Use of substituted hydroquinones as broad-spectrum nitrification inhibitor (NI)

Abstract

Use of a substituted hydroquinone of the structural formula (I). For use as nitrification inhibitor in organic, organomineral and / or inorganic growing media, in particular agricultural, horticultural or forest soils; Preferably, for use as an additive or coating material for organic or inorganic fertilizers, in particular inorganic fertilizers, preferably for nitrogen-containing fertilizers, in particular for ammonium- and / or urea-containing fertilizers, even more preferably for ammonium-containing fertilizers.

Description

[0001] Use of substituted hydroquinones as broad-spectrum nitrification inhibitor (N I ) FIELD OF THE INVENTION

[0002] The present invention relates to the use of substituted hydroquinones as broad-spectrum nitrification inhibitor (Nl) for ammonia-oxidizing bacteria (AOB) and / or ammonia-oxidizing archaea (AOA) and or complete ammonia oxidizing bacteria (comammox), preferably for nitrogen-based inorganic fertilizers such as ammonia-containing or urea-containing inorganic fertilizers, in particular for ammonia-based inorganic fertilizers.

[0003] BACKGROUND

[0004] Hydroquinones have been described as urease inhibitors (Ul) for urea-based fertilizers. Urea, also called carbamide, is an organic compound with chemical formula CO(NH2)2- Urea has two amino groups joined by a carbonyl functional group.

[0005] Urease is a soil enzyme that catalyzes the hydrolysis of urea, forming ammonia and carbon dioxide.

[0006] Carbamic acid spontaneously decomposes into another molecule of ammonia and carbon dioxide:

[0007] Urease

[0008]

[0009] Urea Carbon Dioxide Water Ammonia

[0010] US2019124917A1 and US11542211B2 to Koch Agronomic Services disclose the use of hydroquinones as urease inhibitors (Ul). However, these documents do not disclose the use of substituted hydroquinones for inhibiting ammonia-oxidizing bacteria (AOB) and ammonia-oxidizing archaea (AOA), nor any nitrification inhibiting effect on ammonia-based fertilizers.

[0011] Mazzei et al., Inhibition of Urease by Hydroquinones: A Structural and Kinetic Study, Chem. Eur. J. 2022, 28, describes the use of tert-butyl derivatives of hydroquinones as urease inhibitor (Ul) for urea-containing fertilizers. However, this document does not disclose the use of substituted hydroquinones for nitrification inhibition in ammonia-based fertilizers.

[0012] Suarez-Ojeda et al., Chemosphere 80 (2010), 474-480, describes the use of hydroquinone and p-benzoquinone as nitrification inhibitors (Nl) for sludge from high-strength ammonium wastewaters containing phenolic compounds. However, this document does not disclose the use of substituted hydroquinones for inhibiting both AOA and AOB nor any nitrification inhibiting effect on ammonia-based fertilizers.

[0013] Tert-butyl derivatives of hydroquinones were further described as antioxidants or preservatives in food or biologic matrices, such as WO2023091973.

[0014] Therefore, there is still a need for broad spectrum nitrification inhibitors (Nl) for inhibiting both AOA and AOB and optionally comammox in particular in respect of ammonia-based fertilizers.

[0015] SHORT DESCRIPTION OF THE INVENTION

[0016] The present inventors surprisingly found that substituted hydroquinones can be used for inhibiting both AOA and AOB and optionally comammox preferably for nitrogen-based inorganic fertilizers such as ammonia-containing or urea-containing inorganic fertilizers, in particular for ammonia-based inorganic fertilizers.

[0017] Accordingly, a first aspect of the present invention is the use of a substituted hydroquinone of the structural formula (I)

[0018]

[0019] (I)

[0020] wherein:

[0021] R1 is hydrogen or a C1 to C6 acyclic, branched or cyclic hydrocarbon residue, preferably an acyclic C1 to C4 hydrocarbon optionally with heteroatoms selected from the group consisting of oxygen, nitrogen, chlorine, and sulfur, wherein R1 preferably does not contain any heteroatoms, wherein even more preferably R1 is methyl or hydrogen, and even more preferably is hydrogen;

[0022] R2 is hydrogen or a C1 to C6 acyclic, branched or cyclic hydrocarbon residue, preferably an acyclic C1 to C4 hydrocarbon optionally with heteroatoms selected from the group consisting of oxygen, nitrogen, chlorine, and sulfur, wherein R2 preferably does not contain any heteroatoms, wherein even more preferably R2 is a C1 or a preferably branched C4 hydrocarbon, wherein even more preferably R2 is a methyl or an isobutyl or tert-butyl residue, and even more preferably R2 is a tert-butyl residue;

[0023] R3 is hydrogen or a C1 to C6 acyclic, branched or cyclic hydrocarbon residue, preferably an acyclic C1 to C4 hydrocarbon optionally with heteroatoms selected from the group consisting of oxygen, nitrogen, chlorine, and sulfur, wherein R3 preferably does not contain any heteroatoms, and wherein even more preferably R1 is methyl or hydrogen, and even more preferably is hydrogen; and

[0024] R4 is hydrogen or a C1 to C6 acyclic, branched or cyclic hydrocarbon residue, preferably an acyclic C1 to C4 hydrocarbon optionally with heteroatoms selected from the group consisting of oxygen, nitrogen, chlorine, and sulfur, wherein R4 preferably does not contain any heteroatoms, and wherein even more preferably R1 is methyl or hydrogen, and even more preferably is hydrogen;

[0025] For use as nitrification inhibitor (Nl) in organic, organomineral and / or inorganic growing media, in particular agricultural, horticultural or forest soils;

[0026] Preferably, for use as an additive or coating material for organic or inorganic fertilizers, in particular inorganic fertilizers, preferably for nitrogen-containing fertilizers, in particular for ammonium- and / or urea-containing fertilizers, even more preferably for ammonium-containing fertilizers.

[0027] In another aspect, the substituted hydroquinone of the structural formula (I) is not used for the treatment of wastewater, in particular high-strength ammonium wastewaters containing phenolic compounds.

[0028] In another aspect, the substituted hydroquinone of the structural formula (I) is not

[0029] ■ benzene-1 ,4-diol with R1 , R2, R3 and R4 of the substituted hydroquinone of the structural formula (I) each being hydrogen; or

[0030] ■ p-Benzoquinone.

[0031] In another aspect, the substituted hydroquinone of the structural formula (I) is the 2-tert-butyl-benzene-1 ,4-diol (TBB) of the structural formula (Ila):

[0032]

[0033] or a substituted hydroquinone of the structural formula (lib)

[0034]

[0035] And preferably is the substituted hydroquinone of the formula (Ila). In another aspect, the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) inhibits ammonia-oxidizing archaea (AOA).

[0036] In another aspect, the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) inhibits ammonia-oxidizing bacteria (AOB) and optionally comammox.

[0037] In another aspect, the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) inhibits both AOA and AOB and optionally comammox.

[0038] In another aspect, the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) additionally inhibits urease activity in urea-containing fertilizers.

[0039] In another aspect, the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) additionally inhibit urease activity in urea-containing fertilizers (monotreatment), preferably wherein no further active ingredient is added, preferably wherein no further urease inhibitor is added.

[0040] In another aspect, the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) are administered in the form of a powder, formulation, solution, or dispersion, separately or simultaneously with a fertilizer, or are incorporated into a fertilizer or are applied to an inorganic and / or organic fertilizer and / or organomineral fertilizer.

[0041] In another aspect, the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) is

[0042] ■ applied in the coating of a nitrogen-containing fertilizer granule, preferably, wherein the fertilizer granule is an ammonia-containing or a urea-containing fertilizer, preferably wherein the ammonia-containing fertilizer does not contain any urea, preferably wherein the coating is an oil-based coating, even more preferably wherein the coating serves as a carrier for the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila); and ■ applied on the - optionally pre-coated or pre-treated, such as with anti-dust, or anti-caking agents - fertilizer granules, in particular the nitrogen-containing fertilizer granules, in particular the urea-containing or ammonia-containing fertilizer granules, even more preferably the ammonia-containing fertilizer granules, wherein

[0043] - Preferably the substituted hydroquinone of the formula (I) or (Ila) are directly applied after the coating of the fertilizer granule with one or more coating agents;

[0044] - More preferably the substituted hydroquinone of the formula (I) or (Ila) are applied to the surface of the fertilizer granules, wherein the fertilizer granules optionally are coated with one or more coating agents.

[0045] ■ applied to the slurry of nitrogen-containing fertilizer, in particular a urea- containing or ammonia-containing fertilizer, even more preferably an ammonia- containing fertilizer prior to the granulation or crystallisation.

[0046] In another aspect, the dosage of substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) is 400 g / t to 2 kg / t based on the total weight of the fertilizer.

[0047] In another aspect, the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) are applied in combination or in admixture with one or more of the following compounds:

[0048] the thiazolidine-2-one of the formula (III) (TAO)

[0049]

[0050] ■ 2-(3,4-dimethyl-pyrazol-1 -yl)-succinic acid (DMPSA),

[0051] ■ Dicyandiamide DCD,

[0052] ■ 3,4-dimethylpyrazole (DMP), and

[0053] ■ 3,4-dimethylpyrazolephosphate (DMP(P));

[0054] Wherein preferably the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) are applied in combination or in admixture with DMPSA and TAO.

[0055] In another aspect, no further nitrification inhibitors (Nl) or urease inhibitors (III) are applied.

[0056] Another aspect of the present invention is a composition comprising a

[0057] ■ A hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) and

[0058] ■ TAO and / or

[0059] ■ DMPSA, and

[0060] ■ Optionally DCD

[0061] ■ Optionally DMP(P).

[0062] In another aspect, the composition is applied as a monotreatment for both urease inhibition and nitrification inhibition to urea-containing inorganic fertilizers, wherein no further urease inhibitor is comprised and even more preferably wherein no further nitrification inhibitor other than TAO and / or DMP, DMPSA, optionally DCD, and / or DMP(P) is comprised.

[0063] Another aspect of the present invention is a method for

[0064] ■ the dual inhibition of nitrification through AOA and / or AOB and optionally comammox and for the inhibition of urease through a single compound (monotreatment) in urea-containing inorganic fertilizers, wherein the single compound is the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) optionally in combination with TAO, and / or DMPSA, optionally DMP, DCD, and / or DMP(P) and wherein the single compound is applied to a soil; and / or

[0065] ■ the inhibition of nitrification through ammonia-containing inorganic fertilizers through AOA and AOB and optionally comammox comprising applying the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) optionally in combination with TAO, and / or DMPSA, optionally DMP, DCD, and / or DMP(P) to a soil.

[0066] DETAILED DESCRIPTION OF THE INVENTION

[0067] The invention is now described in further detail.

[0068] Nitrification inhibitor (Nl)

[0069] The substituted hydroquinones of the formula (I) or (Ila) are used as nitrification inhibitors in growing media, in particular agricultural, horticultural or forest soils.

[0070] Preferably, the substituted hydroquinones of the formula (I) and (Ila) are used as an additive or coating material for inorganic fertilizers, preferably for nitrogen-containing fertilizers, in particular for ammonium- and / or urea-containing fertilizers, even more preferably for ammonium-containing fertilizers.

[0071] The term "nitrification inhibitor" (Nl) is to be understood as any chemical substance which slows down or retards the nitrification process which is typically occurring in (fertilized) soil.

[0072] Nitrification inhibitors retard the natural transformation of ammonium into nitrate and target microorganisms, preferably ammonia-oxidizing bacteria (AOB) and / or ammoniaoxidizing archaea (AOA), by inhibiting the activity of bacteria, e.g., AOB and AOA, such as Nitrosomonas spp., Nitrosospira spp. and / or Archaea.

[0073] The nitrification inhibitor is most often combined with a fertilizer, preferably an (ammonium) nitrogen-containing fertilizer, e.g., solid or liquid inorganic, organic and / or organomineral fertilizer, or manure. The term "nitrification" is to be understood as the biological oxidation of ammonia (NH3) or ammonium (NH4+) with oxygen into nitrite (NO2-) followed by the oxidation of these nitrites into nitrates (NO3-) by microorganisms.

[0074] Besides nitrate (NO3-) nitrous oxide is also produced though nitrification. Nitrification is an important step in the nitrogen cycle in soil.

[0075] In one embodiment, the substitute hydroquinone of the formulas (I) or the TBB of the structural formula (Ila) inhibits AOA.

[0076] In one embodiment, the substitute hydroquinone of the formulas (I) or the TBB of the structural formula (Ila) inhibits AOB. In this embodiment, the substrate is preferably not sludge from wastewaters, in particular sludge from high-strength ammonium wastewaters containing phenolic compounds.

[0077] In a preferred embodiment, the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) inhibits both AOA and AOB and optionally comammox.

[0078] Urease inhibitor (Ul)

[0079] The term “urease inhibitor” describes any chemical substance which slows down or retards the activity of the urease enzyme which is typically occurring in (fertilized) soil. Urea has two amino groups joined by a carbonyl functional group. Urease, an enzyme found in selected bacteria, archaea, plants, algae, and fungi, catalyzes the hydrolysis of urea into ammonia and carbamic acid.

[0080] Carbamic acid spontaneously decomposes into another molecule of ammonia and carbonic acid:

[0081] Urease

[0082]

[0083] Urea Carbon Dioxide Water

[0084]

[0085] )nia Nitrification and urease inhibition as monotreatment

[0086] In a preferred embodiment of the present invention, the substituted hydroquinones of the formula (I) or the (Ila) inhibit both nitrification and urease inhibition preferably as a monotreatment by:

[0087] ■ inhibiting the microbial breakdown of urea preferably through AOA and / or AOB;

[0088] ■ inhibiting the microbial breakdown of ammonia through AOA and / or AOB;

[0089] Accordingly, in a preferred embodiment, the substituted hydroquinone of the formula (I) or the TBB of the structural formula (Ila) are used as urease and nitrification inhibitor in urea-fertilized soils as a monotreatment, i.e. without the addition of a further active ingredients, in particular a further urease inhibitor (III).

[0090] Nitrogen loss prevention and yield increase

[0091] In one embodiment of the present invention, the substituted hydroquinone of the formula (I) or the TBB of the structural formula (Ila) are used to improve the utilization of nitrogen in the ammonium- or urea-containing mineral, organic and organomineral fertilizers. In one embodiment, the substituted hydroquinone of the formula (I) or the TBB of the structural formula (Ila) increase, in some cases considerably, the yields and production of biomass of crop plants.

[0092] Equally, the substituted hydroquinone of the formula (I) or the TBB of the structural formula (Ila) may be added to organic fertilizers, such as liquid manure, for example, during the actual storage of such fertilizers. This helps preventing nitrogen nutrient losses by virtue of a decelerated conversion of the individual forms of nitrogen into gaseous, therefore volatile, nitrogen compounds, and, at the same time, to contribute to a lowering of the ammonia load in animal stalls.

[0093] In one embodiment, the substituted hydroquinone of the formula (I) or the TBB of the structural formula (Ila) are used to reduce nitrogen losses which can occur in nitrogencontaining compounds or materials, in particular ammonia-losses in the case of urea-containing fertilizers or laughing gas (N2O) losses in the case of ammonia-containing fertilizers.

[0094] Moreover, the substituted hydroquinone of the formula (I) or the TBB of the structural formula (Ila) may be used on agricultural stovers and grazed land for the purpose of reducing gaseous nitrogen losses in the form of ammonia in the case of ammonia-containing fertilizers and for preventing instances of nitrate leaching.

[0095] In one embodiment, the substituted hydroquinone of the formula (I) or the TBB of the structural formula (Ila) used for preventing or reducing greenhouse gas emissions (GHG) from nitrogen-containing compounds or materials. These materials often contain nitrogen in covalently or ionically bonded form, e.g. in the form of ammonium, protein, nitrate. Thus, the terms “nitrogen” can refer to the elemental form or to compounds or materials containing nitrogen atoms.

[0096] Growing media

[0097] The substituted hydroquinones of the formula (I) or (Ila) are preferably used for the inhibition of nitrification through AOA, AOB and / or Comammox and / or for the inhibition of urease activity in urea-fertilized growing media, such as fertilized soils, preferably ammonia-fertilized soils and / or urea-fertilized soils.

[0098] In a preferred embodiment, the substituted hydroquinone of the structural formula (I) is not used for the treatment of sludge from wastewaters, in particular sludge from high-strength ammonium wastewaters containing phenolic compounds.

[0099] Substituted hydroquinones

[0100] The substituted hydroquinones of the present invention are hydroquinones of the structural formula (I)

[0101]

[0102] (I)

[0103] wherein:

[0104] R1 is hydrogen or a C1 to C6 acyclic, branched or cyclic hydrocarbon residue, preferably an acyclic C1 to C4 hydrocarbon optionally with heteroatoms selected from the group consisting of oxygen, nitrogen, chlorine, and sulfur, wherein R1 preferably does not contain any heteroatoms, wherein even more preferably R1 is hydrogen;

[0105] R2 is hydrogen or a C1 to C6 acyclic, branched or cyclic hydrocarbon residue, preferably an acyclic C1 to C4 hydrocarbon optionally with heteroatoms selected from the group consisting of oxygen, nitrogen, chlorine, and sulfur, wherein R2 preferably does not contain any heteroatoms, wherein even more preferably R2 is a C1 or a preferably branched C4 hydrocarbon, wherein even more preferably R2 is a methyl or an isobutyl or tert-butyl residue, and even more preferably R2 is a tert-butyl residue;

[0106] R3 is hydrogen or a C1 to C6 acyclic, branched or cyclic hydrocarbon residue, preferably an acyclic C1 to C4 hydrocarbon optionally with heteroatoms selected from the group consisting of oxygen, nitrogen, chlorine, and sulfur, wherein R3 preferably does not contain any heteroatoms, and wherein even more preferably R3 is hydrogen; and

[0107] R4 is hydrogen or a C1 to C6 acyclic, branched or cyclic hydrocarbon residue, preferably an acyclic C1 to C4 hydrocarbon optionally with heteroatoms selected from the group consisting of oxygen, nitrogen, chlorine, and sulfur, wherein R4 preferably does not contain any heteroatoms, and wherein even more preferably R4 is hydrogen;

[0108] In a preferred embodiment, the substituted hydroquinone of the structural formula (I) is not

[0109] benzene-1 ,4-diol with R1, R2, R3 and R4 of the hydroquinone of the structural formula (I) each being hydrogen; or ■ p-Benzoquinone.

[0110] In another embodiment, the substituted hydroquinone is a hydroquinone of Examples 1 to 9 of Table 1 below. In a particularly preferred embodiment, the substituted hydroquinone is a substituted hydroquinone of the formula (Ila)

[0111]

[0112] (Ila).

[0113] In another embodiment, the substituted hydroquinone is a substituted hydroquinone of the formula (lib)

[0114]

[0115] And preferably is the substituted hydroquinone of the formula (Ila).

[0116] Combination with further nitrification inhibitors

[0117] In another aspect, the substituted hydroquinones of the formula (I) or (Ila) are administered in combination or in a mixture with one or more compounds selected from the group consisting of 2-(3,4-dimethyl-pyrazol-1-yl)-succinic acid, 2-(4,5-dimethyl-pyrazol-1-yl)-succinic acid, 3,4-dimethylpyrazole (DMP), and 3,4-dimethylpyrazolephosphate (DMP(P)). In a preferred embodiment, the substituted hydroquinones of the formula (I) or (Ila) are administered in combination with a reaction mass of 2-(3,4-dimethyl-pyrazol-1-yl)-succinic acid, and 2-(4,5-dimethyl-pyrazol-1-yl)-succinic acid (DMPSA).

[0118] In a preferred embodiment, the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) are applied in combination or in admixture with one or more of the following compounds:

[0119] the thiazolidine-2-one of the formula (III) (TAO)

[0120]

[0121] ■ DMPSA,

[0122] ■ Dicyandiamide (DCD),

[0123] ■ DMP, and

[0124] ■ DMP(P);

[0125] Wherein preferably the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) are applied in combination or in admixture with DMPSA and TAO.

[0126] In a further preferred embodiment, no further nitrification inhibitors or urease inhibitors are applied either to the substituted hydroquinones of the formula (I) or (Ila) or their combination with or admixture with one or more of the following compounds:

[0127] ■ the thiazolidine-2-one of the formula (III) (TAO)

[0128]

[0129] ■ DMPSA,

[0130] ■ Dicyandiamide DCD,

[0131] ■ DMP, and

[0132] ■ DMP(P);

[0133] Wherein preferably the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) are applied in combination or in admixture with DMPSA and TAO.

[0134] Application of the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila)

[0135] The substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) can be administered in the form of a formulation, solution, or dispersion, separately or simultaneously with a fertilizer, or is incorporated into a fertilizer or is applied to an inorganic and / or organic fertilizer and / or organomineral fertilizer.

[0136] In one embodiment, the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) is used as an additive or coating material for inorganic and / or organic and / or organomineral fertilizers, preferably inorganic fertilizers, more preferably ammonium- and / or urea-containing inorganic nitrogen fertilizers.

[0137] In one embodiment, the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) is ■ applied in the coating of a nitrogen-containing fertilizer granule, preferably, wherein the fertilizer granule is an ammonia-containing or a urea-containing fertilizer, preferably wherein the ammonia-containing fertilizer does not contain any urea, preferably wherein the coating is an oil-based coating, even more preferably wherein the coating serves as a carrier for the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila); and

[0138] ■ applied on the - optionally pre-coated or pre-treated, such as with anti-dust, or anti-caking agents - fertilizer granules, in particular the nitrogen-containing fertilizer granules, in particular the urea-containing or ammonia-containing fertilizer granules, even more preferably the ammonia-containing fertilizer granules, wherein

[0139] - Preferably the substituted hydroquinone of the formula (I) or (Ila) are directly applied after the coating of the fertilizer granule with one or more coating agents;

[0140] - More preferably the substituted hydroquinone of the formula (I) or (Ila) is applied to the surface of the fertilizer granule, wherein the fertilizer granule optionally is coated with one or more coating agents.

[0141] ■ applied to the slurry of nitrogen-containing fertilizer, in particular a urea- containing or ammonia-containing fertilizer, even more preferably an ammonia-containing fertilizer prior to the granulation or crystallisation. Method for preventing nitrification

[0142] A further aspect of the present invention is a method for preventing nitrification, comprising applying the substituted hydroquinone of the formula (I) or the TBB of the structural formula (Ila) to organic, organomineral and / or inorganic growing media, in particular agricultural, horticultural or forest soils.

[0143] A further aspect of the present invention is a method for preventing nitrification, comprising the substituted hydroquinone of the formula (I) or the TBB of the structural formula (Ila) as an additive or coating material for organic or inorganic fertilizers, in particular inorganic fertilizers, preferably for nitrogen-containing fertilizers, in particular for ammonium- and / or urea-containing fertilizers, even more preferably for ammonium-containing fertilizers.

[0144] Mixture and Dosage

[0145] Another aspect of the present invention is a fertilizer mixture, containing:

[0146] A. an inorganic and / or organic and / or organomineral fertilizer and

[0147] B. from 200 g / t to 2000 g / t as compared to total weight of the fertilizer, of the substituted hydroquinone of the formula (I) or the TBB of the structural formula (Ila). Another aspect of the present invention is a method of fertilizing soils exploited agriculturally or horticulturally, wherein a fertilizer mixture contains compounds A and B A. an inorganic and / or organic and / or organomineral fertilizer and

[0148] B. from 200 g / t to 2000 g / t based on the inorganic fertilizer, of the substituted hydroquinone of the formula (I) or the TBB of the structural formula (Ila) or compounds A and B separately, but within a period of 0 to 5 hours, preferably 0 to 1 hour, more preferably approximately at the same time, is applied to the soils.

[0149] SHORT DESCRIPTION OF THE DRAWINGS

[0150] The Figure shows the effect of the TBB of the structural formula (Ila) (“TBB”) and thiazolidine-2-one of the formula (III) (“TAO”).

[0151] TBB of additional nitrification inhibiting effects were obtained when combining 0,84 g TBB / kg ammonium sulphate (AS) with 1,68 g TAO / kg AS (middle column) compared to single applications of 0,84 g TBB / kg ammonium sulfate fertilizer (AS) (left column) and 1 ,68 g TAO / kg AS (right) after incubation 14 days in the soil.

[0152] EXAMPLES

[0153] Nitrification is a microbial process that converts ammonia to nitrate. The first and ratelimiting step of nitrification is ammonia oxidation, a process that can be performed by both ammonia-oxidizing bacteria and ammonia-oxidizing archaea. In agriculture, it is favorable to inhibit this process as it reduces the availability of nitrogen nutrients for the plants and results in nitrogen loss in the environment and greenhouse gas emissions (GHG).

[0154] To identify novel nitrification inhibitors, a small molecule screen using different nitrifying microorganisms or systems as described in Beeckman et al., 2023 (https: / / doi.Org / 10.1016 / i.tim.2O23.10.009) was performed.

[0155] Analysis of the dataset revealed that certain substituted hydroquinones showed strong nitrification inhibition on ammonia-oxidizing archaea.

[0156] This is a novel observation: hydroquinone as such is previously shown by Suarez-Ojeda et al., 2010 (https: / / doi.Org / 10.1016 / i. chemosphere.2010.03.041 ) to inhibit ammonia-oxidizing bacteria, at least in sludge, but not ammonia-oxidizing archaea, while it should not be expected that nitrification inhibitors that target ammonia-oxidizing bacteria also target ammonia-oxidizing archaea or vice versa, as shown by Beeckman et al., 2023 (https: / / d0i.0rg / l 0.1016 / i.tim.2O23.10.009).

[0157] Moreover, the inventors discovered that substitutions on the hydroquinone improve nitrification inhibition in soil.

[0158] The inventors demonstrated that a number of various substituted hydroquinones show the potential to inhibit both ammonia-oxidizing archaea and ammonia-oxidizing bacteria. As such, they have the potential to target more or other ammonia-oxidizing microorganisms than most other nitrification inhibitors, including commonly applied nitrification inhibitors. Especially in combination with other nitrification inhibitors, the substituted hydroquinones show a higher maximum nitrification inhibition potential.

[0159] Table 1 shows the new nitrification inhibitors and their inhibition on the ammonia-oxidizing archaeon Nitrososphaera viennensis and the ammonia-oxidizing bacteria Nitrosomonas europaea and Nitrosospira multiformis.

[0160] Assays were performed and nitrification inhibition % was assessed as described in Beeckman et al., 2023 (https: / / doi.Org / 10.1016 / j.tim.2O23.10.009).

[0161] Unless otherwise specified, an inhibitor concentration of 25 pM (Nitrososphaera viennensis) or 200 pM (Nitrosomonas europaea and Nitrosospira multiformis) was used. Most of the hydroquinones in Table 1 inhibit nitrification or ammonia oxidation from both archaea and bacteria, indicating their action as broad-spectrum nitrification inhibitors.

[0162] Especially for Nitrosospira multiformis, an ammonia-oxidizing bacterium that is in general more abundant in soil than the model Nitrosomonas europaea, the difference between the substituted hydroquinones and the comparative example hydroquinone is clear: while certain substituted hydroquinones result in a strong nitrification inhibition up to 100%, hydroquinone itself is not able to inhibit Nitrosospira multiformis.

[0163] Table 1: Substituted hydroquinones show nitrification inhibition on both the ammonia-oxidizing archaeon Nitrososphaera viennensis and the ammonia-oxidizing bacteria Nitrosomonas europaea and Nitrosospira multiformis.

[0164] Example Structure Nitrification Nitrification Nitrification inhibition [%] inhibition [%] inhibition [%]

[0165]

[0166] Example Structure Nitrification Nitrification Nitrification inhibition [%] inhibition [%] inhibition [%]

[0167]

[0168] Example Structure Nitrification Nitrification Nitrification inhibition [%] inhibition [%] inhibition [%]

[0169]

[0170] To further demonstrate the inhibition of ammonia-oxidizing bacteria in soil, a quantitative PCR experiment was conducted, enabling quantification of the abundance of all ammonia-oxidizing bacteria.

[0171] The primers used in this experiment and the set-up are as in Beeckman et al., 2023 (https: / / doi.orq / 10.1016 / i.tim.2O23.10.009).

[0172] Two different ammonium-treated agricultural soils were used and treated with a mock or with the example 1 (200 pM). For comparison, the commonly used bacteria-targeting nitrification inhibitor DMP (50 pM) was applied as well. After 7 days, samples were taken to assess relative abundances and to compare them to the start. Table 2 shows the relative abundances of ammonia-oxidizing bacteria upon the different treatments and shows a strong growth of ammonia-oxidizing bacteria if no inhibitor is applied. In contrast, both DMP and example 1 result in a reduction of ammonia-oxidizing bacteria in both soils, showing that example 1 targets ammonia-oxidizing bacteria to inhibit nitrification.

[0173] Table 2: Substituted hydroquinone H1 inhibits growth of ammonia-oxidizing bacteria soil.

[0174] Time- Treatment Structure Relative abundance of ammonia- point oxidizing bacteria in soil _

[0175] O d Mock 1.06E+05

[0176] 7 d Mock 1.64E+05

[0177]

[0178] To further validate the action of substituted hydroquinones as nitrification inhibitor, the effect of example 1 and 9 on nitrification in different agricultural soils was tested.

[0179] Additionally, as it is known that nitrification inhibitors that target ammonia-oxidizing archaea may have additive effects when co-applied with bacteria-targeting nitrification inhibitors, several combinations with the commonly used nitrification inhibitor DCD (dicyandiamide) or the recently discovered nitrification inhibitors TAO (1 ,3-thiazolidin-2-one) and unTAO (3H-1 ,3-thiazol-2-one) (W02022053660) were tested.

[0180] All experiments were performed as described in Beeckman et al., 2023 (https: / / doi.orq / 10.1016 / i.tim.2O23.10.009).

[0181] Nitrification inhibition % was assessed after one week of incubation with the inhibitors. Table 3 shows the nitrification inhibition % and shows that example 1 and 9 inhibit nitrification, while the different combinations result in a better inhibition than the single applications. This indicates that the combination of hydroquinones with other nitrification inhibitors results in a broader and more effective nitrification inhibition.

[0182] Table 3: Substituted hydroquinones inhibit nitrification in agricultural soil and result in an additive effect when co-applied with other nitrification inhibitors. Example 1 and 9 were applied at a concentration of 200 pM, DCD was applied at a concentration of 500 pM, and TAO (1,3-thiazolidin-2-one) and unTAO (3H-1,3-thiazol-2-one) were applied at a concentration of 50 pM.

[0183]

[0184]

[0185] In another experiment, the nitrification inhibition of Examples 1 and 5 were tested in one or two agricultural soils and compared to hydroquinone (Table 4).

[0186] All treatments were done at a final dose of 200 pM and performed as described in Beeckman et al., 2023 (https: / / doi.orq / 10.1016 / i.tim.2O23.10.009).

[0187] Table 4 shows that a substitution significantly improves nitrification inhibition activity. Table 4: Substituted hydroquinones in single application

[0188]

[0189] In two other experiments, Examples 1 and 5 were tested alone (Table 5) or in combination with DCD (Table 6) and compared to hydroquinone. These experiments were performed as described in Beeckman et al., 2023 (https: / / doi.orq / 10.1016 / i.tim.2O23.10.009), except that an initial ammonium level of 25 mg N / 100 g soil was provided.

[0190] The substituted and non-substituted hydroquinone were applied at 200 pM, while DCD was in all cases applied at 2 mM.

[0191] Table 5 and Table 6 show that, in most cases, Example 1 and 5 are outperforming the comparative example hydroquinone, indicating that the substitution on position 2 of the hydroquinone is important for optimal activity. Table 5: Substituted hydroquinones nitrification inhibition after 14 days in soil at 200 pM in single application.

[0192]

[0193]

[0194] Table 6: Substituted hydroquinones nitrification inhibition after 14 days in soil at 200 pM in in combination with the nitrification inhibitor DCD (at 2 mM).

[0195] Example Nitrification inhibition [%] in soil

[0196] DCD 62

[0197] 1 + DCD 100

[0198] 5 + DCD 87

[0199] Comparative 66

[0200] example

[0201] (hydroquinone) +

[0202] DCD

Claims

CLAIMS1. Use of a substituted hydroquinone of the structural formula (I)wherein:R1 is hydrogen or a C1 to C6 acyclic, branched or cyclic hydrocarbon residue, preferably an acyclic C1 to C4 hydrocarbon optionally with heteroatoms selected from the group consisting of oxygen, nitrogen, chlorine, and sulfur, wherein R1 preferably does not contain any heteroatoms, wherein even more preferably R1 is methyl or hydrogen, and even more preferably is hydrogen;R2 is hydrogen or a C1 to C6 acyclic, branched or cyclic hydrocarbon residue, preferably an acyclic C1 to C4 hydrocarbon optionally with heteroatoms selected from the group consisting of oxygen, nitrogen, chlorine, and sulfur, wherein R2 preferably does not contain any heteroatoms, wherein even more preferably R2 is a C4 hydrocarbon; wherein even more preferably R2 is a branched hydrocarbon, and whereineven more preferably R2 is a methyl residue or a butyl residue; preferably R2 is a tert-butyl residue;R3 is hydrogen or a C1 to C6 acyclic, branched or cyclic hydrocarbon residue, preferably an acyclic C1 to C4 hydrocarbon optionally with heteroatoms selected from the group consisting of oxygen, nitrogen, chlorine, and sulfur, wherein R3 preferably does not contain any heteroatoms, and wherein even more preferably R3 is methyl or hydrogen; andR4 is hydrogen or a C1 to C6 acyclic, branched or cyclic hydrocarbon residue, preferably an acyclic C1 to C4 hydrocarbon optionally with heteroatoms selected from the group consisting of oxygen, nitrogen, chlorine, and sulfur, wherein R4 preferably does not contain any heteroatoms, and wherein even more preferably R4 is methyl or hydrogen;For use as nitrification inhibitor in organic, organomineral and / or inorganic growing media, in particular agricultural, horticultural or forest soils;Preferably, for use as an additive or coating material for organic or inorganic fertilizers, in particular inorganic fertilizers, preferably for nitrogen-containing fertilizers, in particular for ammonium- and / or urea- containing fertilizers, even more preferably for ammonium-containing fertilizers.

2. Use according to claim 1 , wherein the substituted hydroquinone of the structural formula (I) is not used for the treatment of wastewater, in particular high-strength ammonium wastewaters containing phenolic compounds.

3. Use according to any one of the preceding claims, wherein the substituted hydroquinone of the structural formula (I) is not■ benzene-1 ,4-diol with R1 , R2, R3 and R4 of the substituted hydroquinone of the structural formula (I) each being hydrogen; or ■ p-Benzoquinone.

4. Use according to any one of the preceding claims, wherein the substituted hydroquinone of the structural formula (I) is the 2-tert-butyl-benzene-1 ,4- diol (TBB) of the structural formula (Ila):(Ha),or the substituted hydroquinone of the structural formulaAnd preferably is the substituted hydroquinone of the formula (Ila).

5. Use according to any one of the preceding claims, wherein the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) inhibits Ammonia-Oxidizing Archaea (AOA).

6. Use according to any one of the preceding claims, wherein the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) inhibit Ammonia-Oxidizing Bacteria (AOB) and optionally comammox.

7. Use according to any one of the preceding claims, wherein the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) inhibit both AOA and AOB and optionally comammox.

8. Use according to any one of the preceding claims, wherein the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) additionally inhibit urease activity in urea-containing fertilizers (monotreatment), preferably wherein no further active ingredient is added, preferably wherein no further urease inhibitor is added.

9. Use according to one of the preceding claims, wherein the substituted hydroquinone of the structural formulas (I) or the TBB of the structural formula (Ila) are administered in the form of a powder, formulation, solution, or dispersion, separately or simultaneously with a fertilizer, or are incorporated into a fertilizer or are applied to an inorganic and / or organic fertilizer and / or organomineral fertilizer.

10. Use according to any one of the preceding claims, wherein the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) are■ applied in the coating of a nitrogen-containing fertilizer granule, preferably, wherein the fertilizer granule is an ammonia-containing or a urea-containing fertilizer, preferably wherein the ammonia-containing fertilizer does not contain any urea, preferably wherein the coating is an oil-based coating, even more preferably wherein the coating serves as a carrier for the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila); and■ applied on the - optionally pre-coated or pre-treated, such as with antidust, or anti-caking agents - fertilizer granules, in particular the nitrogen-containing fertilizer granules, in particular the urea-containing or ammonia-containing fertilizer granules, even more preferably the ammonia-containing fertilizer granules, wherein- Preferably the substituted hydroquinone of the formula (I) or (Ila) are directly applied after the coating of the fertilizer granule with one or more coating agents;- More preferably the substituted hydroquinone of the formula (I) or (Ila) are applied to the surface of the fertilizer granule, wherein the fertilizer granules optionally are coated with one or more coating agents.■ applied to the slurry of nitrogen-containing fertilizer, in particular a urea- containing or ammonia-containing fertilizer, even more preferably an ammonia-containing fertilizer prior to the granulation or crystallisation.

11. Use according to any one of the preceding claims, wherein the dosage of substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) is 400 g / t to 2 kg / t based on the total weight of the fertilizer.

12. Use according to any one of the preceding claims, wherein the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) are applied in combination or in admixture with one or more of the following compounds:the thiazolidine-2-one of the formula (III) (TAO)■ a reaction mass of 2-(3,4-dimethyl-pyrazol-1-yl)-succinic acid, and 2-(4,5-dimethyl-pyrazol-1-yl)-succinic acid (DMPSA),■ Dicyandiamide DCD,■ 3,4-dimethylpyrazole (DMP), and■ 3,4-dimethylpyrazolephosphate (DMP(P));Wherein preferably the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) are applied in combination or in a mixture with DMPSA and TAO.

13. Use according to any one of the preceding claims, wherein no further nitrification inhibitor or no further urease inhibitor is applied.

14. Composition comprising a■ A substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) and■ TAO and / or■ DMPSA, and■ Optionally DCD■ Optionally DMP(P).

15. Composition according to claim 14, wherein the composition is applied as a monotreatment for both urease inhibition and nitrification inhibition to urea-containing inorganic fertilizers, wherein no further urease inhibitor is comprised and even more preferably wherein no further nitrification inhibitor other than TAO and / or DMP, DMPSA, optionally DCD, and / or DMP(P) is comprised.

16. A method for■ the dual inhibition of nitrification through AOA and / or AOB and optionally comammox and for the inhibition of urease through a single compound (monotreatment) in urea-containing inorganic fertilizers, wherein the single compound is the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) optionally in combination with TAO, and / or DMPSA, optionally DMP, DCD, and / or DMP(P) and wherein the single compound is applied to a soil; and / or■ the inhibition of nitrification through ammonia-containing inorganic fertilizers through AOA and AOB and optionally comammox comprising applying the substituted hydroquinone of the structural formula (I) or the TBB of the structural formula (Ila) optionally in combination with TAO, and / or DMPSA, optionally DMP, DCD, and / or DMP(P) to a soil.

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