Triazolemethanol as nitrification inhibitors for fertilizer applications

Abstract

Nitrification inhibitor compositions and methods for inhibiting nitrification of ammonia in soil are disclosed. Methods of preparing the nitrification inhibitors are also disclosed.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority from European Application No. 22189690.5 filed on August 10, 2022. The contents of which are incorporated herein by reference in their entirety. Background of the Invention I. Technical field

[0004] The present disclosure generally relates to compositions for maintaining nitrogen levels in soil or reducing nitrogen loss in soil. II. Background Technology

[0005] Nitrogen is one of the most important nutrients for plant growth and productivity. Nitrogen use efficiency (NUE) is defined as the ratio of nitrogen uptake by a crop to total nitrogen fertilizer input. In crops, NUE is notoriously poor, with approximately 50% of nitrogen fertilizer applied to a crop system in the form of ammonia (NH3), nitrate (NO3 - ) and nitrous oxide (N2O, a greenhouse gas) are lost to the environment. Low NUE in the agricultural industry leads to high agricultural production costs, environmental pollution and climate change. These losses are caused by the processes of nitrification and subsequent denitrification catalyzed by soil microorganisms.

[0006] Nitrification is traditionally considered a two-step process in which ammonia (NH3) is first oxidized to nitrite (NO2 - ), which is subsequently oxidized to nitrate (NO3 - ). Recent evidence indicates complete nitrification by Nitrospira bacteria present in natural soil environments.

[0007] Governments around the world have implemented regulations that force the agricultural industry to reduce its environmental impact. One method used to reduce the environmental impact of agriculture includes the use of nitrification inhibitors. Nitrification inhibitors are chemical compounds that can prevent or slow the nitrification of ammonia. These inhibitors help reduce the loss of nitrogen from the soil, which in turn can be used by plants.

[0008] Some plants naturally produce nitrification inhibition through root exudates known as biological nitrification inhibitors (BNIs). These natural compounds include 2-hydroxy-5-methoxy-1,4-benzoquinone (Sorgoleone), methyl 3-(4-hydroxyphenyl) propionate, and 1,9-decanediol. Fertilizer research has led to the development of synthetic nitrification inhibitors (NIs), including chlorpyrifos, dicyandiamide (DCD), and 3,4-dimethylpyrazole phosphate (DMPP). Biological nitrification inhibitors and synthetic nitrification inhibitors have various disadvantages, including instability at high temperatures, instability at high or low pH, unstable efficacy, difficult application, high cost, environmental pollution, and food safety risks. Therefore, there is an unmet need to discover new non-toxic nitrification inhibitors that are effective in a wide range of soil types, pH, and temperatures. Summary of the invention

[0009] Disclosed herein are solutions to at least some of the problems discussed above. In some cases, the solutions lie in nitrification inhibitors disclosed herein and methods for synthesizing the nitrification inhibitors. The nitrification inhibitors disclosed herein may include small molecules, which in some cases can be synthesized in a single step using relatively inexpensive reagents. In some cases, the nitrification inhibitors have a high melting point, which facilitates the formulation of the nitrification inhibitors with molten urea at a temperature of about 132°C to 135°C or above 135°C. The nitrification inhibitors are virtually non-toxic and are as effective or more effective than nitrification inhibitors currently on the market. The nitrification inhibitors can be used in various types of soils and can be used over a wide range of temperatures and pH values. Therefore, certain aspects of the present disclosure relate to compositions that provide reduced nitrification of ammonium nitrogen, the compositions comprising a nitrification inhibitor of Formula I:

[0010]

[0011] wherein R1, R2 and R3 are each independently H, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl, or a salt thereof; in some aspects, R1 is H. In other aspects, R2 is H. In some aspects, R3 is H. In some aspects, the nitration inhibitor is further defined as Formula II:

[0012]

[0013] Some aspects of the present disclosure relate to methods for inhibiting nitrification of ammonia in soil, the methods comprising applying to the soil a composition comprising a nitrification inhibitor of Formula I. The nitrification inhibitor can be applied to the soil by applying directly to the soil, by plowing into the soil, by applying to water in contact with the soil, etc. In some cases, the nitrification inhibitor is applied to the soil at the same time as fertilizer, water, additional soil, soil supplement, seed, plant, etc., or the nitrification inhibitor is applied to the soil at a different time than fertilizer, water, additional soil, soil supplement, seed, plant, etc.

[0014] In some cases, the composition may consist of or consist essentially of a nitrification inhibitor. In some cases, the composition further comprises at least one nitrogen fertilizer component. The at least one nitrogen fertilizer component may be selected from urea, ammonium salts, anhydrous ammonia and combinations thereof. In specific aspects, the at least one nitrogen fertilizer component is urea. In some embodiments, the urea is a solidified urea melt. In some aspects, the composition further comprises a phosphate-based fertilizer. In some cases, the nitrification inhibitor is contained in a solidified urea melt.

[0015] In some aspects, the composition also includes at least one other nitrification inhibitor. The at least one other nitrification inhibitor can be chlorpyrifos, dicyandiamide, ammonium thiosulfate, 3-(4-hydroxyphenyl) methyl propionate, 1,9-decanediol, potassium azide, 2-amino-4-chloro-6-methylpyridine, sulfathiazole, 4-amino-1,2,4-triazole, 2,4-diamino-6-trichloromethyl-s-triazine, potassium ethyl xanthate, guanylthiourea, 4-nitrotrichlorotoluene, 4-methylsulfonyltrichlorotoluene, sodium thiocarbonate, phenylmercuric acetate, 3,4-dimethylpyrazole phosphate or sorgoleone or a combination thereof. In some aspects, the composition also includes at least one urease inhibitor. The at least one urease inhibitor can be at least one of n-butylthiophosphoric acid triamine (NBTPT) and n-propylthiophosphoric acid triamine. In some aspects, the composition also includes at least one other nitrification inhibitor and at least one urease inhibitor.

[0016] In some aspects, the nitrification inhibitor is contained in a carrier. In some aspects, the carrier comprises plaster of Paris, flour, chalk, starch, gluten, kaolin, bentonite, colloidal silicon dioxide, silicon dioxide, dried wine grains and solubles thereof, lignin, synthetic polymers, waxes, chitin, glycosaminoglycans, pectin, hyaluronic acid, chondroitin sulfate, dermatan sulfate, alginic acid, polymannuronic acid, polyguluronic acid, polyglucuronic acid, amylose, amylopectin, callose, chitosan, polygalactomannan, dextran, xanthan gum, keratan sulfate, MgO, CaO, bone powder, rice bran, CaCO3, Na2CO3, K2CO3, KH2PO4, NaHCO3 and / or MgCO3. In some embodiments, the synthetic polymer comprises polybutylene succinate adipate, polylactic acid, polybutylene succinate, cellulose triacetate, cellulose diacetate, cellulose acetate, acetate starch, poly(caprolactone), poly(butylene terephthalate adipate), hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, methylcellulose, ethyl cellulose, ethyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, polyethylene glycol, cyclodextrin, or a combination thereof.

[0017] In some aspects, the composition improves the nitrogen use efficiency (NUE) of the crop. In some aspects, the method further comprises applying a nitrogen fertilizer component to the soil, wherein the nitrogen fertilizer component and the composition are contained in two separate compositions. In some aspects, the two separate compositions are each applied to the soil within one hour. In other aspects, the two separate compositions are applied to the soil separately and each is not applied within one hour. In other aspects, the nitrogen fertilizer component and the nitrification inhibitor are contained in a single composition.

[0018] The following Aspect 1 to Aspect 56 of the present invention are also disclosed.

[0019] Aspect 1 is a method for inhibiting nitrification of ammonia in soil, the method comprising applying to the soil a composition comprising a nitrification inhibitor of formula I:

[0020]

[0021] wherein R1, R2 and R3 are each independently H, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, or a salt thereof.

[0022] Aspect 2 is a method according to aspect 1, wherein the composition further comprises at least one nitrogen fertilizer component.

[0023] Aspect 3 is a method according to aspect 2, wherein the at least one nitrogen fertilizer component is selected from urea, ammonium salts, anhydrous ammonia and combinations thereof.

[0024] Aspect 4 is a method according to any one of aspects 1 to 3, wherein the composition further comprises at least one additional nitrification inhibitor.

[0025] Aspect 5 is a method according to any one of aspects 1 to 4, wherein the at least one additional nitrification inhibitor is selected from chlorpyrifos, dicyandiamide, ammonium thiosulfate, methyl 3-(4-hydroxyphenyl)propionate, 1,9-decanediol, potassium azide, 2-amino-4-chloro-6-methylpyridine, sulfathiazole, 4-amino-1,2,4-triazole, 2,4-diamino-6-trichloromethyl-s-triazine, potassium ethylxanthate, guanylthiourea, 4-nitrotrichlorotoluene, 4-methylsulfonyltrichlorotoluene, sodium thiocarbonate, phenylmercuric acetate, 3,4-dimethylpyrazole phosphate, sorgoleone, and combinations thereof.

[0026] Aspect 6 is a method according to any one of aspects 1 to 5, wherein the composition further comprises at least one urease inhibitor.

[0027] Aspect 7 is a method according to aspect 6, wherein the at least one urease inhibitor is at least one of n-butylthiophosphoric acid triamide and n-propylthiophosphoric acid triamide.

[0028] Aspect 8 is a method according to any one of aspects 1 to 7, wherein the composition improves nitrogen use efficiency (NUE) of crops.

[0029] Aspect 9 is the method according to any one of aspects 1 to 8, wherein the method further comprises applying a nitrogen fertilizer component to the soil, wherein the nitrogen fertilizer component and the composition are contained in two separate compositions.

[0030] Aspect 10 is the method according to aspect 9, wherein the two separate compositions are each applied to the soil within one hour.

[0031] Aspect 11 is the method according to aspect 9, wherein the two separate compositions are applied to the soil separately and are not applied within one hour of each other.

[0032] Aspect 12 is a method according to any one of aspects 1 to 11, wherein R1 is H.

[0033] Aspect 13 is a method according to any one of aspects 1 to 12, wherein R2 is H.

[0034] Aspect 14 is a method according to any one of aspects 1 to 13, wherein R3 is H.

[0035] Aspect 15 is a method according to any one of aspects 1 to 14, wherein the nitrification inhibitor is further defined as a nitrification inhibitor of formula II:

[0036]

[0037] Aspect 16 is a method according to any one of aspects 2 to 15, wherein the nitrogen fertilizer component is urea.

[0038] Aspect 17 is a method according to aspect 16, wherein the urea is a solidified urea melt.

[0039] Aspect 18 is a method according to aspect 17, wherein the nitrification inhibitor is contained in the solidified urea melt.

[0040] Aspect 19 is the method according to any one of aspects 1 to 18, wherein the nitrification inhibitor is contained in a carrier.

[0041] Aspect 20 is a method according to aspect 19, wherein the carrier comprises plaster of Paris, flour, chalk, starch, gluten, kaolin, bentonite, colloidal silicon, silicon dioxide, dried distillers grains and solubles thereof, lignin, synthetic polymers, waxes, chitin, glycosaminoglycans, pectin, hyaluronic acid, chondroitin sulfate, dermatan sulfate, alginic acid, polymannuronic acid, polyguluronic acid, polyglucuronic acid, amylose, amylopectin, callose, chitosan, polygalactomannan, dextran, xanthan gum, keratan sulfate, MgO, CaO, bone powder, rice bran, CaCO3, Na2CO3, K2CO3, KH2PO4, NaHCO3 and / or MgCO3.

[0042] Aspect 21 is a method according to aspect 20, wherein the synthetic polymer comprises polybutylene succinate adipate, polylactic acid, polybutylene succinate, cellulose triacetate, cellulose diacetate, cellulose acetate, acetate starch, poly(caprolactone), poly(butylene terephthalate adipate), hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, methylcellulose, ethyl cellulose, ethyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, cyclodextrin, polyethylene glycol, or a combination thereof.

[0043] Aspect 22 is a fertilizer composition that provides reduced nitrification of ammonium nitrogen, comprising:

[0044] At least one nitrogen (N) fertilizer component, phosphorus (P) fertilizer component, and / or potassium (K) fertilizer component; and a nitrification inhibitor of formula I:

[0045]

[0046] wherein R1, R2 and R3 are each independently H, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, or a salt thereof.

[0047] Aspect 23 is the fertilizer composition of aspect 22, wherein the composition further comprises at least one additional nitrification inhibitor.

[0048] Aspect 24 is a fertilizer composition according to aspect 23, wherein the at least one additional nitrification inhibitor is selected from chlorpyrifos, dicyandiamide, ammonium thiosulfate, methyl 3-(4-hydroxyphenyl)propionate, 1,9-decanediol, potassium azide, 2-amino-4-chloro-6-methylpyridine, sulfathiazole, 4-amino-1,2,4-triazole, 2,4-diamino-6-trichloromethyl-s-triazine, potassium ethylxanthate, guanylthiourea, 4-nitrotrichlorotoluene, 4-methylsulfonyltrichlorotoluene, sodium thiocarbonate, phenylmercuric acetate, 3,4-dimethylpyrazole phosphate, sorgoleone, and combinations thereof.

[0049] Aspect 25 is a fertilizer composition according to any one of aspects 22 to 24, wherein the composition further comprises at least one urease inhibitor.

[0050] Aspect 26 is the fertilizer composition according to aspect 25, wherein the ammonia source is ammonium hydroxide (NH 4 OH) and / or ammonia (NH 3 ).

[0051] Aspect 27 is a fertilizer composition according to any one of aspects 22 to 26, wherein the nitrification inhibitor is contained on the surface of at least one N fertilizer component, P fertilizer component, and / or K fertilizer component.

[0052] Aspect 28 is a fertilizer composition according to any one of aspects 22 to 26, wherein the composition comprises a substantially homogeneous mixture of a nitrification inhibitor and at least one of the N fertilizer component, the P fertilizer component, and / or the K fertilizer component.

[0053] Aspect 29 is the fertilizer composition of any one of aspects 22 to 28, wherein R1 is H.

[0054] Aspect 30 is the fertilizer composition of any one of aspects 22 to 29, wherein R2 is H.

[0055] Aspect 31 is the fertilizer composition of any one of aspects 22 to 30, wherein R3 is H.

[0056] Aspect 32 is a fertilizer composition according to any one of aspects 22 to 31, wherein the nitrification inhibitor is further defined as a nitrification inhibitor of formula II:

[0057]

[0058] Aspect 33 is a fertilizer composition according to any one of aspects 22 to 32, wherein the at least one N fertilizer component, P fertilizer component and / or K fertilizer component comprises urea.

[0059] Aspect 34 is the fertilizer composition according to aspect 33, wherein the nitrification inhibitor is contained in a solidified urea melt.

[0060] Aspect 35 is the fertilizer composition of any one of aspects 22 to 34, wherein the nitrification inhibitor is contained in a carrier.

[0061] Aspect 36 is a fertilizer composition according to aspect 35, wherein the carrier comprises plaster of Paris, flour, chalk, starch, gluten, kaolin, bentonite, colloidal silicon, silicon dioxide, dried distiller's grains and solubles thereof, lignin, synthetic polymers, waxes, chitin, glycosaminoglycans, pectin, hyaluronic acid, chondroitin sulfate, dermatan sulfate, alginic acid, polymannuronic acid, polyguluronic acid, polyglucuronic acid, amylose, amylopectin, callose, chitosan, polygalactomannan, dextran, xanthan gum, keratan sulfate, MgO, CaO, bone powder, rice bran, CaCO3, Na2CO3, K2CO3, KH2PO4, NaHCO3 and / or MgCO3.

[0062] Aspect 37 is a fertilizer composition according to aspect 36, wherein the synthetic polymer comprises polybutylene succinate adipate, polylactic acid, polybutylene succinate, cellulose triacetate, cellulose diacetate, cellulose acetate, acetate starch, poly(caprolactone), poly(butylene terephthalate adipate), hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, methylcellulose, ethyl cellulose, ethyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, cyclodextrin, polyethylene glycol, or a combination thereof.

[0063] Aspect 38 is a composition comprising:

[0064] Nitrification inhibitor of formula I:

[0065]

[0066] wherein R1, R2 and R3 are each independently H, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl, or a salt thereof; and

[0067] Additional inhibitors include urease inhibitors and / or additional nitrification inhibitors.

[0068] Aspect 39 is a composition according to aspect 38, wherein the additional inhibitor comprises a urease inhibitor.

[0069] Aspect 40 is a composition according to aspect 39, wherein the urease inhibitor is selected from n-butylthiophosphoric acid triamide and n-propylthiophosphoric acid triamide, and combinations thereof.

[0070] Aspect 41 is a composition according to any one of aspects 38 to 40, wherein the additional inhibitor comprises the additional nitrification inhibitor.

[0071] Aspect 42 is a composition according to aspect 41, wherein the nitrification inhibitor is selected from chlorpyrifos, dicyandiamide, ammonium thiosulfate, methyl 3-(4-hydroxyphenyl)propionate, 1,9-decanediol, potassium azide, 2-amino-4-chloro-6-methylpyridine, sulfathiazole, 4-amino-1,2,4-triazole, 2,4-diamino-6-trichloromethyl-s-triazine, potassium ethylxanthate, guanylthiourea, 4-nitrotrichlorotoluene, 4-methylsulfonyltrichlorotoluene, sodium thiocarbonate, phenylmercuric acetate, 3,4-dimethylpyrazole phosphate, sorgoleone and combinations thereof.

[0072] Aspect 43 is a composition according to any one of aspects 38 to 42, further comprising a carrier.

[0073] Aspect 44 is a composition according to aspect 43, wherein the carrier comprises plaster of Paris, flour, chalk, starch, gluten, kaolin, bentonite, colloidal silicon, silicon dioxide, dried distillers grains and solubles thereof, lignin, synthetic polymers, waxes, chitin, glycosaminoglycans, pectin, hyaluronic acid, chondroitin sulfate, dermatan sulfate, alginic acid, polymannuronic acid, polyguluronic acid, polyglucuronic acid, amylose, amylopectin, callose, chitosan, polygalactomannan, dextran, xanthan gum, keratan sulfate, MgO, CaO, bone powder, rice bran, CaCO3, Na2CO3, K2CO3, KH2PO4, NaHCO3 and / or MgCO3.

[0074] Aspect 45 is a composition according to aspect 44, wherein the synthetic polymer comprises polybutylene succinate adipate, polylactic acid, polybutylene succinate, cellulose triacetate, cellulose diacetate, cellulose acetate, acetate starch, poly(caprolactone), poly(butylene terephthalate adipate), hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, methylcellulose, ethyl cellulose, ethyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, cyclodextrin, polyethylene glycol, or a combination thereof.

[0075] Aspect 46 is a composition according to any one of aspects 38 to 45, wherein R1 is H.

[0076] Aspect 47 is a composition according to any one of aspects 38 to 46, wherein R2 is H.

[0077] Aspect 48 is a composition according to any one of aspects 38 to 47, wherein R3 is H.

[0078] Aspect 49 is a composition according to any one of aspects 38 to 48, wherein the nitrification inhibitor is further defined as a nitrification inhibitor of formula II:

[0079]

[0080] Aspect 50 is a composition comprising:

[0081] Nitrification inhibitor of formula I:

[0082]

[0083] wherein R1, R2 and R3 are each independently H, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl, or a salt thereof; and

[0084] Solid support.

[0085] Aspect 51 is a composition according to aspect 50, wherein the solid carrier comprises plaster of Paris, flour, chalk, starch, gluten, kaolin, bentonite, colloidal silicon, silicon dioxide, dried distillers grains and solubles thereof, lignin, synthetic polymers, waxes, chitin, glycosaminoglycans, pectin, hyaluronic acid, chondroitin sulfate, dermatan sulfate, alginic acid, polymannuronic acid, polyguluronic acid, polyglucuronic acid, amylose, amylopectin, callose, chitosan, polygalactomannan, dextran, xanthan gum, keratan sulfate, MgO, CaO, bone powder, rice bran, CaCO3, Na2CO3, K2CO3, KH2PO4, NaHCO3 and / or MgCO3.

[0086] Aspect 52 is a composition according to aspect 51, wherein the synthetic polymer comprises polybutylene succinate adipate, polylactic acid, polybutylene succinate, cellulose triacetate, cellulose diacetate, cellulose acetate, acetate starch, poly(caprolactone), poly(butylene terephthalate adipate), hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, methylcellulose, ethyl cellulose, ethyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, cyclodextrin, polyethylene glycol, or a combination thereof.

[0087] Aspect 53 is a composition according to any one of aspects 50 to 52, wherein R1 is H.

[0088] Aspect 54 is a composition according to any one of aspects 50 to 53, wherein R2 is H.

[0089] Aspect 55 is a composition according to any one of aspects 50 to 54, wherein R3 is H.

[0090] Aspect 56 is a composition according to any one of aspects 50 to 55, wherein the nitrification inhibitor is further defined as a nitrification inhibitor of formula II:

[0091]

[0092] The term "nitrification inhibitors" are compounds that inhibit bacteria in the soil from converting nitrogen, such as provided in fertilizer compounds, into nitrates.

[0093] The term "urease inhibitor" is a compound that inhibits the activity of urease, the enzyme that converts urea to ammonia.

[0094] The term "fertilizer" is defined as a substance applied to soil or plant tissue to provide one or more plant nutrients necessary or beneficial to plant growth, and / or a growth promoter or enhancer that promotes or enhances plant growth.

[0095] The term "particle" may include solid materials. Particles may have a variety of shapes, non-limiting examples of which include spheres, spheres, ovals, rods, ellipses, or random shapes.

[0096] The term "particle" may include solid material whose largest dimension is less than a millimeter.

[0097] The term "particulate" or "powder" may include a plurality of particles.

[0098] The term "about" or "approximately" as used herein is defined as close to what is understood by those of ordinary skill in the art. In a non-limiting embodiment, these terms are defined as within ±10% deviation, preferably within ±5%, more preferably within ±1%, and most preferably within ±0.5%.

[0099] The terms "wt %, "volume %" or "mole %" refer to the weight percent, volume percent or mole percent of a component based on the total weight of the material, the total volume of the material or the total moles of the material, respectively. In a non-limiting example, 10 grams of a component in 100 grams of a material is 10 wt % of the component.

[0100] When used with the terms "include" or "comprising", the element without a quantifier can mean "a", but it also has the meaning of "one or more", "at least one" and "one or more than one".

[0101] The phrase "and / or" means "and" or "or". For example, A, B, and / or C includes: A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C. In other words, "and / or" serves as an inclusive "or".

[0102] The words "comprising," "having," "including," or "containing" are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0103] Compositions and methods for use of compositions and methods may "comprise" or "contain," "consist essentially of," or "consist of" any ingredient or any step disclosed throughout the specification. Compositions and methods that "consist essentially of" any ingredient or any step disclosed limit the scope of the claims to the specific materials or steps that do not materially affect the basic and novel characteristics of the claimed invention.

[0104] It is contemplated that any embodiment discussed in this specification may be implemented corresponding to any method or any composition of the present invention, and vice versa. In addition, the composition of the present invention may be used to realize the method of the present invention. Other objects, features and advantages of the present invention will become clear through the following detailed description. However, it should be understood that although the detailed description and specific examples show specific embodiments of the present invention, they are only given by way of illustration, because various changes and modifications within the spirit and scope of the present invention will become apparent to those skilled in the art according to this detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0105] The following drawings constitute part of this specification and are included to further illustrate certain aspects of the present invention. The present invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments provided herein.

[0106] Figure 1 : Chemical pathways for the conversion of ammonia to nitrate and N2O.

[0107] FIG. 2A to FIG. 2B : The active site of ammonium oxidase. Figure 2A is a schematic diagram showing the purported active site of the ammonia oxidase copper metalloenzyme with two copper atoms. Figure 2B This is the ball-and-stick model of the active site of ammonia oxidase. DETAILED DESCRIPTION

[0108] Human activities have brought unprecedented amounts of reactive nitrogen to ecosystems, exerting the greatest impact on the global nitrogen cycle. Agriculture, in particular, is the largest human activity affecting the global nitrogen cycle. In agricultural systems, rapid and uncontrolled nitrification leads to inefficient nitrogen use by crops, resulting in nitrogen leakage and environmental pollution.

[0109] Nitrification is the conversion of ammonia into nitrite (NO2 - ), nitrate (NO3 - ) and nitrous oxide (N2O) process ( Figure 1). This process occurs naturally in the environment and is performed by specialized bacteria. Most nitrification is performed by two groups of ammonia-oxidizing bacteria: Nitrosomonas sp. and Nitrobacter spp. These bacteria are often ubiquitous components of soil microbial populations. Key bacterial enzymes in the nitrification process include ammonia monooxygenase, hydroxylamine dehydrogenase, and nitrite oxidoreductase. Inhibition of the first enzyme in the nitrification process, nitrifying enzyme ammonia monooxygenase, slows down the conversion of NH4 + to NH2OH and slows down fertilizer loss due to nitrification.

[0110] Certain aspects of the present disclosure relate to compositions that inhibit the nitrification process, thereby increasing the life span of nitrogen in the soil. This process is achieved by applying one or more than one nitrification inhibitor compound disclosed herein to plants, soil or crops. The nitrification inhibitors disclosed herein can be combined with additional nitrification inhibitors and / or urease inhibitors that inhibit the conversion of urea to ammonium and carbon dioxide. The nitrification inhibitors disclosed herein include small, low molecular weight organic compounds without chiral centers. The synthesis cost of these compounds is relatively low and can be produced in large quantities at a cost that is only a fraction of other more complex nitrification inhibitors.

[0111] I. Nitrification inhibitors

[0112] Certain embodiments herein relate to compositions comprising a nitrification inhibitor of Formula I:

[0113]

[0114] wherein R1, R2 and R3 are each independently H, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl, or a salt thereof. The composition may also include at least one nitrogen fertilizer component, at least one additional nitrification inhibitor, and / or at least one urease inhibitor. The nitrification inhibitor may be used to inhibit the nitrification of ammonia in the soil by applying the composition to the soil.

[0115] In some aspects, fertilizer nutrients may or may not be included in the nitrification inhibitor. If included, fertilizer nutrients may be selected according to the specific needs of certain types of soil, climate or other growth conditions to maximize the effectiveness of fertilizers in promoting plant growth and crop yield. Other additives may or may not be included in the nitrification inhibitor composition. Non-limiting examples of additives that may or may not be included in the nitrification inhibitor composition of the present invention include nitrogen nutrients, phosphorus nutrients, potassium nutrients, trace element nutrients and / or secondary nutrients. The trace nutrients may be copper, iron, chloride, manganese, molybdenum, or nickel or any combination thereof. The nitrogen nutrients may be urea, ammonium nitrate, ammonium sulfate, diammonium phosphate, monoammonium phosphate, urea-formaldehyde, ammonium chloride and / or potassium nitrate. In some aspects, the secondary nutrients may include calcium, magnesium and / or sulfur, such as lime and / or superphosphate.

[0116] In some cases, the nitrification inhibitor composition may include at least one additional nitrification inhibitor and / or at least one urease inhibitor. Suitable nitrification inhibitors include, but are not limited to, 3,4-dimethylpyrazole phosphate (DMPP), dicyandiamide (DCD), thiourea (TU), 2-chloro-6-(trichloromethyl)-pyridine (chlorpyrifos), 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole sold under the trade name NBTPT, 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercaptobenzothiazole (MBT) or 2-sulfathiazole (ST) and any combination thereof. In one aspect, the nitrification inhibitor may include DMPP, DCD, TU, chlorpyrifos, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, AM, MBT or ST or a combination thereof. In some embodiments, the fertilizer composition may include NBTPT, DMPP, TU, DCD, PPDA, chlorpyrifos, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, AM, MBT, ST or a combination thereof.

[0117] In some cases, a binder may be included in the nitrification inhibitor composition. Exemplary binders include phosphates, polyphosphates, biodegradable polymers, or waxes, or combinations thereof. Suitable waxes include, but are not limited to, vegetable waxes, high melting point waxes, ethylene bis stearamide waxes, paraffin waxes, polyethylene waxes, and olefin waxes. Suitable phosphates include, but are not limited to, diammonium phosphate and monoammonium phosphate. Suitable polyphosphates include, but are not limited to, ammonium polyphosphate. Suitable biodegradable polymers include, but are not limited to, polyacrylamide, polyacrylic acid, polyacrylonitrile, biodegradable polylactic acid, and other biodegradable polymer materials, such as polylactic acid, poly(3-hydroxypropionic acid), polyvinyl alcohol, polyethylene glycol, poly-ε-caprolactone, poly-L-lactide, polybutylene succinate, and biodegradable starch-based polymers. The binder may include plaster of Paris, flour, starch, gluten, kaolin, bentonite, colloidal silicon dioxide, cyclodextrin, or combinations thereof. Suitable flours include, but are not limited to, rice flour, wheat flour, and bleached wheat flour. Suitable starches include, but are not limited to, dextrin-modified starch.

[0118] In some cases, the nitrification inhibitor composition can include a pH buffer. Exemplary pH buffers include MgO, KH2PO4, NaHCO3, chalk, aluminum hydroxide, magnesium hydroxide, aluminum hydroxide / magnesium hydroxide coprecipitate, aluminum hydroxide / sodium bicarbonate coprecipitate, calcium acetate, calcium bicarbonate, calcium borate, calcium carbonate, calcium bicarbonate, calcium citrate, calcium gluconate, calcium hydroxide, dibasic sodium phosphate, dipotassium hydrogenphosphate, dipotassium phosphate, disodium hydrogenphosphate, magnesium acetate, magnesium borate, magnesium bicarbonate, magnesium carbonate, magnesium hydroxide, magnesium lactate, magnesium oxide, magnesium phosphate, magnesium silicate, magnesium succinate, magnesium tartrate, potassium acetate, potassium carbonate, potassium bicarbonate, potassium borate, potassium citrate, potassium metaphosphate, potassium phthalate, potassium phosphate, potassium polyphosphate, potassium pyrophosphate, potassium succinate, potassium tartrate, sodium acetate, sodium bicarbonate, sodium borate, sodium carbonate, sodium citrate, sodium gluconate, sodium hydrogen phosphate, phosphate), sodium hydroxide, sodium lactate, sodium phthalate, sodium phosphate, sodium polyphosphate, sodium pyrophosphate, sodium tartrate, sodium tripolyphosphate, synthetic hydrotalcite, tetrapotassium pyrophosphate, tetrasodium pyrophosphate, tripotassium phosphate, trisodium phosphate and tromethamine and combinations thereof.

[0119] The nitrification inhibitor composition described herein can be included in a composition for application to soil. In some aspects, in addition to the nitrification inhibitor composition described herein, the composition can include fertilizer compounds, trace element nutrients, major nutrients, urea, nitrogen nutrients, pesticides, herbicides, or fungicides, or a combination thereof. The nitrification inhibitor composition described herein can also be included in a mixed composition comprising fertilizer. The fertilizer can be urea, monoammonium phosphate (MAP), diammonium phosphate (DAP), potassium chloride salt (MOP), monopotassium phosphate (MKP), triple superphosphate (TSP), phosphate rock, superphosphate (SSP), ammonium sulfate, etc.

[0120] The nitrification inhibitor formed into particles can have desired physical properties, such as desired levels of abrasion resistance, particle strength, granulation, hygroscopicity, particle shape, and particle size distribution. In some aspects, the nitrification inhibitor composition particles can have a compressive strength greater than 1.5 kgf, such as greater than 1.8 kgf, such as 2 kgf to 6 kgf, or at least any one of the following compressive strengths, equal to any one, or between any two: 2 kgf, 2.5 kgf, 3 kgf, 3.5 kgf, 4 kgf, 4.5 kgf, 5 kgf, 5.5 kgf, and 6 kgf. The bulk density of the fertilizer granules can be 1 g / cm3 to 1.2 g / cm3, or at least any one, at most any one, equal to any one, or between any two of the following densities: 1 g / cm3, 1.02 g / cm3, 1.04 g / cm3, 1.06 g / cm3, 1.08 g / cm3, 1.1 g / cm3, 1.12 g / cm3, 1.14 g / cm3, 1.16 g / cm3, 1.18 g / cm3 and 1.2 g / cm3. In some aspects, under stirring at a speed of 90 rpm to 110 rpm and at ambient temperature, within 5 minutes of adding 100 mg of the fertilizer granules to water, 10 mg or more, such as 10 mg to 40 mg, or at least any one, at most any one, equal to any one, or between any two of the following masses of the fertilizer granules can be dissolved in 1 mL of water at pH 7: 10 mg, 11 mg, 12 mg, 13 mg, 14 mg, 15 mg, 16 mg, 17 mg, 18 mg, 19 mg, 20 mg, 21 mg, 22 mg, 23 mg, 24 mg, 25 mg, 26 mg, 27 mg, 28 mg, 29 mg, 30 mg, 31 mg, 32 mg, 33 mg, 34 mg, 35 mg, 36 mg, 37 mg, 38 mg, 39 mg, and 40 mg. In some aspects, the fertilizer granules can lose less than 0.13 wt %, such as 0.02 wt % to 0.12 wt %, or up to any one of, equal to any one of, or between any two of the following wt % in an attrition loss test: 0.02 wt %, 0.03 wt %, 0.04 wt %, 0.05 wt %, 0.06 wt %, 0.07 wt %, 0.08 wt %, 0.09 wt %, 0.1 wt %, 0.11 wt %, and 0.12 wt %. The following attrition loss test can be used to measure attrition loss.

[0121] Abrasion loss test: weigh single particles with a size of 2mm to 4mm and a total volume of 100cm 3A plurality of sieved nitrification inhibitor particles (W1) were prepared and placed in a test drum together with 50 stainless steel balls with a total weight of 100 grams. The test drum was sealed and rotated at 30 rpm for 10 minutes. The balls were then separated from the sample and the material was sieved on a 2 mm sieve using a vibrating sieve. The total weight of the particles on the 2 mm sieve was then reweighed (W2). The results were calculated as weight loss % using the following formula:

[0122]

[0123] In some cases, the nitrification inhibitor composition can be extruded prior to drying. The extruder can extrude the nitrification inhibitor composition at a pressure of at least, at a pressure of at most, at a pressure of, or between any two of the following pressures: 1 bar, 2 bar, 3 bar, 4 bar, 5 bar, 6 bar, 7 bar, 8 bar, 9 bar, 10 bar, 11 bar, 12 bar, 13 bar, 14 bar, 15 bar, 16 bar, 17 bar, 18 bar, 19 bar, 20 bar, 21 bar, 22 bar, 23 bar, 24 bar, 25 bar, 26 bar, 27 bar, 28 bar, 29 bar, 30 bar, 31 bar, 32 bar, 33 bar, 34 bar, 35 bar, 36 bar, 37 bar, 38 bar, 39 bar, and 40 bar. The extruder may extrude the nitrification inhibitor composition at, at least at, at most at, at, or between any two of -20° C., -15° C., -10° C., 0° C., 5° C., 10° C., 15° C., 20° C., 25° C., 30° C., 35° C., 40° C., 45° C., and 50° C. The extrudate may be sliced ​​or divided prior to drying, for example, by a die.

[0124] In certain aspects, the desired final nitrification inhibitor product, such as granules, may have a particle size of 0.5 mm to 5 mm, or 1 mm to 4 mm, and a screen of one particle size or more than one particle size may be used to obtain particles having a particle size less than 0.5 mm or 1 mm, and / or having a particle size greater than 4 mm or greater than 5 mm. In certain aspects, the nitrification inhibitor composition may be prepared in a spheroidizer as a sphere and / or a spherical shape. In some cases, the nitrification inhibitor composition is contacted with the spheroidizer for at least any one, at most any one, equal to any one, or between any two of the following times: 5 seconds, 10 seconds, 15 seconds, 20 seconds, 25 seconds, 30 seconds, 35 seconds, 40 seconds, 50 seconds, or 60 seconds. In some cases, the spheronizer has a turntable or rotatable disc that can rotate at least any one, at most any one, equal to any one, or between any two of the following rotation speeds: 200 rpm, 500 rpm, 1000 rpm, 1500 rpm, 2000 rpm, 2500 rpm, 3000 rpm, 3500 rpm, 4000 rpm, 4500 rpm, 5000 rpm. In certain aspects, the nitrification inhibitor composition can be dried in a dryer at a temperature of 40° C. to 85° C., or at least any one, at most any one, equal to any one, or between any two of the following temperatures: 40° C., 45° C., 50° C., 55° C., 60° C., 65° C., 70° C., 75° C., 80° C., and 85° C. In some aspects, the dryer can be a fluidized bed dryer, a drum dryer, or an airflow dryer. In some aspects, the nitrification inhibitor composition can be dried with a hot air flow having at least any one of the following flow rates, at most any one, equal to any one, or between any two: 100 cubic meters / hour, 150 cubic meters / hour, 200 cubic meters / hour, 250 cubic meters / hour, 300 cubic meters / hour, 350 cubic meters / hour, 400 cubic meters / hour, 450 cubic meters / hour, and 500 cubic meters / hour, and / or rotated at at least any one of the following speeds, at most any one, equal to any one, or between any two: 5 rpm, 10 rpm, 15 rpm, 20 rpm, 25 rpm, 30 rpm, 35 rpm, 40 rpm, 45 rpm, and 50 rpm.

[0125] III. How to use nitrification inhibitors

[0126] The nitrification inhibitor, including nitrification inhibitor particles and compositions containing the nitrification inhibitor, can be used in a method for inhibiting the nitrification of ammonia in soil. This method may include applying an effective amount of a composition and / or mixture containing the nitrification inhibitor of the present invention to the soil. The method may include increasing the growth and yield of crops, trees, ornamental plants, etc., such as palm, coconut, rice, wheat, corn, barley, oats and / or soybeans. The method may include applying the nitrification inhibitor composition of the present invention to at least one of soil, organisms, liquid carriers, liquid solvents, etc. The one or more compositions containing the nitrification inhibitor are applied to plants and / or soil by any suitable application method.

[0127] Non-limiting examples of plants that can benefit from the nitrification inhibitors of the present invention include lianas, trees, shrubs, culms, ferns, etc. The plants may include orchard crops, lianas, ornamental plants, food crops, timber, and harvested plants. The plants may include gymnosperms, angiosperms, and / or ferns.

[0128] The effectiveness of the compositions comprising nitrification inhibitors of the present invention can be determined by analyzing nitrification activity as described below. It is understood that different soils have different properties that may affect the effectiveness of the nitrification inhibitor compositions. The effectiveness of the nitrification inhibitor compositions can also be directly compared to other nitrification inhibitor compositions by conducting side-by-side comparisons in the same soil under the same conditions.

[0129] Example

[0130] The present invention will be described in more detail by specific examples. The following examples are provided only for illustrative purposes and are not intended to limit the present invention in any way. Those skilled in the art will easily recognize various non-critical parameters that can be changed or altered to produce substantially the same results.

[0131] Example 1 Molecular Modeling Studies

[0132] Molecular modeling methods were used to predict the relative binding affinity of the compounds of Formula I compared to the nitration inhibitors dicyandiamide (DCD) and 3,4-dimethylpyrazole phosphate (DMPP) at the active site of a simulated ammonia monooxygenase (also known as nitrase). Figure 2A The crystal structure of ammonia monooxygenase is unknown, however, the literature has revealed information through homology modeling and other indirect methods that indicate that ammonia monooxygenase is a copper metalloenzyme. The Cu site model of ammonia monooxygenase shows that two Cu(II) ions are separated by The atoms of Cu2S2 rhombus are out of plane The angle between the two CuS2 planes is 170.1°. Cu1 binds to Met-A, His-A, and Cys-A of both chains in a distorted tetrahedral geometry, while Cu2 binds to residues Met-B, His-B, and Cys58-B of both chains, also in a distorted tetrahedral geometry ( Figure 2A ). Figure 2A Both copper atoms depicted in the figure are in the +1-oxidation state. Based on the available information about the active site, a density functional theory (DFT) model was used to examine the geometry of the active site of ammonia monooxygenase. The active site geometry was minimized using the B3LYP functional implemented in the Gaussian 09 software package in conjunction with the 6-31G(d,p) basis set for nonmetallic elements such as C, H, N, and O ( Figure 2B ), while for metallic Cu an effective core pseudopotential (SDD) and the associated basis set with polarization functions were used. Analytical frequency calculations verified all stationary points. The Gibbs energies were calculated at 298.15°K and atmospheric pressure assuming ideal gas properties using unscaled simple harmonic oscillation frequencies obtained within the rigid rotor approximation (unless otherwise stated).

[0133] Candidate inhibitors of Formula II and commercial inhibitors DCD and DMPP (for benchmarking purposes) were introduced and the geometry of the ligand receptor complex was minimized using the DFT method. The binding energy (BE) of the inhibitor within the active site was estimated using equation (1):

[0134] E 结合 =Energy (酶-抑制剂复合物) -[energy (活性部位) +Energy (抑制剂 )] --- Equation (1)

[0135] Table 1 - Calculated DFT binding energies

[0136]

[0137] During competitive inhibition, an effective inhibitor molecule with a higher binding energy within the enzyme active site will have a lower IC50 value. The BE of the candidate Formula II and the benchmark were estimated, as shown in Table 1. The binding energy of Formula II is in the range close to the benchmark, indicating that Formula II has a comparable affinity for ammonia monooxygenase.

[0138] Example II - Synthesis of Nitrification Inhibitors

[0139] Synthesis of the compound of formula II (1H-1,2,4-triazol-1-yl)-methanol: 6.9 g (0.1 mole) of 1,2,4-triazole, 3.0 g (0.1 mole) of polyformaldehyde and a catalytic amount of triethylamine were placed in a flask, and the flask was immersed in an oil bath maintained at 80°C to 90°C for 1 hour.

[0140]

[0141] The solidified melt was recrystallized from acetone to obtain 9.0 g of the compound of formula II. The yield was 91%. 1 H-NMR and 13 C-NMR and LC-MS analysis confirmed the identity of the compound of formula II, and the data were consistent with the literature (Asian J. Chem. 2014, 26, 883-886).

[0142] Example III - Nitration Activity Analysis

[0143] Crop soil and water are mixed to form sludge. Freshly obtained sludge contains a large amount of nitrate nitrogen, so the sludge is pretreated to reduce the possibility of denitrification during analysis. Ethylene glycol is added to the sludge, and the resulting sludge is purged with nitrogen for 24 hours to remove nitrate nitrogen. After 24 hours, the sludge is aerated to remove any residual chemical oxygen demand (COD) that may be present. COD refers to the amount of oxygen required to degrade all oxidizable compounds in the sample being tested.

[0144] A nitrification batch test was carried out under nitrification conditions. The activity of the nitrification inhibitor compound of formula II was compared with the activity of the nitrification inhibitor dicyandiamide (DCD). COD and NH4-N were added to the sludge together with one of the compound of formula II or DCD. COD, NH4-N concentration and NO3-N concentration were monitored over time (t = 0 hours, 2 hours, 4 hours, 6 hours, 8 hours, 24 hours and 29 hours). The removal of COD and NH4-N was calculated from the analytical results. Ethylene glycol was included in the test as a reference.

[0145] The pH and oxygen levels were also monitored during the test. At the beginning of the test, the pH was maintained between 7 and 8 by adding 1N HCl or 1N NaOH. Oxygen was continuously injected into the sludge solution throughout the test to obtain maximum aeration.

[0146] Table 2 includes the concentrations evaluated in the five batch tests. The sample concentrations were approximately 10% compared to the concentration of NH4-N.

[0147] Table 2

[0148]

[0149] The conversion results of COD, NH4-N and NO3-N for the reference sample and the four samples are shown in the table below. The values ​​shown in brackets are below the limit of quantification and are indicative. The measurements taken at time = 0 were taken 60 seconds after the sludge was mixed with the specified substances. The nitrification process of DCD and the compound of formula II was normal during the first 8 hours, and the nitrification rate increased thereafter. The NH4-N concentration and the NO3-N concentration were tested at 29 hours to verify that the nitrification process was still ongoing.

[0150] Table 3 - DCD results

[0151] Time (hours) <![CDATA[NH4-N (mg / L)]]> <![CDATA[NO3-N (mg / L)]]> <![CDATA[COD (mg O2 / L)]]> 0 45.9 8.6 757 2 43.0 5.5 558 4 39.4 8.9 360 6 39.7 7.4 190 8 33.2 7.3 121 24 9.9 39.0 48 29 4.0 47.2 -

[0152] Table 4 - Results of compounds of formula II

[0153] Time (hours) <![CDATA[NH4-N (mg / L)]]> <![CDATA[NO3-N (mg / L)]]> <![CDATA[COD (mg O2 / L)]]> 0 45.2 8.8 718 2 41.6 13.8 497 4 40.3 11.8 314 6 42.0 7.2 204 8 37.9 ＜2.3(1.5) 158 24 23.8 16.2 60 29 22.9 20.4 -

[0154] As shown in Tables 3 and 4 above, both the compound of formula II and DCD effectively inhibited the nitrification of ammonia nitrogen (NH4-N) in the sludge. Table 5 below shows that the compound of formula II was more effective in inhibiting nitrification within the first 24 hours. Denitrification occurred even after the sludge was pretreated. This may be attributed to the high activity of the bacteria contained in the sludge.

[0155] Table 5 - NH4-N conversion rate

[0156]

[0157] ***

[0158] In light of the present disclosure, all methods disclosed and claimed herein can be carried out and implemented without undue experimentation. Although the compositions and methods of the present invention have been described according to preferred embodiments, it will be apparent to those skilled in the art that the steps or sequence of steps of the methods and methods described herein may be changed without departing from the concept, spirit and scope of the present invention. More specifically, it will be apparent that certain chemically and physiologically related reagents may replace the reagents described herein while achieving the same or similar results. All such similar substitutions and modifications apparent to those skilled in the art are considered to be within the spirit, scope and concept of the present invention as defined by the appended claims.

Claims

1. A method for inhibiting nitrification of ammonia in soil, comprising applying to the soil a composition comprising a nitrification inhibitor of formula I: wherein R1, R2 and R3 are each independently H, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, or a salt thereof.

2. The method of claim 1, wherein the composition further comprises at least one nitrogen fertilizer component.

3. The method of claim 2, wherein the at least one nitrogen fertilizer component is selected from the group consisting of urea, ammonium salts, anhydrous ammonia, and combinations thereof.

4. The method according to any one of claims 1 to 3, wherein the composition further comprises at least one additional nitrification inhibitor.

5. The method of claim 4, wherein the at least one additional nitrification inhibitor is selected from the group consisting of chlorpyrifos, dicyandiamide, ammonium thiosulfate, methyl 3-(4-hydroxyphenyl)propionate, 1,9-decanediol, potassium azide, 2-amino-4-chloro-6-methylpyridine, sulfathiazole, 4-amino-1,2,4-triazole, 2,4-diamino-6-trichloromethyl-s-triazine, potassium ethylxanthate, guanylthiourea, 4-nitrobenzotrichloride, 4-methylsulfonylbenzotrichloride, sodium thiocarbonate, phenylmercuric acetate, 3,4-dimethylpyrazole phosphate, sorgoleone, and combinations thereof.

6. The method according to any one of claims 1 to 5, wherein the composition further comprises at least one urease inhibitor.

7. The method of claim 6, wherein the at least one urease inhibitor is at least one of n-butylthiophosphoric acid triamide and n-propylthiophosphoric acid triamide.

8. The method according to any one of claims 1 to 7, wherein the method increases the nitrogen use efficiency (NUE) of crops.

9. The method according to any one of claims 1 to 8, wherein the method further comprises applying a nitrogen fertilizer component to the soil, wherein the nitrogen fertilizer component and the composition are contained in two separate compositions.

10. The method according to any one of claims 1 to 9, wherein R1 is H, R2 is H, and / or R3 is H.

11. The method according to any one of claims 1 to 10, wherein the nitrification inhibitor is further defined as a compound of formula II:

12. A composition comprising: Nitrification inhibitor of formula I: wherein R1, R2 and R3 are each independently H, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl, or a salt thereof; and One or more of the following substances: additional inhibitors comprising urease inhibitors and / or additional nitrification inhibitors; a solid support; and / or At least one nitrogen (N) fertilizer component, phosphorus (P) fertilizer component, and / or potassium (K) fertilizer component.

13. The fertilizer composition according to claim 12, wherein: The at least one additional nitrification inhibitor is selected from the group consisting of chlorpyrifos, dicyandiamide, ammonium thiosulfate, methyl 3-(4-hydroxyphenyl)propionate, 1,9-decanediol, potassium azide, 2-amino-4-chloro-6-methylpyridine, sulfathiazole, 4-amino-1,2,4-triazole, 2,4-diamino-6-trichloromethyl-s-triazine, potassium ethylxanthate, guanylthiourea, 4-nitrobenzotrichloride, 4-methylsulfonylbenzotrichloride, sodium thiocarbonate, phenylmercuric acetate, 3,4-dimethylpyrazole phosphate, sorgoleone, and combinations thereof; The at least one urease inhibitor is at least one of n-butylthiophosphoric acid triamide and n-propylthiophosphoric acid triamide; The carrier comprises plaster of Paris, flour, chalk, starch, gluten, kaolin, bentonite, colloidal silicon dioxide, silicon dioxide, dried wine grains and solubles thereof, lignin, synthetic polymers, waxes, chitin, glycosaminoglycans, pectin, hyaluronic acid, chondroitin sulfate, dermatan sulfate, alginic acid, polymannuronic acid, polyguluronic acid, polyglucuronic acid, amylose, amylopectin, callose, chitosan, polygalactomannan, dextran, xanthan gum, keratan sulfate, MgO, CaO, bone powder, rice bran, CaCO3, Na2CO3, K2CO3, KH2PO4, NaHCO3 and / or MgCO3; and / or The at least one nitrogen (N) fertilizer component, phosphorus (P) fertilizer component, and / or potassium (K) fertilizer component comprises at least one nitrogen fertilizer component.

14. The fertilizer composition of any one of claims 12 to 13, wherein R1 is H, R2 is H, and / or R3 is H.

15. The fertilizer composition according to any one of claims 12 to 14, wherein the nitrification inhibitor is further defined as a compound of formula II:

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