an aromatic ring system (e.g., a 6-membered aromatic ring, such as an aryl or heteroaromatic moiety, such as a heteroaryl). In some embodiments, the aromatic ring system is substituted with one or more hydrophilic groups (i.e., hydroxyl (-OH), alkoxide (-O(C2-C6 alkyl)), ester (-C(=O)O(C1-C6 alkyl)) and / or acyl (-C(=O)(C1-C6 alkyl))). Exemplary aromatic-containing additives include, but are not limited to, butylated hydroxyanisole, eugenol, salicylaldehyde, acetophenone, methyl salicylate, or combinations thereof.

[0080] In some embodiments, the additive component comprises an acid-containing additive, which can be any compound containing one or more carboxylic acid (-COOH) groups, sulfonic acid (-SO3H) groups, and / or phosphoric acid (-PO3H) groups. In some embodiments, the acid-containing additive contains a C2-C 10 alkyl chain that can be saturated or unsaturated. In some embodiments, the acid-containing additive is a cycloaliphatic acid. Exemplary acid-containing additives include, but are not limited to, itaconic acid, adipic acid, maleic acid, octanoic acid, ethyl maltol, ascorbic acid, levulinic acid, or combinations thereof.

[0081] In some embodiments, the additive component comprises an ester-containing additive. In some embodiments, the ester-containing additive is a substituted or unsubstituted C2-C 12 alkyl ester. In some embodiments, such esters are substituted with a hydrophilic group such as hydroxyl (-OH). Exemplary ester-containing additives include, but are not limited to, triethyl citrate, isobornyl acetate, propylene carbonate, ethyl lactate, or combinations thereof.

[0082] In some embodiments, the additive component comprises a glycol-containing additive, which is an alkyl compound containing at least two hydroxyl (-OH) groups. Exemplary glycol-containing additives include, but are not limited to, diethylene glycol monoethyl ether, ethylene glycol, monobutyl ether, or combinations thereof.

[0083] In some embodiments, the additive component comprises stereoisomers. In some embodiments, the additive component comprises enantiomers. In such embodiments, the additive component may comprise at least about 50%, about 60%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 98%, about 99%, about 99.5% or at least about 99.8% enantiomeric excess (ee) enantiomeric purity. In some embodiments, the additive component comprises diastereomers. In such embodiments, the additive component may comprise at least about 50%, about 60%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 98%, about 99%, about 99.5% or at least about 99.8% diastereomeric excess (de) diastereomeric purity. In some embodiments, the additive component is racemic.

[0084] C. Organic Solvents

[0085] In some embodiments, the organic solvent is one or more polar organic solvents. In some embodiments, one or more polar organic solvents are EPA-approved. EPA-approved solvents are those solvents found in the electronic version of the Federal Regulations, such as in Title 40, Chapter I, Subchapter E, Part 180. EPA-approved solvents include, but are not limited to, the solvents listed in Table 1.

[0086] Table 1. EPA-Approved Solvents

[0087]

[0088]

[0089] In some embodiments, the organic solvent is selected from sulfones, sulfoxides, aromatic solvents, halogenated solvents, glycol solvents, fatty acid solvents and acetate-containing solvents, ketone-containing solvents, ether polyol-containing solvents, amide-containing solvents and combinations thereof. In some embodiments, the organic solvent is environmentally friendly, such as a green solvent, a safe solvent or a combination thereof.

[0090] In some embodiments, one or more organic solvents are relatively water-free. 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 water based on the total weight of the solvent. In some embodiments, the organic solvent is a liquid at 20 °C.

[0091] In some embodiments, the organic solvent is a sulfone. A sulfone is a solvent containing a sulfonyl functional group attached to two carbon atoms and is represented by the general structural formula R'-S(=O)2-R”, where the two R groups contain carbon atoms. Sulfone solvents can be, but are not limited to, sulfolane, methylsulfolane (3-methylsulfolane), dimethyl sulfone, or combinations 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”, where the two R groups contain carbon atoms. Sulfoxide solvents can be, but are not limited to, dimethyl sulfoxide.

[0092] In some embodiments, the organic solvent is an ether polyol. An ether polyol contains multiple hydroxyl groups. Ether polyol solvents can be, but are not limited to, polyethylene glycol, polypropylene glycol, polyalkylene glycols, and related compounds. In some embodiments, 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 combinations thereof. Exemplary polypropylene glycols include, but are not limited to, dipropylene glycol, tripropylene glycol, or combinations thereof. In some embodiments, polypropylene glycol has three terminal alcohols. Exemplary polypropylene glycols with three terminal alcohols (referred to as propoxylated glycerol) include, but are not limited to, Dow PT250 (which is a glycerol ether polymer with a molecular weight of 250 and three terminal hydroxyl groups) and Dow PT700 (which is a glycerol ether polymer with a molecular weight of 700 and three terminal hydroxyl groups). In some embodiments, the ether polyol comprises a polyethylene or polypropylene glycol in a molecular weight range between about 200 and about 10,000 Da. In some embodiments, one or more of the hydroxyl groups present in the ether polyol are 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, diethylene glycol n-butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, dipropylene glycol ethyl ether acetate, or combinations thereof.

[0093] In some embodiments, the organic solvent is a glycol solvent. A glycol is an alcohol containing two hydroxyl (-OH) groups attached to different carbon atoms (e.g., terminal carbon atoms). Exemplary glycol solvents include, but are not limited to, ethylene glycol and / or propane-1,2,3-triol.

[0094] In some embodiments, the organic solvent is a fatty acid solvent. Generally, a fatty acid is characterized as a compound having a carboxylic acid and an aliphatic chain containing multiple carbon atoms, which can be saturated or unsaturated. In some embodiments, the fatty acid contains between 3 and about 20 carbon atoms. Examples of fatty acid solvents include, but are not limited to, dialkylamides of fatty acids (e.g., dimethylamides). Examples of dimethylamides of fatty acids include, but are not limited to, dimethylamide of octanoic acid, C8-C 10Dimethylamides of fatty acids (Agnique AMD810), dimethyl lactamides (Agnique AMD3L), or combinations thereof.

[0095] 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 solvents include, but are not limited to, isophorone, trimethylcyclohexanone, or combinations thereof.

[0096] 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 combinations thereof.

[0097] In some embodiments, the organic solvent is an amide-containing solvent, which can be any solvent containing an amide functional group (-NR'C(=O)R”; where R is an alkyl group). Examples of amide-containing solvents include, but are not limited to, Rhodiasolv ADMA10 (CAS Registry Number 14433-76-2; N,N-dimethyloctanamide), Rhodiasolv ADMA810 (CAS Registry Number 1118-92-9 / 14433-76-2; blend of N,N-dimethyloctanamide and N,N-dimethyldecanamide), Rhodiasolv PolarClean (CAS Registry Number 1174627-68-9; methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate), or combinations thereof.

[0098] 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-trichloroethane.

[0099] 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, naphthylene, or combinations thereof. In some embodiments, the aromatic hydrocarbon is substituted. Examples of substituted aromatic hydrocarbons include, but are not limited to, alkyl-substituted benzene and / or alkyl-substituted naphthalene. Examples of alkyl-substituted benzene include xylene, toluene, propylbenzene, or combinations thereof. In some embodiments, the organic solvent contains xylene. In some embodiments, the aromatic hydrocarbon is a mixture of substituted and unsubstituted aromatic hydrocarbons, such as, but not limited to, a mixture of cycloalkane and alkyl-substituted naphthalene.

[0100] 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 Registry Number 64742-95-6), which is a hydrocarbon combination obtained by distilling an aromatic stream mainly composed of aromatic hydrocarbons (C8 to C 10 ); or Aromatic 200, a solvent containing a mixture of the following: aromatic hydrocarbons (C 11 -C 14 ) present in an amount of 50-85% by weight based on the total weight of the Aromatic 200 composition; naphthalene (CAS Registry Number 91-20-3) present in an amount of 5-20% by weight; aromatic hydrocarbons (C 10 ), excluding naphthalene, present in an amount of 5-15% by weight; and aromatic hydrocarbons (C 15 -C 16 ) present in an amount of 5-15% by weight. In some embodiments, the aromatic hydrocarbon is a mixture of Aromatic 100 and Aromatic 200.

[0101] In some embodiments, the organic solvent is a green solvent. Exemplary green solvents other than those mentioned above include (but are not limited to) water, methanol, acetone, dimethyl carbonate, ethyl acetate, propyl acetate, 1-propanol, 1-butanol, toluene, dimethyl sulfoxide (DMSO), acetic acid, acetonitrile, tetrahydrofuran (THF), ethylene glycol, 2-methyltetrahydrofuran, methyl tert-butyl ether, methylcyclohexane, xylene, cyclohexane, isooctane, heptane, methyl ethyl ketone, ethylene glycol, methyl tert-butyl ether, toluene, cyclohexane, methylcyclohexane, or a combination thereof. In some embodiments, the green solvent contains DMSO. In some embodiments, the green solvent contains xylene.

[0102] In some embodiments, the organic solvent is a safe solvent. Exemplary safe solvents other than those already mentioned above include (but are not limited to) simple alcohols (such as methanol, ethanol, isopropanol, etc.) and / or alkanes (such as heptane, hexane, etc.).

[0103] In some embodiments, the organic solvent is the same as the additive component described above, meaning that the organic solvent is selected from the additive components described above.

[0104] In some embodiments, a composition containing tert-butylhydroquinone (and optional additive components) can be formulated with two or more different solvent types. The tert-butylhydroquinone (and optional additive components) can be formulated in two different solvent types that can exhibit high solvation, lack of volatility, and suitable environmental and toxicological characteristics. The two different solvent types can be selected from two different aromatic solvents, two different sulfones, two different amide-containing solvents, two different ether polyols, two different sulfoxides, two different amide-containing solvents, two different fatty acid solvents, two different green solvents, two different safe solvents, or a sulfoxide and an aromatic solvent. In some embodiments, the two different solvent types are xylene and dimethyl sulfoxide. The amount of each solvent type present in the composition can vary. In some embodiments, based on the total weight of the composition, the first solvent of two or more different solvent types (e.g., xylene) is present in an amount in the range of about 10% to about 90%, about 20% to about 80%, about 25% to about 70%, about 30% to about 60%, about 35% to about 55%, or about 40% to about 50% w / w. In some embodiments, based on the total weight of the composition, the first solvent of two or more different solvent types is present in an amount less than about 95%, about 90%, about 85%, about 80%, about 75%, about 70%, about 65%, about 60%, about 55%, 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% w / w. In some embodiments, based on the total weight of the composition, the second solvent of two or more different solvent types (e.g., dimethyl sulfoxide (DMSO)) is present in an amount in the range of about 10% to about 90%, about 20% to about 80%, about 25% to about 70%, about 30% to about 60%, about 35% to about 55%, about 40% to about 50% w / w. In some embodiments, based on the total weight of the composition, the second solvent of two or more different solvent types is present in an amount less than about 95%, about 90%, about 85%, about 80%, about 75%, about 70%, about 65%, about 60%, about 55%, about 50%, about 45%, about 40%, about 35%, about 30%, about 25%, about 20%, about 15%, about 10%, about 5%, or less than 1% w / w.

[0105] In some embodiments, the relative amounts of the two different solvent types can vary. For example, in some embodiments, the first solvent and the second solvent are present in the urease inhibitor composition in amounts in the range of about 100:1 to about 1:100, about 75:1 to about 1:75, about 50:1 to about 1:50, about 25:1 to about 1:25, about 10:1 to about 1:10, about 5:1 to about 1:5, about 3:1 to about 1:3, about 2:1 to about 1:2, or about 1:1 weight ratio of the first solvent to the second solvent. In some embodiments, the first solvent is dimethyl sulfoxide and the second solvent is xylene, and they are present in the urease inhibitor composition in amounts in the range of about 1:2 to about 2:1 or about 1:1 weight ratio.

[0106] The organic solvent can be present in the composition in an amount of 0.1% w / w to about 99.9% w / w, based on the total weight of the urease inhibitor composition. In some embodiments, based on the total weight of the composition, the amount of the organic solvent is less than about 95%, about 90%, about 85%, about 80%, about 75%, about 70%, about 65%, about 60%, about 55%, about 50%, about 45%, about 40%, about 35%, about 30%, about 25%, about 20%, about 15%, about 10%, or less than about 5% w / w. In embodiments, based on the total weight of the composition, the amount of the organic solvent is about 5% to about 98%, about 10% to about 90%, about 20% to about 80%, about 25% to about 75%, about 30% to about 70%, about 35% to about 65%, about 40% to about 60%, or about 45% to about 55% w / w.

[0107] In some embodiments, the urease inhibitor compositions disclosed herein can be formulated to include one or more co-formulants. Exemplary co-formulants include (but are not limited to) any co-formulants known in the art, such as solvents, surface-active ingredients (i.e., surfactants), dispersants, carriers, stabilizers, wetting agents, emulsifiers, defoamers, preservatives, dyes, and the like.

[0108] In some embodiments, the urease inhibitor compositions disclosed herein are formulated to be free of any co-formulants. In some embodiments, the urease inhibitor composition consists of tBHQ and an organic solvent. In some embodiments, the urease inhibitor composition consists of tBHQ, an organic solvent, and an additive component.

[0109] III. Agricultural Compositions

[0110] Any of the described urease inhibitor compositions can be combined with one or more other ingredients selected from the group consisting of: fertilizers; agricultural active compounds; seeds; compounds having urease inhibition activity, nitrification inhibition activity, pesticides, herbicides, insecticides, fungicides, acaricides, and the like.

[0111] In some embodiments, the described urease inhibitor composition can be mixed with a fertilizer product in liquid form or can be applied as a surface coating to a fertilizer product in solid form.

[0112] In some embodiments, the described urease inhibitor composition is thoroughly mixed with a fertilizer product in liquid form. In such products containing a combined fertilizer / urease inhibitor composition, tert-butylhydroquinone (or the urease inhibitor composition) can be present in such combined products at a level of from about 0.001 g to about 20 g per 100 g of fertilizer, from about 0.01 to 7 g per 100 g of fertilizer, from about 0.08 g to about 5 g per 100 g of fertilizer, or from about 0.09 g to about 2 g per 100 g of fertilizer. In the case of products containing a combined fertilizer / urease inhibitor composition, the combined product can be applied such that the amount of tert-butylhydroquinone (or the urease inhibitor composition) applied is at a level of from about 10 to 150 g per acre of soil, from about 30 to 125 g per acre of soil, or from about 40 to 120 g per acre of soil.

[0113] In some embodiments, the described urease inhibitor composition is applied to the surface of the fertilizer in liquid form or in the form of a dispersion. When the urease inhibitor composition is used as a coating, the urease inhibitor composition can comprise from about 0.005 wt% to about 15 wt% of the coated fertilizer product, from about 0.01 wt% to about 10 wt% of the coated fertilizer product, from about 0.05 wt% to about 2 wt% of the coated fertilizer product, or from about 0.5 wt% to about 1 wt% of the coated fertilizer product.

[0114] In some embodiments, the fertilizer coated with the described urease inhibitor composition is a solid urea-containing fertilizer. In some embodiments, the solid urea-containing fertilizer is in the form of granules or pellets. In some embodiments, the shape of the granules or pellets is round (e.g., spherical or egg-shaped), but is not limited thereto. Additional shapes include cubes, rectangles, and / or irregular shapes.

[0115] In some embodiments, the granule / pellet urea-containing fertilizer contains granules / pellets having an average screen size range of 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 granule / pellet urea-containing fertilizer contains granules / pellets having an average screen size range of 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 (d50) of the granular / pelleted urea-containing fertilizer is in the range of about 0.1 to 3.5 mm, about 0.5 to about 2.5 mm, or 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 (d50) of the granular / pelleted 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 / pelleted urea-containing fertilizer contains granules / pellets having a size guide number (SGN) in the range of about 10 to about 500, about 50 to about 450, about 75 to about 400, about 80 to about 250, or about 90 to about 230.

[0118] In some embodiments, the granular / pelleted urea-containing fertilizer contains granules / pellets having a uniformity index (UI) in the range of about 30 - 40, 30 - 50, 35 - 45, 40 - 60, 40 - 50, or 50 - 60 (indicating uniform particle size).

[0119] In some embodiments, the granular / pelleted urea-containing fertilizer contains granules / pellets having a particle density in the range of about 10 - 150 lbs / ft 3 、30 - 100 lbs / ft 3 、about 45 - 85 lbs / ft 3 or about 45 - 60 lbs / ft 3 of the granules / pellets.

[0120] In some embodiments, the granular / pelleted urea-containing fertilizer contains granules / pellets having a bulk density of about 10 - 150 lbs / ft 3 、30 - 100 lbs / ft 3 、about 45 - 75 lbs / ft 3 、about 50 - 70 lbs / ft 3 or about 60 - 70 lbs / ft 3 of the granules / pellets. In some embodiments, the bulk density is the "loose" bulk density.

[0121] Granulation (including urea) of fertilizers can be carried out using any known granulation method in the art. In some embodiments, dry granulation methods (such as compaction granulation methods) can be used to achieve granulation of urea-containing fertilizers. During the physical process, fine powdered urea-containing particles are formed into granules without compromising the chemical stability and / or structural integrity of the urea source used. This enables the product to be handled, blended, and spread uniformly in farmland while maintaining its unique chemical properties. In some embodiments, granulation of urea-containing fertilizers can be achieved via pan granulation, drum granulation, extrusion, palletization, particle comminution, but is not limited thereto.

[0122] A. Fertilizer

[0123] In some embodiments, the agricultural product is a fertilizer. The fertilizer can be a solid fertilizer, such as (but not limited to) granular fertilizer, and the urease inhibitor composition can be applied to the fertilizer in the form of a liquid dispersion. However, the fertilizer can also be in liquid form, and the urease inhibitor composition in liquid form can be mixed with the liquid fertilizer. The fertilizer can be selected from the group consisting of: starter fertilizers, phosphate-based fertilizers, nitrogen-containing fertilizers, phosphorus-containing fertilizers, potassium-containing fertilizers, calcium-containing fertilizers, magnesium-containing fertilizers, boron-containing fertilizers, chlorine-containing fertilizers, zinc-containing fertilizers, manganese-containing fertilizers, copper-containing fertilizers, urea and ammonium nitrite fertilizers and / or and / or molybdenum-containing substance fertilizers. In some embodiments, the fertilizer is or contains urea and / or ammonia, including anhydrous ammonia fertilizer. In some embodiments, the fertilizer contains plant-available nitrogen, phosphorus, potassium, sulfur, calcium, magnesium or micronutrients. In some embodiments, the fertilizer is a solid, granular, fluid suspension, gas or solid solution fertilizer. In some embodiments, the fertilizer contains micronutrients. Micronutrients are essential elements that plants require in small amounts. In some embodiments, the fertilizer contains metal ions selected from the group consisting of: Fe, Mn, Mg, Zn, Cu, Ni, Co, Mo, V and Ca. In some embodiments, the fertilizer contains gypsum, members of the kieserite group, potassium products, potassium magnesium sulfate, elemental sulfur or potassium magnesium sulfate. These fertilizers can be granular, liquid, gaseous or mixtures (such as suspensions of solid fertilizer particles in liquid substances). For example, in some embodiments, the fertilizer is a urea-containing fertilizer in solid form. In another embodiment, the fertilizer is a urea-containing fertilizer in liquid form.

[0124] In some embodiments, the urease inhibitor composition is combined with any suitable liquid fertilizer or used as a coating for any suitable solid fertilizer for application to farmland and / or crops.

[0125] The described urease inhibitor composition can be applied by applying the fertilizer. The urease inhibitor composition can be applied before, after or simultaneously with the application of the fertilizer.

[0126] Fertilizer products containing urease inhibitor compositions can be applied in any manner that benefits the crop of interest. In some embodiments, the product is applied to the growth medium in a band or row application. In some embodiments, the product is applied to the growth medium before sowing or transplanting the desired crop plants or throughout the growth medium. In some embodiments, the product is applied to the root zone of growing plants.

[0127] Plants and / or crops include plants such as cereals, fruit trees, fruit shrubs, cereals, legumes, and combinations thereof. Exemplary crops include (but are not limited to) rye, oats, corn, rice, sorghum, triticale, rapeseed, rice, soybeans, sugar beets, sugar cane, turf, fruit trees, palm trees, coconut trees or other nuts, grapes, fruit shrubs, fruit tree plants, beets, fodder beets, pome fruits, stone fruits, apples, pears, plums, peaches, almonds, cherries, and berries such as strawberries, raspberries, and blackberries; legumes such as kidney beans, lentils, peas, soybeans, peanuts; oil plants such as rapeseed, mustard, sunflowers; cucurbitaceae such as zucchini, cucumbers, melons; fiber plants such as cotton, flax, hemp, jute; citrus fruits such as oranges, lemons, grapefruits, and tangerines; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, sweet potatoes, yams, peppers; and ornamental plants such as flowers, shrubs, broadleaf trees, and evergreens such as conifers, cereals, wheat, barley, oats, winter wheat, spring wheat, winter barley, spring barley, triticale, rye, winter durum wheat, spring durum wheat, winter oats, spring oats, forage grains, ryegrass, cocksfoot, fescue, timothy, seed grass, and lawns and any combination thereof.

[0128] B. Seeds

[0129] Some embodiments describe agricultural seeds coated with a urease inhibitor composition as disclosed herein. The urease inhibitor composition can be present in the seed product at a level of about 0.001 wt% to about 10 wt%, about 0.004 wt% to about 2 wt%, about 0.01 wt% to about 1 wt%, or about 0.1 wt% to about 1 wt% (or not more than about 10 wt%, about 9 wt%, about 8 wt%, about 7 wt%, about 6 wt%, about 5 wt%, about 4 wt%, about 3 wt%, about 2 wt%, about 1 wt%, about 0.5 wt%, about 0.1 wt%, about 0.01 wt%, or not more than 0.001 wt%) based on the total weight of the coated seed product. The seeds can be, but are not limited to, wheat, barley, oats, triticale, rye, rice, corn, soybeans, cotton, or rapeseed.

[0130] C. Others

[0131] In some embodiments, a urease inhibitor compound, a nitrification inhibitor compound, a pesticide, a herbicide, an insecticide, a fungicide, and / or an acaricide are combined with the urease inhibitor compositions disclosed herein. As used herein, "pesticide" refers to any reagent having pesticidal activity (e.g., herbicides, insecticides, fungicides) and is preferably selected from the group consisting of insecticides, herbicides, and mixtures thereof, but generally does not include materials claimed to have a plant fertilizing effect, such as sodium borate and zinc compounds, such as zinc oxide, zinc sulfate, and zinc chloride. For a non-limiting list of pesticides, see "Farm Chemicals Handbook 2000, 2004" (Meister Publishing Co, Willoughby, OH), which is hereby incorporated by reference in its entirety.

[0132] 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, etc.,

[0133] 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, carbondisulfide, 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, methyl chlorpyrifos, 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, Saifuling, 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 methylsulfonate, 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, dinobutonDinocap, Dinocap-4, Dinocap-6, Dinocton, Dinopenton, Dinoprop, Dinosam, Dinosulfon, Dinotefuran, Dinoterbon, Diofenolan, Dioxabenzofos, Dioxacarb, Dioxathion, Diphenyl sulfone, Disulfiram, Disulfoton, Dithicrofos, DNOC, Dofenapyn, Doramectin, Ecdysterone, Emamectin, EMPC, Empenthrin, Endosulfan, Endothion, Endrin, EPN, Epofenonane, Eprinomectin, Esfenvalerate, Etaphos, Ethiofencarb, Ethion, Ethiprole, Ethoate methyl, Ethoprophos, Ethyl DDD, Ethyl formate, Ethylene dibromide, Ethylene dichloride, Ethylene oxide, Etofenprox, Etoxazole, Etrimfos, EXD, Famphur, Fenamiphos, Fenazaflor, Fenazaquin, Fenbutatin oxide, Fenchlorphos, Fenethacarb, Fenfluthrin, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpirithrin, Fenpropathrin, Fenpyroximate, Fenson, Fensulfothion, Fenthion, Ethyl fenthion, Fentrifanil, Fenvalerate, FipronilFlonicamid, Fluacrypyrim, Fluazuron, Flubendiamide, Flubenzimine, Flucofuron, Flucycloxuron, Flucythrinate, Fluenetil, Flufenerim, Flufenoxuron, Flufenprox, Flumethrin, Fluorbenside, Fluvalinate, Fonofos, Formetanate, Formothion, Formparanate, Fosmethilan, Fospirate, Fosthiazate, Fosthietan, Butathiofos, 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, Methyl Iodide, 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 IIIChloropentacyclo (kelevan), kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, lithidathion, 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, methyl chloroform, dichloromethane, 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, oxydisulfoton, p-dichlorobenzene, parathion, methyl parathion, penfluron, pentachlorophenolPermethrin, Phenkapton, Phenothrin, Phenthoate, Phorate, Phosalone, Phosfolan, Phosmet, Phosnichlor, Phosphamidon, Phosphine, Phosphocarb, Phoxim, Methyl Phoxim, Pirimetaphos, Pirimicarb, Pirimiphos Ethyl, Pirimiphos Methyl, Potassium Arsenite, Potassium Thiocyanate, pp'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, Methyl Quinalphos, 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.

[0134] Exemplary fungicides include (but are not limited to) acibenzolar, acyl amino acid fungicides, acypetacs, aldimorph, aliphatic nitrogen-containing 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, benzoyl aniline fungicides, benzimidazole fungicides, benzimidazole precursor fungicides, benzimidazole-based carbamate 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, phenyl carbamate 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 (imidazole), conazole fungicides (triazole), copper(II) acetate, copper(II) basic carbonate, copper fungicides, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride basic, 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, dichlorobenzene, 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, dithiocarbamate fungicides, DNOC, dodemorph, dodicindodine, donatodine, drazoxolon, edifenphos, epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, ethylene oxide, ethylmercury 2,3-dihydroxypropylthiol, 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, furanilide fungicide, furaniline fungicide, furcarbanil, furconazole, cis-furconazole, furfural, furmecyclox, furophanate, glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene, hexachlorobutadieneHexachlorophene, hexaconazole, hexylthiofos, hydrargaphen, hymexazol, imazalil, imibenconazole, imidazole fungicides, iminoctadine, inorganic fungicides, inorganic mercury fungicides, methyl iodide, ipconazole, iprobenfos, iprodione, iprovalicarb, isopropyl alcohol, isoprothiolane, isovaledione, isopyrazam, kasugamycin, ketoconazole, kresoxim-methyl, limesulfur / lime sulphur, mancopper, mancozeb, maneb, mebenil, mecarbinzid, mepanipyrim, mepronil, mercuric chloride (obsolete), mercuric oxide (obsolete), mercurous chloride (obsolete), metalaxyl, metalaxyl-M (also known as mefenoxam), metam, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl isothiocyanate, methyl mercuric benzoate, methyl mercuric dicyandiamide, methyl mercuric pentachlorophenol, metiram, metominostrobin, metrafenone, metsulfovax, milneb, morpholine fungicides, myclobutanil, myclozolin, N-(ethylmercury)-p-toluenesulfonanilide, nabam, natamycin, nystatin, β-nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone, ofurace, oprodione, organic mercury fungicides, organophosphorus fungicides, organotin fungicides (obsolete), o-phenylphenol, orysastrobinoxadixyl, oxathiin fungicides, oxazole fungicides, oxine copper, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, pentachlorophenol, penthiopyrad, phenylmercuriurea, phenylmercury acetate, phenylmercury chloride, phenylmercury derivatives of catechol, phenylmercury nitrate, phenylmercury salicylate, phenylthioamide fungicides, phosdiphen, phosphites, phthalide, phthalimide fungicides, picoxystrobin, piperalin, polyurethanes, polydithiocarbamate 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 o-phenylphenate, sodium pentachlorophenate, sodium polysulfide, spiroxamineStreptomycin, 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, thienyl fungicides, thioquinox, thiram, tiadinil, tioxymid, tivedo, tolclofos-methyl, tolnaftate, tolylfluanid, methylmercuric acetate, triadimefon, triadimenol, triamiphos, triarimol, triazbutil, triazine fungicides, triazole fungicides, triazoxide, tributyltin oxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, unclassified fungicides, undecylenic acid, uniconazole, uniconazole-P, urea fungicides, validamycin, valinamide fungicides, vinclozolin, voriconazole, zarilamid, zinc naphthenate, zineb, ziram, and / or zoxamide.

[0135] In some embodiments, the compositions of the presently disclosed subject matter are products of pesticidal / urease inhibitor compositions comprising a pesticide and tert-butylhydroquinone (and optionally an additive component). In some embodiments, the pesticide is a herbicide, an insecticide, or a combination thereof.

[0136] The amount of the urease inhibitor composition in the product of the pesticidal / urease inhibitor composition can vary. In some embodiments, based on the total weight of the product of the pesticidal / urease inhibitor composition (considered as 100 wt%), the urease inhibitor composition is present in an amount at a level of about 0.05 wt% to about 10 wt% (more preferably from about 0.1 wt% to about 4 wt%, and most preferably from about 0.2 wt% to about 2 wt%).

[0137] Exemplary classes of acaricides include, but are not limited to, botanical acaricides, bridged diphenyl acaricides, carbamate acaricides, oxime carbamate acaricides, hydrazine carbamate acaricides, dinitrophenol acaricides, formamidine acaricides, isoxaline acaricides, macrolide acaricides, avermectin acaricides, milbemycin acaricides, mite growth regulators, organochlorine acaricides, organophosphate acaricides, organothiophosphate acaricides, phosphonate acaricides, phosphoramidothiolate acaricides, organotin acaricides, phenylsulfonamide acaricides, pyrazole carboxamide acaricides, pyrethroid acaricides, quaternary ammonium acaricides, pyrethrin acaricides, pyrrole acaricides, quinoline acaricides, strobilurin acaricides, tetronic acid acaricides, tetrahydrothiazole acaricides, thiocarbamate acaricides, thiourea acaricides, and unclassified acaricides. Examples of acaricides for these classes include, but are not limited to, botanical acaricides - carvacrol, sanguinarine; bridged diphenyl acaricides - azobenzene, bromopropylate, benzyl benzoate, bromopropylate, chlorobenzilate, chlorfenson, chlorobenzilate, dicofol, ethyl chlorobenzilate, propyl chlorobenzilate, cyflumetofen, DDT, kelthane, diphenyl sulfone, fenpyroximate, chlorbenside, flufenerim, fluacrypyrim, hexachlorophene, phenproxide, propargite, tetradifon, chinomethionat; carbamate acaricides - benomyl, carbaryl, carbofuran, carbosulfan, methomyl, propoxur, pyridaben, aldicarb; oxime carbamate acaricides - demeton-S-methyl, butocarboxim, oxamyl, pirimicarb, thiofanox; hydrazine carbamate acaricides - bifenazate; dinitrophenol acaricides - binapacryl, dinocap, dinobuton, dinocap, dinocap-4, dinocap-6, dinocap-o, dinopentyl, dinooctyl, dinobutyl, DNOC; formamidine acaricides - amitraz, chlordimeform, formetanate, formparanate, formparanate-methyl, formetanate hydrochloride, monomethylformamidine; isoxazoline acaricides - afoxolaner, fluralaner, lotilaner, sarolaner; macrolide acaricides - milbemycin; avermectin acaricides - abamectin, doramectin, eprinomectin, ivermectin, selamectin; milbemycin acaricides - milbemycin, milbemycin oxime, moxidectin; mite growth regulators - clofentezine, hexythiazox, flufenzine, fenpyroximate, chlorfluazuron, flubenzimine, flucycloxuron, flufenoxuron, clofentezine; organochlorine acaricides - bromocyclen, toxaphene, DDT, dicofol, endosulfan, lindane; organophosphate acaricides - clofentezine, crotoxyphos, dichlorvos, heptenophos, malathion, methidathion, naled, TEPP, trichlorfon;Organic thiophosphate miticides - Sevin, demeton, coumaphos, chlorpyrifos-methyl, azinphos-methyl, benalaxyl, bromophos, bromophos-ethyl, carbophenothion, chlorpyrifos, diazinon, dichlorvos, dimethoate, disulfoton, endosulfan, ethion, ethoprophos, fenitrothion, fenthion, fosthiazate, heptenophos, isofenphos-methyl, malathion, methamidophos, methidathion, monocrotophos, omethoate, oxydemeton-methyl, phorate, phosalone, phosmet, pirimiphos-methyl, profenofos, prothiofos, pyraclofos, quinalphos, quinothiophos, sulprofos, temephos, terbufos, triazophos, trichlorfon; Phosphonate miticides - trichlorfon; Phosphorothioamide miticides - isocarbophos, dimethoate, phenthoate; Phosphorodiamide miticides - dimefox, mipafox, schradan; Organotin miticides - azocyclotin, cyhexatin, fenbutatin oxide, triazophos; Phenylthioamide miticides - iprobenfos; Phthalimide miticides - chlorpyrifos-methyl, endosulfan; Pyrazole miticides - pyridaben, fenpyroximate; Phenylpyrazole miticides - acetoprole, fipronil, vaniliprole; Pyrazolecarboxamide miticides - pyflubumide, deflufenican; Pyrethroid miticides - allethrin, bifenthrin, brofluthrinate, cyfluthrin, cypermethin, alpha-cypermethin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalerate, permethin; Pyrethroether miticides - pyridaben; Aminopyrimidine miticides - pyrimidifen; Pyrrole miticides - clofentezine; Quaternary ammonium miticides - sanguinarine; Quinoxaline miticides - chinomethionat, chlorfenson; Methoxyacrylate strobilurin miticides - bifujunzhi, pyrimidifen, flufenoxystrobin, pyriminostrobin; Sulfite miticides - chinomethionat, omethoate; Tetronic acid miticides - tebufenpyrad; Tetrazine miticides, clofentezine, flufenzine; Thiazolidine miticides - flubenthiavalicarb, hexythiazox; Thiocarbamate miticides - carbaryl; Thiourea miticides - chlorbenzuron, teflubenzuron; Unclassified miticides - quinomethionate, acrinathrin, amitraz, arsenic oxide, clomipramine, closantel, crotamiton, cycloprate, flufenerim, disulfoton, etoxazole, fenazaquin, flubenzimine, MNAF, hexaflumuron, streptomycin, bifenazate, spirodiclofen, sulfluramid, sulfur, thuricide, benpyrin.

[0138] In some embodiments, the acaricide may also be selected from abamectin, fenthion, quinomethionate, acetamiprid, methomyl, allethrin, aluminum phosphide, aminocarb, clofentezine, azadiractin, ethion, malathion, Bacillus thuringiensis, bendiocarb, beta-cyfluthrin, bifenthrin, beta-cypermethrin, bomyl, bufencarb, calcium cyanide, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, chlorfenson, chlorobenzilate, chloropicrin, chlorpyrifos, clofestanol, clofentezine, clothianidin, coumaphos, crotoxyphos, crotoxyphos + dichlorvos, cryolite, cyfluthrin, cyhexatin, cypermethrin, deet, deltamethrin, demeton, dimethoate, dimethomorph, dichloropropene, dichlorvos, dicofol, disulfoton, dikar (fungicide + acaricide), dimethachlor, difenoconazole, dinotefuran, dichlorvos, emamectin benzoate, endosulfan, endrin, etofenprox, ethoprophos, ethylene dibromide, ethylene dichloride, etoxazole, famphur, fenobucarb, fenpropathrin, fenpyroximate, fenothiocarb, fenthion, flonicamid, flucythrinate, fonofos, formetanate hydrochloride, gamma-cyhalothrin, fenpyroximate, hexakis, hexythiazox, imidacloprid, lime, indoxacarb, imidacloprid, kerosene, kinoprene, lambda-cyhalothrin, lead arsenate, lindane, malathion, mephosfolan, metaldehyde, metam-sodium, methidathion, methomyl, metoxychlor, metolcarb, methyl bromide, methyl parathion, mevinphos, milky disease spore, naled, naphthalene, nicotine sulfate, novaluron, omethoate, methomyl, oxythioquinox, p-dichlorobenzene, parathion, PCP, permethrin, petroleum, phorate, phosalone, phosfolan, pirimiphos-methyl, piperonyl butoxide, pyrethrins: see allethrin, permethrin, fenpropathrin, deltamethrin, pyrethrum, pydrin, pyrethrins, rotenone, s-methidathion, pesticidal soap, sodium fluoride, spinosad, spirodiclofen, sulprofos, sulfotep, tebufenozide, tefluthrin, tetradifon, thiamethoxam, thiodicarb, toxaphene, tralomethrin, trimethacarb, and tetrachlorvinphos.

[0139] IV. Method

[0140] In some embodiments, the urease inhibitor composition is used directly. In other embodiments, the urease inhibitor composition is formulated in a manner that facilitates its use in the context of productive agriculture. The urease inhibitor compositions used in these methods include tert-butylhydroquinone, an organic solvent, and an optional additive component as described above. The urease inhibitor composition can be used, for example, in the following methods:

[0141] A. Methods for improving plant growth and / or plant health and / or soil fertilization

[0142] B. Methods for inhibiting urease activity

[0143] C. Methods for inhibiting ammonia release or evolution

[0144] D. Methods for improving soil conditions

[0145] E. Methods for preparing urease inhibitor compositions

[0146] A. The method for improving plant growth comprises contacting a urease inhibitor composition containing tert-butylhydroquinone, an organic solvent, and an optional additive component as disclosed herein with the soil. In some embodiments, the urease inhibitor composition is applied to the soil before the germination of the planted crop. In some embodiments, the urease inhibitor composition is applied to the soil adjacent to the plant and / or the bottom of the plant and / or the root zone of the plant.

[0147] The method for improving plant growth can also be achieved by coating seeds with a urease inhibitor composition containing tert-butylhydroquinone (and an optional additive component) in the form of a liquid dispersion, and the liquid dispersion forms a dry residue after drying. In these embodiments, the seed coating provides tert-butylhydroquinone (and an optional additive component) very close to the seeds at the time of planting, so that tert-butylhydroquinone can exert its beneficial effects in the environment where it is most needed. That is, tert-butylhydroquinone (and an optional additive component) provides an environment conducive to enhancing plant growth in an area where the action can be localized around the desired plant. In the case of seeds, the coating containing tert-butylhydroquinone (and an optional additive component) provides enhanced opportunities for seed germination, subsequent plant growth, and increased plant nutrient utilization.

[0148] B. The method for inhibiting / reducing urease activity, the method comprises applying a urease inhibitor composition containing tert-butylhydroquinone (and an optional additive component) to the soil. In some embodiments, the urease inhibitor composition is applied to the soil before the germination of the planted crop. In some embodiments, the urease inhibitor composition is applied to the soil adjacent to the plant and / or the bottom of the plant and / or the root zone of the plant.

[0149] C. A method for inhibiting / reducing ammonia release or precipitation in an affected area comprises applying a urease inhibitor composition containing tert-butylhydroquinone (and optionally an additive component) to the affected area. The affected area can be the soil adjacent to plants, fields, pastures, livestock or poultry confinement facilities, pet bedding, manure collection areas, the vertical walls forming enclosures or a top cover substantially covering the area, and in these cases, the urease inhibitor can be directly applied to the manure in the collection area. The urease inhibitor component is preferably applied at a level of about 0.005 to about 3 gallons per ton of manure, in the form of an aqueous dispersion with a pH of about 1 to about 5.

[0150] D. A method for improving soil conditions selected from the group consisting of nitrification processes, urease activity, and combinations thereof, which comprises the step of applying an effective amount of the described tBHQ-containing urease inhibitor urease inhibitor composition to the soil. In some embodiments, the urease inhibitor composition is mixed with solid, liquid or gaseous urea-containing fertilizers and especially solid fertilizers; in the latter case, the urease inhibitor composition is applied in the form of an aqueous dispersion to the (urea-containing) fertilizer surface and then dried so that the urease inhibitor composition is present on the solid fertilizer in the form of a dry residue. Based on the total weight of the urease inhibitor composition / fertilizer product considered as 100% by weight, the urease inhibitor composition is generally applied at a level of about 0.01% to about 10% by weight. When the fertilizer is an aqueous liquid fertilizer, the urease inhibitor composition is added thereto under mixing.

[0151] E. A method for preparing a urease inhibitor composition, which comprises contacting tert-butylhydroquinone with one or more organic solvents to form a mixture. In some embodiments, an additive component is added to the formed mixture.

[0152] In some embodiments, the above methods A, B and C comprise contacting the desired area with the urease inhibitor composition at a ratio of about 100 g to about 120 g of urease inhibitor composition per acre. In some embodiments, the urease inhibitor composition can be present in the solution in an amount of about 0.5 lb to about 4 lb / US gallon, or about 1 lb to about 3 lb / US gallon or about 2 lb / US gallon. In some embodiments, the method comprises contacting the desired area at a ratio of about 0.5 to about 4 qt / A or about 1 to about 2 qt / A.

[0153] Specific embodiments of the subject matter described herein include:

[0154] 1. A method for inhibiting urease activity, the method comprising applying a urease inhibitor composition to the soil, wherein the urease inhibitor composition comprises:

[0155] tert-butylhydroquinone; and

[0156] Organic solvent.

[0157] 2. The method according to embodiment 1, wherein the amount of tert-butylhydroquinone in the composition is from about 0.1% to about 65% based on the total weight of the composition.

[0158] 3. The method according to embodiment 1 or 2, wherein the organic solvent is selected from sulfoxides, aromatic solvents, green solvents, safe solvents and combinations thereof.

[0159] 4. The method according to any one of the above embodiments, wherein the organic solvent comprises dimethyl sulfoxide.

[0160] 5. The composition according to any one of the above embodiments, wherein the organic solvent comprises dimethyl sulfoxide and xylene.

[0161] 6. The method according to embodiment 5, wherein the dimethyl sulfoxide and xylene are present in a weight ratio of from about 1:2 to about 2:1.

[0162] 7. The method according to any one of the above embodiments, wherein the urease inhibitor composition further comprises an additive component.

[0163] 8. The method according to embodiment 7, wherein the additive component is selected from additives containing an α,β-unsaturated carbonyl system, acid-containing additives, ester-containing additives, aromatic additives, ethylene glycol-containing additives and combinations thereof.

[0164] 9. The method according to embodiment 8, wherein the additive component is an additive containing an α,β-unsaturated carbonyl system, which is selected from citral, mesityl oxide, α-amyl cinnamaldehyde, coumarin and combinations thereof.

[0165] 10. The method according to embodiment 8, wherein the additive component is an aromatic additive, which is selected from butylated hydroxyanisole, eugenol, salicylaldehyde, acetophenone, methyl salicylate and combinations thereof.

[0166] 11. The method according to embodiment 8, wherein the additive component is an acid-containing additive, which is selected from itaconic acid, adipic acid, maleic acid, octanoic acid, ethyl maltol, ascorbic acid, levulinic acid and combinations thereof.

[0167] 12. The method according to embodiment 8, wherein the additive component is an ester-containing additive, which is selected from triethyl citrate, isobornyl acetate, propylene carbonate, ethyl lactate and combinations thereof.

[0168] 13. The method according to embodiment 8, wherein the additive component is an ethylene glycol-containing additive, which is selected from diethylene glycol monoethyl ether, ethylene glycol, monobutyl ether and combinations thereof.

[0169] 14. According to the method described in any one of Embodiments 7 to 13 above, wherein the tert-butylhydroquinone and the additive component are present in a weight ratio of from about 1:10 to about 10:1.

[0170] 15. According to the method described in any one of Embodiments 7 to 14, wherein the additive component is present in an amount of from about 1 wt% to about 50 wt% based on the total weight of the composition.

[0171] 16. According to the method described in any one of the above embodiments, wherein the urease inhibitor composition further comprises a surfactant, a dispersant, an emulsifier, an antifoaming agent, a stabilizer, or a combination thereof.

[0172] 17. According to the method described in any one of the above embodiments, wherein at least about 50% of the urease activity is inhibited.

[0173] 18. A method of fertilizing soil and / or improving plant growth and / or health, which comprises contacting a urease inhibitor composition with the soil, wherein the urease inhibitor composition comprises:

[0174] tert-butylhydroquinone; and

[0175] an organic solvent.

[0176] 19. According to the method described in Embodiment 18, wherein the amount of tert-butylhydroquinone in the composition is from about 0.1 wt% to about 65 wt% based on the total weight of the composition.

[0177] 20. According to the method described in Embodiment 18, wherein the organic solvent is selected from sulfoxides, aromatic solvents, green solvents, safe solvents, and combinations thereof.

[0178] 21. According to the method described in Embodiment 18, wherein the organic solvent comprises dimethyl sulfoxide.

[0179] 22. According to the method described in Embodiment 18, wherein the organic solvent comprises dimethyl sulfoxide and xylene.

[0180] 23. According to the method described in Embodiment 22, wherein the dimethyl sulfoxide and the xylene are present in a weight ratio of from about 1:2 to about 2:1.

[0181] 24. According to the method described in any one of Embodiments 18 to 23, wherein the urease inhibitor composition further comprises an additive component.

[0182] 25. According to the method described in Embodiment 24, wherein the additive component is selected from additives containing an α,β-unsaturated carbonyl system, acid-containing additives, ester-containing additives, aromatic additives, and ethylene glycol-containing additives.

[0183] 26. The method according to embodiment 25, wherein the additive component is an additive containing an α,β-unsaturated carbonyl system, which is selected from citral, mesityl oxide, α-amyl cinnamaldehyde, coumarin, and combinations thereof.

[0184] 27. The method according to embodiment 25, wherein the additive component is an aromatic additive, which is selected from butylated hydroxyanisole, eugenol, salicylaldehyde, acetophenone, methyl salicylate, and combinations thereof.

[0185] 28. The method according to embodiment 25, wherein the additive component is an acid-containing additive, which is selected from itaconic acid, adipic acid, maleic acid, octanoic acid, ethyl maltol, ascorbic acid, levulinic acid, and combinations thereof.

[0186] 29. The method according to embodiment 25, wherein the additive component is an ester-containing additive, which is selected from triethyl citrate, isobornyl acetate, propylene carbonate, ethyl lactate, and combinations thereof.

[0187] 30. The method according to embodiment 25, wherein the additive component is an ethylene glycol-containing additive, which is selected from diethylene glycol monoethyl ether, ethylene glycol, monobutyl ether, and combinations thereof.

[0188] 31. The method according to any one of embodiments 24 to 30, wherein tert-butylhydroquinone and the additive component are present in a weight ratio of about 1:10 to about 10:1.

[0189] 32. The method according to any one of embodiments 24 to 31, wherein the additive component is present in an amount of about 1 wt% to about 50 wt% based on the total weight of the composition.

[0190] 33. The method according to any one of embodiments 24 to 32, wherein the urease inhibitor composition further comprises a surfactant, a dispersant, an emulsifier, an antifoaming agent, a stabilizer, or a combination thereof.

[0191] 34. An agricultural composition, comprising:

[0192] a urease inhibitor composition; and

[0193] a solid urea-containing fertilizer,

[0194] wherein the urease inhibitor composition comprises

[0195] tert-butylhydroquinone; and

[0196] an organic solvent, and

[0197] wherein the surface of the urea-containing fertilizer is coated with the urease inhibitor composition.

[0198] 35. The agricultural composition according to embodiment 34, wherein the solid urea-containing fertilizer is in the form of granules or pellets.

[0199] 36. The agricultural composition according to embodiment 35, wherein the average particle size (d50) of the solid urea-containing fertilizer granules is in the range of about 0.5 to about 2.5 mm.

[0200] 37. The agricultural composition according to embodiment 35, wherein the screen aperture size of the urea-containing fertilizer granules is in the range of about 16 mesh to about 100 US mesh.

[0201] 38. The agricultural composition according to embodiment 34, wherein the urease inhibitor composition is present in an amount of about 0.001 wt% to about 10 wt% based on the total weight of the agricultural composition.

[0202] 39. The agricultural composition according to embodiment 34, wherein the amount of tert-butylhydroquinone in the composition is about 0.1% to about 99.9%.

[0203] 40. The agricultural composition according to embodiment 34, wherein the organic solvent is selected from sulfones, aromatic solvents, green solvents, safe solvents, and combinations thereof.

[0204] 41. The agricultural composition according to embodiment 34, wherein the organic solvent comprises dimethyl sulfoxide.

[0205] 42. The agricultural composition according to embodiment 34, wherein the organic solvent comprises dimethyl sulfoxide and xylene.

[0206] 43. The agricultural composition according to embodiment 42, wherein dimethyl sulfoxide and xylene are present in a weight ratio of about 1:2 to about 2:1.

[0207] 44. The agricultural composition according to any one of embodiments 34 to 43, wherein the urease inhibitor composition further comprises an additive component.

[0208] 45. The agricultural composition according to embodiment 44, wherein the additive component is selected from additives containing an α,β-unsaturated carbonyl system, acid-containing additives, ester-containing additives, aromatic additives, and ethylene glycol-containing additives.

[0209] 46. The agricultural composition according to embodiment 44, wherein the additive component is an additive containing an α,β-unsaturated carbonyl system, which is selected from citral, mesityl oxide, α-amyl cinnamaldehyde, coumarin, and combinations thereof.

[0210] 47. The agricultural composition according to embodiment 44, wherein the additive component is an aromatic additive selected from butylated hydroxyanisole, eugenol, salicylaldehyde, acetophenone, methyl salicylate, and combinations thereof.

[0211] 48. The agricultural composition according to embodiment 44, wherein the additive component is an acid-containing additive selected from itaconic acid, adipic acid, maleic acid, octanoic acid, ethyl maltol, ascorbic acid, levulinic acid, and combinations thereof.

[0212] 49. The agricultural composition according to embodiment 44, wherein the additive component is an ester-containing additive selected from triethyl citrate, isobornyl acetate, propylene carbonate, ethyl lactate, and combinations thereof.

[0213] 50. The agricultural composition according to embodiment 44, wherein the additive component is an ethylene glycol-containing additive selected from diethylene glycol monoethyl ether, ethylene glycol, monobutyl ether, and combinations thereof.

[0214] 51. The agricultural composition according to any one of embodiments 44 to 50, wherein tert-butylhydroquinone and the additive component are present in a weight ratio of about 1:10 to about 10:1.

[0215] 52. The agricultural composition according to any one of embodiments 44 to 51, wherein the additive component is present in an amount of about 1 wt% to about 50 wt% based on the total weight of the composition.

[0216] 53. The agricultural composition according to any one of embodiments 44 to 52, wherein the urease inhibitor composition further comprises a surfactant, a dispersant, an emulsifier, an antifoaming agent, a stabilizer, or combinations thereof.

[0217] 54. A method for preparing the agricultural composition according to embodiment 34, the method comprising applying a urease inhibitor composition in liquid or dispersion form to the surface of a solid urea-containing fertilizer, thereby coating the solid urea-containing fertilizer, wherein the urease inhibitor composition comprises:

[0218] tert-butylhydroquinone; and

[0219] an organic solvent.

[0220] 55. The method according to embodiment 54, wherein the solid urea-containing fertilizer is in the form of granules or pellets.

[0221] 56. The method according to embodiment 55, wherein the average particle size (d50) of the solid urea-containing fertilizer granules is in the range of about 0.5 to about 2.5 mm.

[0222] 57. The method according to embodiment 55, wherein the sieve pore size of the urea-containing fertilizer granules ranges from about 16 mesh to about 100 US mesh.

[0223] 58. The method according to embodiment 54, wherein the urease inhibitor composition is applied in an amount of about 0.001 wt% to about 10 wt% based on the total weight of the agricultural composition.

[0224] 59. The method according to embodiment 54, wherein the amount of tert-butylhydroquinone in the composition is about 0.1 wt% to about 99.9 wt% based on the total weight of the composition.

[0225] 60. The method according to embodiment 54, wherein the organic solvent is selected from sulfoxides, aromatic solvents, green solvents, safe solvents, and combinations thereof.

[0226] 61. The method according to embodiment 60, wherein the organic solvent comprises dimethyl sulfoxide.

[0227] 62. The method according to embodiment 61, wherein the organic solvent comprises dimethyl sulfoxide and xylene.

[0228] 63. The method according to embodiment 62, wherein dimethyl sulfoxide and xylene are present in a weight ratio of about 1:2 to about 2:1.

[0229] 64. The method according to any one of embodiments 54 to 63, wherein the urease inhibitor composition further comprises an additive component.

[0230] 65. The method according to embodiment 64, wherein the additive component is selected from additives containing an α,β-unsaturated carbonyl system, acidic additives, ester-containing additives, aromatic additives, and ethylene glycol-containing additives.

[0231] 66. The method according to embodiment 65, wherein the additive component is an additive containing an α,β-unsaturated carbonyl system, which is selected from citral, mesityl oxide, α-amyl cinnamaldehyde, coumarin, and combinations thereof.

[0232] 67. The method according to embodiment 65, wherein the additive component is an aromatic additive, which is selected from butylated hydroxyanisole, eugenol, salicylaldehyde, acetophenone, methyl salicylate, and combinations thereof.

[0233] 68. The method according to embodiment 65, wherein the additive component is an acidic additive, which is selected from itaconic acid, adipic acid, maleic acid, octanoic acid, ethyl maltol, ascorbic acid, levulinic acid, and combinations thereof.

[0234] 69. The method according to embodiment 65, wherein the additive component is an ester-containing additive selected from triethyl citrate, isobornyl acetate, propylene carbonate, ethyl lactate, and combinations thereof.

[0235] 70. The method according to embodiment 65, wherein the additive component is an ethylene glycol-containing additive selected from diethylene glycol monoethyl ether, ethylene glycol, monobutyl ether, and combinations thereof.

[0236] 71. The method according to any one of embodiments 64 to 70, wherein tert-butylhydroquinone and the additive component are present in a weight ratio of about 1:10 to about 10:1.

[0237] 72. The method according to any one of embodiments 64 to 71, wherein the additive component is present in an amount of about 1 wt% to about 50 wt% based on the total weight of the composition.

[0238] 73. The method according to any one of embodiments 64 to 72, wherein the urease inhibitor composition further comprises a surfactant, a dispersant, an emulsifier, an antifoaming agent, a stabilizer, or combinations thereof.

[0239] 74. A urease inhibitor composition comprising:

[0240] tert-butylhydroquinone;

[0241] an additive selected from additives containing an α,β-unsaturated carbonyl system, acid-containing additives, ester-containing additives, aromatic additives, ethylene glycol-containing additives; and

[0242] an organic solvent,

[0243] wherein tert-butylhydroquinone and the additive component are present in synergistic amounts.

[0244] 75. The composition according to embodiment 74, wherein tert-butylhydroquinone is present in an amount of about 0.1 wt% to about 65 wt% based on the total weight of the composition.

[0245] 76. The composition according to embodiment 74, wherein the additive is present in an amount of about 1 wt% to about 50 wt% based on the total weight of the composition.

[0246] 77. The composition according to any one of embodiments 74 to 76, wherein tert-butylhydroquinone and the additive component are present in a weight ratio of about 1:10 to about 10:1.

[0247] 78. The composition according to any one of embodiments 74 to 77, wherein the organic solvent is selected from sulfoxides, aromatic solvents, green solvents, safe solvents, and combinations thereof.

[0248] 79. The composition according to any one of embodiments 74 to 78, wherein the organic solvent comprises dimethyl sulfoxide.

[0249] 80. The composition according to embodiment 79, wherein the organic solvent comprises dimethyl sulfoxide and xylene.

[0250] 81. The composition according to embodiment 80, wherein dimethyl sulfoxide and xylene are present in a weight ratio of about 1:2 to about 2:1.

[0251] 82. The composition according to any one of embodiments 74 to 81, wherein the additive component is selected from additives containing an α,β-unsaturated carbonyl system, acid additives, ester additives, aromatic additives, ethylene glycol-containing additives, and combinations thereof.

[0252] 83. The composition according to embodiment 82, wherein the additive component is an additive containing an α,β-unsaturated carbonyl system, which is selected from citral, mesityl oxide, α-amyl cinnamaldehyde, coumarin, and combinations thereof.

[0253] 84. The composition according to embodiment 82, wherein the additive component is an aromatic additive, which is selected from butylated hydroxyanisole, eugenol, salicylaldehyde, acetophenone, methyl salicylate, and combinations thereof.

[0254] 85. The composition according to embodiment 82, wherein the additive component is an acid additive, which is selected from itaconic acid, adipic acid, maleic acid, octanoic acid, ethyl maltol, ascorbic acid, levulinic acid, and combinations thereof.

[0255] 86. The composition according to embodiment 82, wherein the additive component is an ester additive, which is selected from triethyl citrate, isobornyl acetate, propylene carbonate, ethyl lactate, and combinations thereof.

[0256] 87. The composition according to embodiment 82, wherein the additive component is an ethylene glycol-containing additive, which is selected from diethylene glycol monoethyl ether, ethylene glycol, monobutyl ether, and combinations thereof.

[0257] 88. The composition according to any one of embodiments 74 to 87, wherein the urease inhibitor composition further comprises a surfactant, a dispersant, an emulsifier, an antifoaming agent, a stabilizer, or a combination thereof.

[0258] 89. The composition according to any one of embodiments 74 to 88, wherein at least about 50% of the urease activity is inhibited.

[0259] V. Examples

[0260] It should be understood that the following examples are provided for illustration only and none of them should be considered restrictive.

[0261] Example 1: Screening of Urease Inhibitor Compositions

[0262] Evaluate the testing of tert-Butylhydroquinone (tBHQ) in combination with additive components. Screen various different classes of potential urease inhibitor (UI) compounds as potential additive components. For example, various groups of hypophosphorous acid, catechol, hydroquinone, triazoles, coumarins, α-hydroxy ketones, oximes, protocatechuic acid, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), phosphoramides, and certain sulfur compounds (to name just a few). tBHQ was selected as the primary urease inhibitor due to its initial properties, availability, and safety profile. Several different modes of action (MOA) were proposed for the UI compounds as the primary modes of action, such as but not limited to Ni(II) binding and mobile flap folding.

[0263] These studies further explored the performance of higher levels (>10 quarts / ton) of tBHQ and the selected additives in the field to make the ratio compatible with commercially available products, i.e., in the range of 3 quarts / ton. Synergistic additives and safer and more environmentally friendly solvents were identified, all of which are commercially available in ton (and higher) quantities.

[0264] A. Materials and Protocols

[0265] Obtain tBHQ (the primary active ingredient (AI)), solvents, and additives (co-active agents) from commercial suppliers. Developed a Draeger tube protocol and used soil from the NCSU Ag research facility in Oxford, North Carolina. Prepare samples by co-dissolving in a suitable solvent by rolling on a sample roller for 2 - 4 hours at ambient temperature and let it stand over the weekend to ensure no turbidity and / or precipitation. In 12 mL cylindrical glass vials, the typical sample size is 4 - 4.5 g. Apply these clear (sometimes faintly peach-colored) solutions to urea pellets at 3 quarts / ton (L, representing the low ratio) and 6 quarts / ton (H, representing the high ratio) respectively. Plot the readings where time is the independent variable and NH3 (on a linear Draeger scale) is recorded on the y-axis to produce an output that is generally "S"-shaped. Include UTC and urea controls as well as formulation A and formulation B (tBHQ in an organic solvent) in all rounds. Store the samples under ambient conditions for 6 months (or 12 months) to observe any precipitation, thickening, or turbidity.

[0266] B. Results and Discussion

[0267] The following candidates are tBHQ + [x co - surfactant + y solvent], where x and y vary. The results of many rounds of evaluation are obtained and discussed in more detail below. The evaluation data of approximately 70 candidates are presented, including candidate numbers (i.e., UI#), chemical names, and CAS numbers. Generally, when the graph of a candidate is close to the x - axis (indicating a lower volatility rate), the candidate shows good performance. The solid line represents the low ratio and the dashed line represents the high ratio; except (Formulation A) and Formulation B, UTC is always closest to the x - axis, and the urea control is usually the left - most line in the graph. Most experiments take 2 weeks to complete, while for the preferred candidates, some experiments take 3 weeks (or 4 weeks) to complete. A longer period of suppressing volatility can be a good indicator of the expected excellent performance.

[0268] Round 1:

[0269] Evaluate the following compounds:

[0270] Urease inhibitor composition# Reagent CAS number of additive component UI#89 tBHQ + isophorone 78-59-1 UI#90 tBHQ + citral 5392-40-5 UI#91 tBHQ + α-hexylcinnamaldehyde 101-86-0 UI#92 tBHQ + trans-cinnamaldehyde 14371-10-9 UI#93 tBHQ + mesityl oxide 141-79-7 UI#94 tBHQ + diethyl maleate 141-05-9

[0271] Result:

[0272] Table 2

[0273] Time (hours) ---> 16 24 40 48 67 89 115 140 159 183 205 234 254 Soil, untreated 0 0 0 0 0 0 0 0 0.33 1.67 2 3.67 6.33 Urea 0 0 5 23.3 150 150 150 150 150 150 150 150 150 Formulation A 0 0 0 0 0 0 0 1.33 2.67 6 10.7 26 40.3 Formulation B 0 0 0 0 0 0 0 0.67 3 17.7 71.7 125.3 150 UI#89 0 0 0 0 0 0 3 44 124.7 150 150 150 150 UI#90 0 0 0 0 0 0 4.67 69.3 101 101.3 102 116.7 150 UI#91 0 0 0 0 0 0 1.33 7.67 80 150 150 150 150 UI#92 0 0 0 0 0 0.67 3.33 86.7 150 150 150 150 150 UI#93 0 0 0 0 0 0 1 33.7 90.7 150 150 150 150 UI#94 0 0 0 0 0 0 1.67 57.3 145 150 150 150 150

[0274] Round 2:

[0275] Evaluate the following compounds:

[0276] Urease inhibitor composition# Reagent CAS number of additive component UI#93 tBHQ + mesityl oxide 141-79-7 UI#95 Mesityl oxide 141-79-7 UI#96 α-amylcinnamaldehyde 122-40-7 UI#97 tBHQ + α-amylcinnamaldehyde 122-40-7 UI#98 tBHQ + coumarin 91-64-5 UI#99 tBHQ + ethyl sorbate 2396-84-1

[0277] Result:

[0278] Table 3

[0279] Time (hours) ---> 16 24 41 48 67 88 106 130 148 175 196 214 232 Soil, untreated 0 0 0 0 0 0 0 0 0 0.33 0.67 1 2.67 Urea 0 0 3 9.33 143.3 150 150 150 150 150 150 150 150 Formulation A 0 0 0 0 0 0 0 0.33 1.67 3.33 4 6.67 9 Formulation B 0 0 0 0 0 0 0.67 13.3 64.3 101.3 102 104 107 UI#93 repeated 0 0 0 0 0 0 1.67 49.3 89.3 112.7 150 150 150 UI#95 0 0 4 44.3 150 150 150 150 150 150 150 150 150 UI#96 0 0 2 18 133.3 150 150 150 150 150 150 150 150 UI#97 0 0 0.33 0.33 0.33 0.67 3 36 54.7 90 127.3 150 150 UI#98 0 0 0 0 0 0 1 2 9 54.3 59.3 81.3 111 UI#99 0 0 0 0 0 0 1 24 109 150 150 150 150

[0280] Round 3:

[0281] Evaluate the following compounds

[0282] Urease inhibitor composition# Reagent CAS number of additive component UI#100 tBHQ + butylated hydroxyanisole 25013-16-5 UI#101 tBHQ + chalcone 614-47-1 UI#102 tBHQ + phenylbutazone 1896-62-4 UI#103 tBHQ + itaconic acid 97-65-4 UI#104 tBHQ + thymol 89-83-8 UI#105 tBHQ + vanillin 121-33-5

[0283] Result:

[0284] Table 4

[0285] Time (hours) ---> 16 23 41 50 64 88 107 131 149 173 197 220 244 Soil, untreated 0 0 0 0 0 0 0 0 0 0.67 2.33 3.33 3.33 Urea 0 0 6.33 45.3 150 150 150 150 150 150 150 150 150 Formulation A 0 0 0 0 0 0 0 2.33 4.67 10 20 44 70 Formulation B 0 0 0 0 0 0 0 1.67 22.7 51.3 51.3 52 53.7 UI#100 0 0 0 0 0 0 0 10.7 43.3 100.7 150 150 150 UI#101 0 0 0 0 0 4 101 114 141.7 150 150 150 150 UI#102 0 0 0 0 0 0 2.33 31 87.3 150 150 150 150 UI#103 0 0 0 0 0 0 0 1 3 28 110.3 150 150 UI#104 0 0 0 0 0 0.67 45.7 100.7 110.7 141.7 150 150 150 UI#105 0 0 0 0 0 0 7 109 136.7 150 150 150 150

[0286] Round 4:

[0287] Evaluate the following compounds:

[0288] Urease inhibitor composition# Reagent CAS number of additive component UI#106 tBHQ + anisaldehyde 123-11-5 UI#107 tBHQ + dimethyl succinate 106-65-0 UI#108 tBHQ + eugenol 97-53-0 UI#109 tBHQ + levulinic acid 123-76-2 UI#110 tBHQ + salicylaldehyde 90-02-8 UI#111 tBHQ + triethyl citrate 77-93-0

[0289] Result / Notes

[0290] Table 5

[0291] Time (hours) ---> 15 22 39 48 63 90 118 137 169 193 208 Soil, untreated 0 0 0 0 0 0 0 0 0.33 1 2 Urea 0 0 5 52.3 150 150 150 150 150 150 150 Formulation A 0 0 0 0 0 0 0 1 6 9 13.7 Formulation B 0 0 0 0 0 0 15 39 53 58 65.7 UI#106 0 0 0 0 0 0 40 128.3 150 150 150 UI#107 0 0 0 0 0 1 40 105 150 150 150 UI#108 0 0 0 0 0 0 25 53 102 150 150 UI#109 0 0 0 0 0 0 27.3 106 150 150 150 UI#110 0 0 0 0 0 0 41.7 92 135 150 150 UI#111 0 0 0 0 0 0 0.33 6 60 88.3 150

[0292] The 5th round evaluated the following compounds:

[0293] Urease inhibitor composition# Reagent CAS number of additive component UI#112 tBHQ + acetophenone 98-86-2 UI#113 tBHQ + isobornyl acetate 125-12-2 UI#114 tBHQ + dipropylene glycol monomethyl ether 34590-94-8 UI#115 tBHQ + propylene carbonate 108-32-7 UI#116 tBHQ + tetraethylene glycol 112-60-7

[0294] Result:

[0295] Table 6

[0296]

[0297] The 6th round evaluated the following compounds:

[0298] Urease inhibition composition# Reagent CAS number of additive component UI#117 tBHQ + adipic acid 124-04-9 UI#118 tBHQ + maleic acid 110-16-7 UI#119 tBHQ + malic acid 6915-15-7 UI#120 tBHQ + octanoic acid 124-07-2 UI#121 tBHQ + sorbic acid 110-44-1 UI#122 tBHQ + succinic acid 110-15-6

[0299] Result:

[0300] Table 7:

[0301] Time (hours) ---> 16 22 41 48 64 88 120 140 163 191 212 232 264 288 312 333 353 Soil, untreated 0 0 0 0 0 0 0 0 0.33 2.33 2.33 3 5 16 24.3 36 42 Urea 0 0 5.67 33.3 150 150 150 150 150 150 150 150 150 150 150 150 150 Formulation A 0 0 0 0 0 0 0 0 0 0 2.33 3 10 20 36.7 46.7 57.3 Formulation B 0 0 0 0 0 0 0 0 3.67 39 100 102 101 101 101.7 103.3 120 UI#117 0 0 0 0 0 0 0 0 1 1.33 10.3 39 56 67 80 103.3 148.3 UI#118 0 0 0 0 0 0 0 1 30.7 52.3 87.3 145 150 150 150 150 150 UI#119 0 0 0 0 0 0 0 0 1.67 50.3 53.3 90 150 150 150 150 150 UI#120 0 0 0 0 0 0 0.33 2 7.67 53 77.7 102.3 108 133.3 150 150 150 UI#121 0 0 0 0 0 0 3.33 51.3 79.7 107.3 135 150 150 150 150 150 150 UI#122 0 0 0 0 0 0 0 0.33 4.33 87.7 145 150 150 150 150 150 150

[0302] The 7th round evaluated the following compounds:

[0303] Urease inhibitor composition# Reagent CAS number of the additive component UI#123 tBHQ + 3,3-dimethylacrylic acid 541-47-9 UI#124 tBHQ + dimethyl sulfone 67-71-0 UI#125 tBHQ + ethyl lactate 97-64-3 UI#126 tBHQ + ethyl maltol 4940-11_8 UI#127 tBHQ + 85% lactic acid 50-21-5 UI#128 tBHQ + (L)-tartaric acid 87-69-4

[0304] Results / Notes:

[0305] Table 8

[0306] Time (hours) ---> 17 24 42 48 65 90 117 145 162 186 210 232 Soil, untreated 0 0 0 0 0 0 0 0 0 0 1.33 3.67 Urea 0 0 1.67 12.3 126.7 150 150 150 150 150 150 150 Formulation A 0 0 0 0 0 0 0 1.33 4 18 38 52.7 Formulation B 0 0 0 0 0 0 0 0 2.33 35.3 103 134.3 UI#123 0 0 0 0 0 0 7.33 136.7 150 150 150 150 UI#124 0 0 0 0 0 0 38.3 133.3 150 150 150 150 UI#125 0 0 0 0 0 0 1 50.7 52.3 95.3 101 102.3 UI#126 0 0 0 0 0 0 0 52 71 120 150 150 UI#127 0 0 0 0 0 0 1.67 99.3 133.3 133.3 150 150 UI#128 0 0 0 0 0 0 1 103.3 150 150 150 150

[0307] The 8th round evaluated the following compounds:

[0308] Urease inhibitor composition# Reagent CAS number of the additive component UI#129 tBHQ + L-ascorbic acid 50-81-7 UI#130 tBHQ + butyl lactate 138-22-7 UI#131 tBHQ + diethyl L-(+)-tartrate 87-91-2 UI#132 tBHQ + poly(isobutylene-alt-maleic anhydride) 26426-80-2 UI#133 tBHQ + 2,6-pyridinedicarboxylic acid 499-83-2 UI#134 tBHQ + 4-carboxybenzaldehyde 619-66-9

[0309] Results:

[0310] Table 9

[0311]

[0312]

[0313] The 9th round evaluated the following compounds:

[0314] Urease inhibitor composition Reagent CAS number UI#135 tBHQ + butyl benzoate 98-73-7 UI#136 tBHQ + diacetone alcohol 123-42-2 UI#137 tBHQ + diethyl adipate 141-28-6 UI#138 tBHQ + diethylene glycol monobutyl ether 112-34-5 UI#139 tBHQ + diethylene glycol monoethyl ether 111-90-0 UI#140 ethylene glycol monobutyl ether 111-76-2 UI#141 tBHQ + isophorone 78-59-1

[0315] Results:

[0316] Table 10

[0317] Time (hours) ---> 18 24 43 48 67 96 120 139 163 187 211 235 Soil, untreated 0 0 0 0 0 0 0 0 0 0 0 0 Urea 0 0 8.67 40.7 150 150 150 150 150 150 150 150 Formulation A 0 0 0 0 0 0 1.33 4 16 48.7 95 145 Formulation B 0 0 0 0 0 0 0 1.67 26.7 101 114 150 UI#135 0 0 0 0 0 2.33 50.7 69.7 101 126 150 150 UI#136 0 0 0 0 0 0 5.67 68.7 136.7 150 150 150 UI#137 0 0 0 0 0 0 1.67 24.7 109 150 150 150 UI#138 0 0 0 0 0 0.33 27.33 53 105 150 150 150 UI#139 0 0 0 0 0 0 1.33 45.7 55 101.7 136.7 150 UI#140 0 0 0 0 0 0.33 25.67 70.7 101.7 124 150 150 UI#141 0 0 0 0 0 0 1.67 48 150 150 150 150

[0318] The 10th round evaluated the following compounds:

[0319] Urease inhibitor composition# Reagent CAS number of the additive component UI#142 tBHQ + anisaldehyde 123-11-5 UI#143 tBHQ + DBE-4 106-65-0 UI#144 tBHQ + levulinic acid 123-76-2 UI#145 tBHQ + PGME 107-98-2 UI#146 tBHQ + PGMEA 108-65-6 UI#147 tBHQ + methyl salicylate 119-36-8 UI#148 tBHQ + salicylaldehyde 90-02-8

[0320] Results:

[0321] Table 11

[0322]

[0323] The 11th round evaluated the following compounds:

[0324] Urease inhibitor composition# Reagent CAS number of the additive component UI#149 tBHQ + citral 5392-40-5 UI#150 tBHQ + MOx 141-79-7 UI#151 tBHQ + coumarin 91-64-5 UI#152 tBHQ + itaconic acid 97-65-4 UI#153 tBHQ + triethyl citrate 77-93-0 UI#154 tBHQ + acetophenone 98-86-2 UI#155 tBHQ + isobornyl acetate 125-12-2

[0325] Results:

[0326] Table 12

[0327]

[0328] The 12th round evaluated the following compounds:

[0329] Urease inhibitor composition# Reagent CAS number of the additive component UI#156 tBHQ + adipic acid 124-04-9 UI#157 tBHQ + maleic acid 110-16-7 UI#158 tBHQ + malic acid 6915-15-7 UI#159 tBHQ + octanoic acid 124-07-2 UI#160 tBHQ + salicylic acid 69-72-7 UI#161 tBHQ + levulinic acid 123-76-2 UI#162 tBHQ + L-ascorbic acid 50-81-7

[0330] Results:

[0331] Table 13

[0332]

[0333]

[0334] Example 2: Biometer type volatilization study

[0335] The objective of the study was to compare the NH3 volatilization values from soils fertilized with urea that had received different treatments.

[0336] 1. Materials and methods

[0337] 1.1. Ammonia volatilization experiment

[0338] Laboratory tests were conducted to compare the rates and cumulative amounts of ammonia volatilization. The soil (sandy loam) used was sampled, dried at 40 °C, and ground to pass through a 2 mm sieve mesh. To characterize the soil, different physicochemical properties were measured (Table 14): exchangeable bases (Ca +2 , K + , Mg+2 , Na + (Haby et al., 1990), cation exchange capacity (CEC) (Chapman, 1965), soil organic matter (SOM) (Walkley and Black, 1934), pH (1:2.5 soil to water ratio), initial ammonium and nitrate content (Bremner and Keeney, 1965), and soil texture (Bouyoucos, 1963). To determine the bulk density of the 2 mm sample, the soil was filled in a 1 L container and weighed.

[0339] Table 14. Physicochemical properties of the soil used in the incubation experiment

[0340] Soil properties Unit Value [[ID=13 <![CDATA[g kg -1 > 20.8 ​ 5.24 ​ <![CDATA[mmhos cm -1 > 0.27 ​ <![CDATA[meq 100g -1 > 10.2 <![CDATA[Exchangeable Ca +2 > <![CDATA[meq 100g -1 > 3.5 <![CDATA[Exchangeable Mg +2 > <![CDATA[meq 100g -1 > 0.89 <![CDATA[Exchangeable Na + > <![CDATA[meq 100g -1 > 0.27 <![CDATA[Exchangeable K + > <![CDATA[meq 100g -1 > 1.13 ​ <![CDATA[meq 100g -1 > 5.79 ​ <![CDATA[mmhos cm -1 > 0.27 ​ ％ 56.7 ​ <![CDATA[g kg -1 > 810 ​ <![CDATA[g kg -1 > 104 ​ <![CDATA[g kg -1 > 86 <![CDATA[N-NO3 - > <![CDATA[mg kg -1 > 19.6 <![CDATA[N-NH4 + > <![CDATA[mg kg -1 > 14 ​ <![CDATA[g cm -3 > 1.23 ​ <![CDATA[cm 3 cm -3 > 0.42

[0341] The experiment consisted of 80 experimental units, consisting of 1.3 L containers (diffusion chambers). 800 g of soil sample was weighed into each container. Half of the soil was thoroughly mixed with reagent-grade micronized CaCO3 to increase its base saturation from 57% to 70% (CaCO3 ratio equivalent to 1.6 Mg ha -1 ). The soil in all containers was moistened with demineralized water to increase its water content to 70% of the water-holding capacity. The soil was mixed while gradually applying water with a spray bottle to ensure uniform wetting. The diffusion chambers were hermetically closed and kept in an incubator at 25 °C for 10 days. During the pre-incubation period, the chambers were opened every two days to avoid anoxic conditions.

[0342] After pre-incubation, the fertilization treatments described in Table 15 were applied, with each treatment replicated four times. For this purpose, the fertilization treatments received urea at a rate of 1500 mg N kg -1 . The fertilizer was evenly applied to the soil surface.

[0343] Table 15. N-fertilizer treatments and their identification names

[0344]

[0345] 50 ml plastic containers with 20 ml of 1N NaOH (i.e., NH3 trap) were placed inside each experimental unit. These traps were placed above a plastic tripod to allow gas exchange over all soil surfaces. The diffusion chambers were hermetically closed and randomly placed in an incubator at 25 °C. At different sampling times (1, 2, 3, 4, 5, 7, 9, 11, 15, 19, 23, and 30 days after fertilizer application), the traps were replaced. The extracted traps were immediately covered with caps and stored at 4 °C until they were analyzed for NH4 +Analysis was carried out (less than 3 h after the trap was changed). NH4 in the trap was determined by steam microdistillation (Bremner and Keeney, 1965). + Determination of concentration.

[0346] Since none of the fertilization treatments showed NH3 volatilization values equal to or lower than T2 (control) after day 11, data collection continued for all treatments throughout the 30-day incubation period. After the experiment ended, the soil was dried at 40 °C and ground to pass through a 2-mm sieve. Subsequently, the soil pH value (1:2.5 soil-to-water ratio) and N-NH4 + and N-NO3 - concentrations in these soil samples were determined (Bremner and Keeney, 1965).

[0347] 1.2. Data analysis

[0348] The experiment was designed as a randomized block (DBC) with two factors (fertilization treatment and lime treatment). The results were analyzed by analysis of variance to determine the differences between treatments. Subsequently, the treatment means were compared using the Tukey test (p < 0.05). The ammonia volatilization results were compared in two different ways. First, the ammonia volatilization rates at each time were compared. These volatilization rates were calculated as: the amount of N-NH3 in the trap at time X divided by the time (d) elapsed between time X and time X - 1. Second, the cumulative N volatilized at each time was calculated by subsequently adding the amount of N-NH3 to the time at each experimental unit.

[0349] To determine the proportion of N recovered in the fertilizer in the form of mineral N or volatilized N at the end of the experiment, the following N balance was carried out:

[0350]

[0351] Since in the fertilization treatments, the N derived from mineralization could not be distinguished without isotope dilution analysis, the N mineralization obtained in the control treatment (T2) was used for the remaining treatments. Therefore, by using the same mineralization results in all treatments, no priming effect occurred in the fertilization treatments.

[0352] 2. Results and discussion

[0353] 2.1. Soil mineral N after 30 days of incubation

[0354] The N-NH4 + concentration in the soil after the incubation period was not affected by the lime treatment (Table 16). However, compared to T2 (control), N-NH4 +Increased concentration. Among the fertilization treatments, only T7 and T10 showed different N-NH4 + concentrations, as the N-NH4 + concentration of the latter was 14% higher than that of T7.

[0355] The treatments receiving lime showed higher N-NO3- concentrations than those not receiving lime (104.6 and 87.6 mg kg -1 respectively) (Table 16). However, this difference was not reflected in the total mineral N, as N-NO3 - represented only 11% of the mineral N in the fertilization treatments. Compared with T2, the N-NO3 - concentrations in the fertilization treatments were generally higher (+59%), and there was no difference from the control treatment except for T9 and T10.

[0356] Table 16. Results of the analysis of variance of N-NH4 + , N-NO3 - and mineral N (N-NH4 + +N-NO3 - )(mg kg -1 ).

[0357]

[0358] The N-NH4 + concentration in the soil of T2 after 30 days of incubation was 45 times lower than that during the initial period (Table 13, ​ ). Conversely, the N-NO3 - concentration in T2 increased 2.5 times during the incubation period. Therefore, the amount of N mineralized in the control treatment during the incubation period was calculated to be 43 mg N / kg soil.

[0359] 2.2. Soil pH after 30 days of incubation

[0360] A significant interaction between the fertilization treatment and the lime treatment on soil pH was observed (Table 17). The lime treatment increased the soil active acidity only in the unfertilized treatments, where the soil pH of T2 lime increased by 8% compared with T2 ( ​ ). The soil pH of the fertilization treatments was on average 55% higher than that of T2, as the hydrolysis of urea consumes protons, thus increasing the soil pH:

[0361] CO(NH2)2 + H+ + H2O → 2 NH4 + + HCO3 -

[0362] No effect of lime treatment on pH was observed in the fertilization treatments. In this sense, an increase in soil pH decreases urease activity (Cabrera et al., 1991). Therefore, the reasons for the lack of effect of lime treatment on pH in the fertilization treatments are: 1) the effect of urea hydrolysis on soil pH is greater, masking the effect of lime treatment; and / or 2) there is an interaction between lime treatment and urea hydrolysis such that the effects of the two processes on soil pH are not additive.

[0363] Table 17. Results of the analysis of variance of pH measured at the end of cultivation

[0364]

[0365] In the fertilization treatments, only T10 lime and T3 had different pH values, as the former had a slightly higher pH than the latter (+3.7%). The most obvious difference between each treatment was the application of lime. However, since the application of CaCO3 did not affect the pH of any other fertilization treatment, it could not be admitted that lime treatment was the main cause of the pH difference between T10 lime and T3. The difference between these treatments was related to the difference in the N-NO3 - concentration observed. In all fertilization treatments, the N-NO3 - concentration of T10 lime was the lowest (Figure 15), indicating that the nitrification process was effectively restricted. Considering that nitrification causes proton release, which can partially compensate for the effect of lime treatment and / or urea hydrolysis on soil pH, the change in nitrification rate can partially explain the difference in soil pH between treatments.

[0366] NH4++3 H2O→NO3 - +8e - +10H +

[0367] 2.3. N-NH3 volatilization rate

[0368] The results of the NH3 volatilization rate study are as follows. On the first day, the NH3 emissions of T1 lime were 30 times the average of the remaining treatments (Table 18). On the second day, the emissions of all treatment groups increased, except for T2 (control group), T8, and T9, in which no effect of lime treatment was observed. Also on that day, the NH3 emissions of T3, T5, and T7 (which were treated with 1.5, 1.5, and 2 L of Mg -1 of the corresponding products respectively) were those of the treatments with a larger ratio of product application (2, 2, and 3 L of Mg for T4, T6, and T8 respectively -1) is more than twice the NH3 emissions. Therefore, in the early stage after fertilizer application, the product application rate of urea is an important factor, which was observed in the application of three of the four evaluated products (formulation C, formulation D, and formulation A). In addition, even with a greater application rate of these products, they are still unable to reduce NH3 volatilization as effectively as formulation B.

[0369] On the 3rd day, the effects of fertilizer and lime treatments on the NH3 volatilization rate were significant (Table 17). Here, the general trend of reducing NH3 volatilization is contrary to the previously observed results. The soil treated with lime tended to emit more NH3 on the 1st and 2nd days, but now the emission rate has decreased by 8%. In addition, compared with T3, T4, T5, T6, T7, and T8, the treatment of untreated urea (T1) showed a lower NH3 emission rate. As in the previous days, T9 and T10 were not different from T2. Until the 3rd day, during the quantification of NH3, when NaOH (50% w / w) was added, the content of the trap turned slightly pink. This observation and the strong smell of the treatment receiving formulation B indicate that the product is volatile and the generated gas is soluble in the H2SO4 trap.

[0370] On the 4th day, no effect of lime treatment was observed (Table 18). Among the evaluated treatments, the emission rate of T8 was 70% higher than that of T6 (which was not different from T1), and the emission rates of T3, T4, T5, and T7 were between the two treatments (i.e., T8 and T6). In addition, the emission rates of T9 and T10 were lower and not different from T2. On the 5th day, the magnitude of the difference between each treatment began to narrow, where the NH3 emissions of T6 were 30% higher than those of T7, and the values of T1, T3, T4, T5, and T8 were between those two treatments (i.e., T6 and T7). Similarly, the emission rates of T9 and T10 were lower and not different from T2.

[0371] On the 7th and 9th days, a correlation between lime treatment and fertilization treatment was observed (Table 18). On the 7th day, the most significant change was observed under T9 lime. Before the 7th day, the daily NH3 emission rate of T9 lime was similar to that of the control group (T2). However, on the 7th day, the NH3 emissions of T9 lime were 10 times the average emissions of T2, T2 lime, T9, T10, and T10 lime. On the 9th day, the effect was even greater, and among all treatments, the volatilization rates of T9 and T9 lime were the highest. In addition, on this day, there was no difference between T1, T3, T4, T5, T6, T7, and T8 (with or without lime), but the NH3 emitted was still more than that of T2 and T10 (with or without lime).

[0372] On the 11th day, the treatment (T10) receiving the maximum ratio of formulation B began to differ from the control group (T2), while T9 still had the highest volatilization rate among all treatments. This trend reversed on the 15th day, when T10 had the highest volatilization rate. From this day on, the NH3 volatilization rate in all treatments decreased over time, but the overall trend was T10>T9>T1=T3=T4=T5=T6=T7=T8>T2. Except on the 19th day, there was no interaction between lime treatment and fertilization.

[0373] Table 18. Results of the analysis of variance of N-HN3 emission rates

[0374]

[0375] 2.4. Cumulative volatilized N-NH3

[0376] During the entire cultivation process, except on the 1st day (Table 19), no effect of lime application on the cumulative release amount of NH3 was observed. Therefore, except on that day, these results (Table 20) describe the average cumulative volatilization amount of NH3 in the limed and unlimed experimental units in each treatment. In fact, lime treatment affects the volatilization rate of NH3 (Section 2.3), but does not affect the cumulative emissions, indicating that the effect of lime treatment on the volatilization rate is compensated throughout the period. That is, for example, if the NH3 emission rate of T1 lime is higher than that of T1 on the 1st day, then the emission rate in the following days is proportionally lower than that of T1.

[0377] On the 1st day and as observed for the volatilization rate (Table 18), the NH3 emissions of all treated samples were the same, except for T1 lime, whose NH3 emissions were 30 times the average of the remaining treatments (data not shown). On the 2nd day, the cumulative emissions of the treated urea (T3 to T10) were lower compared to normal urea (T1) (Table 20), and in some cases (T4, T8, T9, and T10) there was no difference from the unfertilized soil (T2). The trend on the 3rd day was similar to that observed on the 2nd day, but T3 and T5 (the lowest ratios of formulation C and formulation D) were not different from the untreated urea (T1), and only the treatments with formulation B (T9 and T10) had the same cumulative amount of NH3 emissions as the control (T2). On the 4th and 5th days, only the cumulative emissions of T6, T8, and T9 were lower than those of the untreated urea (T1), and T8 and T9 were not different from T2. However, on the 7th day, the efficiency of T6 in reducing NH3 emissions was no longer significant compared to T1.

[0378] On the 9th day, the cumulative NH3 release of the formulation B at the lowest ratio (T9) began to differ from that of the control group (T2). By the 15th day, even the treatment with the formulation B at the maximum ratio (T10) began to show a higher cumulative NH3 emission than T2. From this day until the 23rd day, the general trend was: T1, T3, T4, T5, T6, T7, T8 > T10 > T9 > T2. By the end of the experiment, only the cumulative emission of T10 was lower than that of T1.

[0379] Table 19. Results of the analysis of variance of cumulative N-HN3 emissions (mg N)

[0380]

[0381]

[0382] Table 20. Comparison of the average values of cumulative N-NH3 (mg) released by each experimental unit during the 30-day cultivation experiment

[0383]

[0384] * Since no effect of the lime treatment was observed from the 2nd day to the 30th day (Table 19), the data provided represent the average values between the treatments with lime and without lime.

[0385] ** The data for the 1st day are not presented in the table because a significant lime treatment × fertilizer treatment was observed on this day. The results from the 1st day are discussed in this article.

[0386] 2.5. Recovery of the applied N

[0387] At the end of the experiment, the percentage of the recovered fertilizer-N (in the form of NH3 or mineral N) in the soil ranged from 65% to 92%. No effect of the lime treatment on this variable was observed. On the contrary, the treatment with urea had a significant effect (p = 0.0391). Among the treatments evaluated, the recovery rates of T4 and T8 were higher than that of T9 (Table 21). The differences observed in the recovery of fertilizer-N can be attributed to N losses by denitrification, N fixation in the microbial biomass, or N accumulation in chemical forms not calculated in the study (e.g., in the form of urea).

[0388] Table 21. Results of N% from the recovered fertilizer at the end of the experiment.

[0389]

[0390] 3. Conclusions

[0391] Among the treatments evaluated, compared with untreated urea, only at 14.0 L Mg-1 Applying formulation B at a ratio can reduce the cumulative amount of NH3 volatilized during the 30-day cultivation period. Considering the high volatilization rate of NH3 by formulation B (14.0 L Mg -1 ) in the later stage of cultivation, if the cultivation period is extended, the cumulative volatilization of the treatment will be comparable to that of other treatments. However, in all cases, the treatment with urea causes a decrease in the volatilization rate at a certain moment during cultivation. This effect depends on the product, ratio, and application of lime. Therefore, the use of materials (depending on the product and ratio) can be evaluated as a strategy to help synchronize the availability of N with plant requirements, thereby limiting possible N losses.

[0392] 4. References

[0393] Bremner, J.M. and Keeney, D.R. (1965). Steam distillation methods for determination of ammonium, nitrate and nitrite. Analytica chimica acta, 32, 485 - 495.

[0394] Bouyoucos, G.J. (1936). Directions for making mechanical analyses of soils by the hydrometer method. Soil Science, 42(3), 225 - 230.

[0395] Cabrera, M.L., Kissel, D.E. and Bock, B.R. (1991). Urea hydrolysis in soil: Effects of urea concentration and soil pH. Soil Biology and Biochemistry, 23(12), 1121 - 1124.

[0396] Chapman, H.D. (1965). Cation-exchange capacity. Methods of Soil Analysis: Part 2 Chemical and Microbiological Properties, 9, 891 - 901.

[0397] Haby, V.A., Russelle, M.P., & Skogley, E.O. (1990). Testing soils for potassium, calcium, and magnesium. Soil testing and plant analysis, 3, 181 - 227.

[0398] Walkley, A., & Black, I.A. (1934). An examination of the Degtjareff method for determining soil organic matter, and a proposed modification of the chromic acid titration method. Soil Science, 37(1), 29 - 38.

Claims

1. A method for inhibiting urease activity and / or fertilizing soil, the method comprising applying a urease inhibitor composition to the soil, wherein the urease inhibitor composition comprises: tert-Butylhydroquinone in an amount of about 0.1 wt% to about 65 wt% based on the total weight of the composition; and an organic solvent selected from the group consisting of sulfoxides, aromatic solvents, green solvents, safe solvents, and combinations thereof.

2. The composition according to claim 1, wherein the organic solvent comprises dimethyl sulfoxide, xylene, or a combination thereof.

3. The method according to claim 2, wherein dimethyl sulfoxide and xylene are present in a weight ratio of about 1:2 to about 2:

1.

4. The method according to claim 1, wherein the urease inhibitor composition further comprises an additive component selected from the group consisting of additives containing an α,β-unsaturated carbonyl system, acid-containing additives, ester-containing additives, aromatic additives, ethylene glycol-containing additives, and combinations thereof.

5. The method according to claim 4, wherein the additive component is an additive containing an α,β-unsaturated carbonyl system, which is selected from citral, mesityl oxide, α-amyl cinnamaldehyde, coumarin, and combinations thereof.

6. The method according to claim 4, wherein the additive component is an aromatic additive, which is selected from butylated hydroxyanisole, eugenol, salicylaldehyde, acetophenone, methyl salicylate, and combinations thereof.

7. The method according to claim 4, wherein the additive component is an acid-containing additive, which is selected from itacoic acid, adipic acid, maleic acid, octanoic acid, ethyl maltol, ascorbic acid, levulinic acid, and combinations thereof.

8. The method according to claim 4, wherein the additive component is an ester-containing additive, which is selected from triethyl citrate, isobornyl acetate, propylene carbonate, ethyl lactate, and combinations thereof.

9. The method according to claim 4, wherein the additive component is a diol-containing additive, which is selected from diethylene glycol monoethyl ether, ethylene glycol, monobutyl ether, and combinations thereof.

10. The method according to claim 4, wherein tert-butylhydroquinone and the additive component are present in a weight ratio of about 1:10 to about 10:

1.

11. The method according to claim 4, wherein the additive component is present in an amount of about 1 wt% to about 50 wt% based on the total weight of the composition.

12. The method according to claim 1, wherein the urease inhibitor composition further comprises a surfactant, a dispersant, an emulsifier, an antifoaming agent, a stabilizer, or a combination thereof.

13. The method according to claim 1, wherein at least about 50% of the urease activity is inhibited.

14. The method according to claim 1, wherein the method improves plant growth and / or plant health.

15. An agricultural composition, which comprises: a urease inhibitor composition; and a solid urea-containing fertilizer, wherein the urease inhibitor composition comprises tert-Butylhydroquinone; and an organic solvent selected from the group consisting of sulfones, aromatic solvents, green solvents, safe solvents, and combinations thereof, wherein the urease inhibitor composition is present in an amount of from about 0.001 wt% to about 10 wt% based on the total weight of the agricultural composition, and wherein the surface of the solid urea-containing fertilizer is coated with the urease inhibitor composition.

16. The agricultural composition according to claim 15, wherein the solid urea-containing fertilizer is in the form of granules or pellets.

17. The agricultural composition according to claim 16, wherein the average particle size (d50) of the solid urea-containing fertilizer granules ranges from about 0.5 to about 2.5 mm.

18. The agricultural composition according to claim 16, wherein the screen aperture size of the solid urea-containing fertilizer granules ranges from about 16 mesh to about 100 US mesh.

19. The agricultural composition according to claim 15, wherein the organic solvent comprises dimethyl sulfoxide, xylene or a combination thereof.

20. The agricultural composition according to claim 19, wherein dimethyl sulfoxide and xylene are present in a weight ratio of from about 1:2 to about 2:

1.

21. The agricultural composition according to claim 15, wherein the urease inhibitor composition further comprises an additive component selected from the group consisting of additives containing an α,β-unsaturated carbonyl system, acid-containing additives, ester-containing additives, aromatic additives, and diol-containing additives.

22. The agricultural composition according to claim 21, wherein the additive component is an additive containing an α,β-unsaturated carbonyl system, which is selected from citral, mesityl oxide, α-amyl cinnamaldehyde, coumarin and combinations thereof.

23. The agricultural composition according to claim 21, wherein the additive component is an aromatic additive, which is selected from butylated hydroxyanisole, eugenol, salicylaldehyde, acetophenone, methyl salicylate and combinations thereof.

24. The agricultural composition according to claim 21, wherein the additive component is an acid-containing additive, which is selected from itaconic acid, adipic acid, maleic acid, octanoic acid, ethyl maltol, ascorbic acid, levulinic acid and combinations thereof.

25. The agricultural composition according to claim 21, wherein the additive component is an ester-containing additive, which is selected from triethyl citrate, isobornyl acetate, propylene carbonate, ethyl lactate and combinations thereof.

26. The agricultural composition according to claim 21, wherein the additive component is a diol-containing additive, which is selected from diethylene glycol monoethyl ether, ethylene glycol, monobutyl ether and combinations thereof.

27. The agricultural composition according to claim 21, wherein tert-butylhydroquinone and the additive component are present in a weight ratio of from about 1:10 to about 10:

1.

28. The agricultural composition according to claim 21, wherein the additive component is present in an amount of from about 1 wt% to about 50 wt% based on the total weight of the composition.

29. The agricultural composition according to claim 21, wherein the urease inhibitor composition further comprises a surfactant, a dispersant, an emulsifier, a defoamer, a stabilizer or a combination thereof.

30. A method for preparing an agricultural composition according to claim 15, the method comprising applying a urease inhibitor composition in liquid or dispersion form to the surface of a solid urea-containing fertilizer, thereby coating the solid urea-containing fertilizer.

31. A urease inhibitor composition, comprising: tert-Butylhydroquinone, present in an amount of about 0.1 wt% to about 65 wt% based on the total weight of the composition; an additive selected from additives containing an α,β-unsaturated carbonyl system, acid-containing additives, ester-containing additives, aromatic additives, diol-containing additives; and an organic solvent selected from sulfoxides, aromatic solvents, green solvents, safe solvents and combinations thereof, wherein the additive is present in an amount of about 1 wt% to about 50 wt% based on the total weight of the composition, and wherein tert-butylhydroquinone and the additive component are present in synergistic amounts.

32. The composition according to claim 31, wherein tert-butylhydroquinone and the additive are present in a weight ratio of about 1:10 to about 10:

1.

33. The composition according to claim 31, wherein the organic solvent comprises dimethyl sulfoxide, xylene or a combination thereof.

34. The composition according to claim 33, wherein dimethyl sulfoxide and xylene are present in a weight ratio of about 1:2 to about 2:

1.

35. The composition according to claim 31, wherein the additive component is selected from additives containing an α,β-unsaturated carbonyl system, acid-containing additives, ester-containing additives, aromatic additives, diol-containing additives and combinations thereof.

36. The composition according to claim 35, wherein the additive component is an additive containing an α,β-unsaturated carbonyl system, selected from citral, mesityl oxide, α-amyl cinnamaldehyde, coumarin and combinations thereof.

37. The composition according to claim 35, wherein the additive component is an aromatic additive, selected from butylated hydroxyanisole, eugenol, salicylaldehyde, acetophenone, methyl salicylate and combinations thereof.

38. The composition according to claim 35, wherein the additive component is an acid-containing additive, selected from itaconic acid, adipic acid, maleic acid, octanoic acid, ethyl maltol, ascorbic acid, levulinic acid and combinations thereof.

39. The composition according to claim 35, wherein the additive component is an ester-containing additive, selected from triethyl citrate, isobornyl acetate, propylene carbonate, ethyl lactate and combinations thereof.

40. The composition according to claim 35, wherein the additive component is a glycol-containing additive, selected from diethylene glycol monoethyl ether, ethylene glycol, monobutyl ether and combinations thereof.

41. The composition according to claim 31, wherein the urease inhibitor composition further comprises a surfactant, a dispersant, an emulsifier, an antifoaming agent, a stabilizer or a combination thereof.

42. The composition according to claim 31, wherein at least about 50% of the urease activity is inhibited.

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