Nitro-oxidation process-derived cellulosic liquid fertilizer compositions and methods of enhanced agricultural use

Abstract

A liquid fertilizer composition includes an aqueous phase, dispersed cellulosic fibers including carboxylated cellulose microfibers and / or carboxylated cellulose nanofibers, dissolved nitrogen that includes nitrate and optionally ammonium, dissolved phosphorus, dissolved potassium, oxidized organic carbon compounds, and a nitro-oxidized effluent.

Description

Attorney Docket No. 201291.13. PCTNITRO-OXIDATION PROCESS-DERIVED CELLULOSIC LIQUID FERTILIZER COMPOSITIONS AND METHODS OF ENHANCED AGRICULTURAL USE CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Patent Application No. 63 / 723,151 filed on November 21, 2024. The entire contents of this application are hereby incorporated by reference.BACKGROUND OF THE INVENTION1. Field of the Invention

[0002] The present invention relates generally to agricultural fertilizers and soil amendments. More particularly, the present invention relates to liquid fertilizer compositions and methods of using liquid fertilizers.2. Description of the Related Art

[0003] Sustained crop production requires continuous replenishment of essential plant nutrients, particularly N, P, and K. Conventional synthetic fertilizers are widely used to meet this demand. However, a substantial fraction of applied nutrients is lost from the soil-plant system through leaching, run-off, volatilization, and other transformation pathways. In many agricultural systems, nutrient use efficiency for N and P is estimated to be relatively low, such that only a minority of applied nutrient is taken up by the plants, while the remainder contributes to nutrient depletion in fields and to environmental pollution in surrounding ecosystems.

[0004] Low nutrient use efficiency is largely associated with the high water solubility of common N- and P-based fertilizers. When such fertilizers are applied to soil, rainfall or irrigation can rapidly dissolve and transport the nutrients beyond the root zone or into surface waters, resulting in both agronomic and environmental losses. Potassium fertilizers are generally less prone to leaching than N and P fertilizers, but K losses can still occur, especially in sandy soils and soils with low organic matter content. These inefficiencies necessitate higher fertilizer application rates, increasing input costs for farmers and contributing to eutrophication, greenhouse gas emissions, and broader perturbation of nutrient cycles.

[0005] To address these challenges, there is growing interest in fertilizer technologies that better synchronize nutrient release with plant demand and that mitigate nutrient losses from soil. Among the approaches under exploration, nanotechnology has emerged as a promising tool for designing advanced delivery systems for agrochemicals. Nanoscale materials typically exhibit increased surface area and tunable surface chemistry relative to their bulk counterparts, allowing for controlled interaction with nutrient ions and the surrounding soil matrix. By appropriate engineering—such as coating, capping, embedding, intercalation, and functionalization—nanostructured carriers can be developed to regulate the rate and timing of nutrient release to plants.

[0006] Within this context, nanocellulose has attracted considerable attention. Cellulose is the most abundant biopolymer on earth and can be sourced from a wide variety of agricultural and food residues. Numerous methods have been developed for converting bulk cellulose into cellulose nanofibers or other nanocellulose structures that possess enhanced functionality compared to untreated cellulose. One notable route involves oxidative processes (for example, TEMPO-mediated oxidation) to introduce carboxyl or other functional groups onto cellulose chains, thereby improving dispersibility, surface reactivity, and affinity for nutrient ions.

[0007] More recently, nitro-oxidation processes (NOPs) have been demonstrated as an efficient, low-cost, and environmentally favorable means of producing carboxylated cellulose nanofibers directly from agricultural residues. In these NOPs, nitric acid serves both as a nitrating and oxidizing agent, simultaneously breaking down lignocellulosic biomass and introducing functional groups into the resulting fibers. Unlike many nanocellulose production methods that generate chemical wastes requiring disposal or regeneration, the effluents from nitro-oxidation can, after neutralization, be repurposed directly as liquid fertilizers. These effluents typically contain dissolved and colloidal nutrients, oxidized organic compounds, and substantial quantities of dispersed cellulosic fibers, including cellulose nanofibers derived from the original biomass feedstock.

[0008] The use of cellulose nanofibers and related nanocellulose materials as modifiers of macronutrient availability for plant fertilization has been reported. Such materials may act as sorbents or carriers for nutrient ions, potentially reducing leaching and providing a moregradual nutrient supply. However, prior work has generally focused on nanocellulose produced through multi-step processes in which the nanocellulose is isolated and purified as a separate material before being incorporated into fertilizer formulations or growing media. These approaches often require additional processing steps, reagents, and handling, limiting their scalability and cost-effectiveness, and they do not necessarily leverage the full nutrient content of the process effluents.

[0009] Despite the recognition of (i) the need to improve N, P, and K use efficiency, (ii) the potential of nanocellulose to modulate nutrient dynamics, and (iii) the advantages of nitrooxidation as a zero-waste route to nanocellulose from organic residues, there remains a lack of fertilizer products and methods that directly exploit nitro-oxidation process streams as integrated liquid fertilizers. In particular, known liquid fertilizer compositions do not include unseparated nitro-oxidation effluent— with its inherent mixture of cellulose nanofibers, oxidized organic compounds, and dissolved nutrients— formulated to control NPK leaching losses, retain nutrients in soil, and sustain plant growth.

[0010] There is therefore a need for improved fertilizer compositions and methods that:1. utilize nitro-oxidation process-derived cellulosic fibers and oxidized organic matrices;2. upcycle diverse organic waste feedstocks such as spent grain, animal manure, food waste, palm residues, and other lignocellulosic materials;3. provide slow-release and enhanced-efficiency delivery of N, P, and K; and 4. reduce nutrient run-off and leaching while maintaining or improving crop productivity.SUMMARY OF THE INVENTION

[0011] To overcome the problems described above, example embodiments of the present invention provide liquid fertilizer compositions and methods that utilize nitro-oxidation process (NOP) effluents obtained from organic waste feedstocks as slow-release and enhanced-efficiency fertilizers. In the NOP, lignocellulosic or organic materials such as food waste, spent grains, palm residues, animal manures, and fiber crops are contacted with nitric acid under controlled conditions to generate a reaction liquor containing dissolved inorganic nutrients,oxidized organic compounds, and dispersed cellulosic fibers, including cellulose nanofibers. After optional separation of coarse solids, neutralization, and adjustment with supplemental nutrient salts, the resulting effluent is used directly as a liquid fertilizer without discarding or regenerating the reaction medium, thereby enabling a substantially zero-waste process that simultaneously upcycles organic residues and produces value-added agricultural inputs.

[0012] In an example embodiment, fertilizer compositions include: (i) nitro-oxidation process-derived cellulosic fibers and / or cellulose nanofibers; (ii) plant-available nitrogen, including nitrate and optionally ammonium; (iii) plant-available phosphorus and potassium; and (iv) oxidized organic carbon species originating from the processed biomass. The compositions may be formulated to define N:P:K ratios, for example about 3-1-2 or 3-0-3 on a weight basis, and can further include secondary and micronutrients such as calcium, magnesium, iron, and manganese. In certain example embodiments, additional cellulose nanofibers isolated from NOP solids are re-introduced into the liquid fertilizer at controlled concentrations to enhance nutrient sorption and release properties and to provide structural or soil-conditioning benefits.

[0013] Other example embodiments provide methods for fertilizing plants and soils by applying an agriculturally effective amount of the NOP-derived fertilizer compositions to a soil, growth medium, or turf surface. Application can be carried out by soil drench, fertigation, spray, banding, or incorporation into soilless substrates, and is suitable for field crops, vegetable crops, horticultural crops, and turf grasses. As shown by lettuce pot studies, NOP fertilizers formulated from food waste, spent grain, palm waste, and horse manure and adjusted to deliver the same nominal NPK dose as a commercial soluble fertilizer are capable of sustaining or increasing plant biomass, with the horse-manure-derived fertilizer in particular providing higher lettuce yields than a commercial control fertilizer. At the same time, the NOP fertilizers reduce cumulative leaching losses of nitrogen, phosphorus, and potassium from soil relative to the commercial fertilizer, thereby improving nutrient use efficiency and mitigating nutrient run-off.

[0014] Example embodiments of the present invention provide turf fertilizer formulations in which NOP effluents are combined with nitrogen and potassium sources, optionally iron and manganese, and optionally cellulose nanofibers to yield products having, for example, NPKvalues of about 3-0-0 or about 3-0-3. When applied to turf grass at agronomic nitrogen rates, such formulations support turf growth and re-growth after cutting that is comparable to or better than urea-based controls, increase ground coverage, and deliver micronutrients to the foliage. Formulations containing cellulose nanofibers exhibit enhanced turf coverage, and formulations containing iron and manganese produce darker green turf, demonstrating that NOP-based systems can be engineered to provide both macronutrient delivery and cosmetic performance.

[0015] Collectively, the compositions and methods of the example embodiments provide a versatile platform for converting diverse organic wastes into high-performance liquid fertilizers that (i) recover and concentrate plant-essential macro- and micro-nutrients from the original feedstocks, (ii) incorporate functional cellulosic nanofibers and oxidized organics that modulate nutrient dynamics in soil, (iii) reduce nutrient leaching and associated environmental losses, while maintaining or improving crop and turf productivity, and (iv) operate with minimal or no process waste, offering both agronomic and environmental advantages over conventional fertilizer technologies.

[0016] The fertilizers of example embodiments include nitro-oxidation process (NOP)-derived cellulosic fibers (e.g., cellulose microfibers (CMF) and / or cellulose nanofibers (CNFs)), nutrient solutions, and oxidized organic compounds. The example embodiments further relate to slow-release and enhanced-efficiency formulations that modulate nitrogen (N), phosphorus (P), and potassium (K) availability in soil, reduce nutrient losses caused by leaching and run-off, and enable the upcycling of organic waste materials into value-added agricultural inputs.

[0017] According to an example embodiment of the present invention, a liquid fertilizer composition include an aqueous phase, dispersed cellulosic fibers including carboxylated cellulose microfibers and / or carboxylated cellulose nanofibers, dissolved nitrogen, dissolved phosphorus, dissolved potassium, an oxidized organic carbon compound, and a nitro-oxidized effluent.

[0018] The dispersed cellulosic fibers can include nitro-oxidized cellulosic fibers. The carboxylated cellulose nanofibers can have a diameter in a range of about 5 nm–about 500 nm and a carboxyl content of at least about 0.1 mmol / g. The nitro-oxidized effluent can include atleast about 30 wt% to about 40 wt% of a total of the dissolved nitrogen, at least about 10 wt% of a total of the dissolved phosphorus, and at least about 10 wt% of a total of the dissolved potassium.

[0019] The nitro-oxidized effluent can be obtained by nitro-oxidation of an organic waste feedstock with nitric acid, and the organic waste feedstock can be selected from the group including food waste, brewery spent grain, distillery spent grain, coffee grounds, animal manures, agricultural residues, crop vines, fruit rinds and / or peels, vegetable rinds and / or peels, palm residues, sugarcane bagasse, hardwood residues, softwood residues, aquatic biomass, or a combination thereof.

[0020] The liquid fertilizer composition can have an N:P:K ratio by weight in a range of about 1:0.1:0.5 to about 10:5:10. The liquid fertilizer composition can have an N:P:K ratio of about 3:1:2, about 3:0:3, about 24:0:0, about 13:0:0, about 7:0:7, about 17:0:0, about 3:0:0, or about 7:0:0. The liquid fertilizer composition can have an N: K ratio of about 3:3 and can contain substantially no phosphorus other than phosphorus included in the nitro-oxidized effluent. A total nitrogen concentration can be from about 0.01 wt%-about 10 wt%, and a total potassium concentration can be from about 0.01 wt%-about 15 wt%. The dispersed cellulosic fibers can be present at a concentration of about 0.01 wt%-about 5 wt% of the liquid fertilizer composition.

[0021] The oxidized organic carbon compounds can include one or more of a low molecular weight carboxylic acid, a polycarboxylate, a humic-like substance, a lignin-derived aromatic, and a hemicellulose-derived oligosaccharide. The liquid fertilizer composition can further include one or more selected from the group including calcium, magnesium, sulfur, iron, manganese, zinc, copper, boron, molybdenum, chlorine, and a combination thereof. 14. The liquid fertilizer composition can further include iron and / or manganese in amounts effective to enhance leaf greenness of turf grass relative to an identical liquid fertilizer composition without iron and / or manganese. The carboxylated cellulose nanofibers can be present in the liquid fertilizer composition at a concentration of about 0.01 wt% to about 1 wt% of the liquid fertilizer composition. The liquid fertilizer composition can be substantially free of heavy metals selected from the group including arsenic, cadmium, lead, mercury, and a combination thereof.

[0022] When the liquid fertilizer composition is applied to soil at a given nitrogen application rate and evaluated using a five-week weekly leaching protocol, the cumulative nitrogen leaching loss from the soil can be at least about 10% lower than a cumulative nitrogen leaching loss obtained with a reference fertilizer consisting essentially of water-soluble urea applied at the given nitrogen application rate and evaluated using the five-week weekly leaching protocol.

[0023] The liquid fertilizer composition can be a pumpable liquid with a total solids content in range of about 0.1 wt%-about 20 wt%. The liquid fertilizer composition can be free of synthetic polymeric slow-release coatings.

[0024] The dissolved nitrogen can include proteins, organic nitrogen-containing compounds, nitrate, ammonium, or a mixture thereof. The dissolved phosphorus can include ortho-phosphate, phosphate esters, phosphonates, or a mixture thereof. The oxidized organic carbon compounds can include hemi-cellulose, lignin, acid hydrolyzed derivative of hemicellulose, acid hydrolyzed derivative of lignin, or a mixture thereof. The nitro-oxidized effluent can include at least a portion of each of the dispersed cellulosic fibers, the dissolved nitrogen, the dissolved phosphorus, the dissolved potassium, and the oxidized organic carbon compounds.

[0025] According to an example embodiment of the present invention, a method of fertilizing plants includes applying to soil or a growth medium with an agriculturally effective amount of the liquid fertilizer composition according to another example embodiment of the present invention.

[0026] The plants can include a leafy vegetable crop. The leafy vegetable crop can be lettuce. The plants can include turf grass. The liquid fertilizer composition can be applied by at least one of soil drench, fertigation, in-furrow application, side-dressing, or surface spraying. The liquid fertilizer composition can be applied at a rate corresponding to about 10 kg of nitrogen per hectare-about 400 kg of nitrogen per hectare.

[0027] When the liquid fertilizer composition is applied to soil at a given nitrogen application rate and evaluated using a five-week weekly leaching protocol, a cumulative nitrogen leaching loss from the soil can be at least about 10% lower than a cumulative nitrogenleaching loss obtained with a reference fertilizer consisting essentially of water-soluble urea applied at the given nitrogen application rate and evaluated using the five-week weekly leaching protocol. When the liquid fertilizer composition is applied to soil at a given phosphorus application rate and evaluated using a five-week weekly leaching protocol, a cumulative phosphorus leaching loss from the soil can be at least about 5% lower than a cumulative phosphorus leaching loss obtained with a reference fertilizer consisting essentially of water-soluble urea applied at the given phosphorus application rate and evaluated using the five-week weekly leaching protocol. When the liquid fertilizer composition is applied to soil at a given potassium application rate and evaluated using a five-week weekly leaching protocol, a cumulative potassium leaching loss from the soil can be at least about 5% lower than a cumulative potassium leaching loss obtained with a reference fertilizer consisting essentially of water-soluble urea applied at the given potassium application rate and evaluated using the five-week weekly leaching protocol.

[0028] The liquid fertilizer composition can be a turf fertilizer composition including iron and / or manganese and is applied to turf grass to improve turf coloration and coverage. The turf fertilizer composition can further include carboxylated cellulose nanofibers and can provide improved turf coverage relative to an identical composition without carboxylated cellulose nanofibers.

[0029] According to an example embodiment of the present invention, a method of improving nutrient use efficiency in soil includes applying to the soil the liquid fertilizer composition of another example embodiment of the present invention such that (i) plant-available nitrogen in the soil is maintained at levels sufficient for plant growth and (ii) at least one of nitrogen, phosphorus, or potassium leaching losses from the soil is reduced relative to an equivalent application of a reference fertilizer consisting essentially of water-soluble urea.

[0030] According to an example embodiment of the present invention, a method of producing a liquid fertilizer composition includes (a) providing an organic waste feedstock, (b) contacting the organic waste feedstock with an aqueous nitric acid solution under conditions sufficient to nitro-oxidize the organic waste feedstock and to produce a reaction mixture including an acidic aqueous phase and a suspended cellulosic-solid phase, (c) separating at leasta portion of the suspended cellulosic-solid phase from the reaction mixture to obtain a nitrooxidized effluent and isolated cellulose nanofibers, (d) neutralizing the nitro-oxidized effluent with a base to obtain a neutralized effluent, and (e) formulating the neutralized effluent into the liquid fertilizer composition.

[0031] The step (b) can be carried out with nitric acid at a concentration in the range of about 1 wt% to about 70 wt%, at a temperature of about 10°C-about 120°C, and for a time of about 0.25 hours-about 24 hours. The step (b) can include contacting the organic waste feedstock with a nitrite salt. The nitrite salt in step (b) can include potassium nitrite. The base in step (d) can be selected from the group including an ammonium hydroxide, a potassium hydroxide, a sodium hydroxide, a calcium hydroxide, and a combination thereof. The neutralized effluent can be adjusted to a pH in the range of about 5.0–about 8.5. The method can further include, after step (d), adding one or more nutrient salts selected from the group including a nitrogen salt, a phosphorus salt, a potassium salt, a secondary salt, and a micronutrient salt. The method can further include dispersing the isolated cellulose nanofibers into the neutralized effluent prior to or during step (e). All or substantially all of the neutralized effluent can be formulated into the liquid fertilizer composition without discharge of a separate liquid waste stream. The organic waste feedstock can include at least one of food waste, brewery spent grain, palm waste, or horse manure. The method can further include concentrating or diluting the neutralized effluent to obtain a total nitrogen concentration suitable for direct agricultural application. The liquid fertilizer composition can have an N:P:K ratio of about 3:1:2, about 3:0:3, about 24:0:0, about 13:0:0, about 7:0:7, about 17:0:0, about 3:0:0, or about 7:0:0.

[0032] According to an example embodiment of the present invention, a method of upcycling organic waste including converting the organic waste feedstock into the liquid fertilizer composition of another embodiment of the present invention by the method of another embodiment of the present invention and then applying the liquid fertilizer composition to soil, a growth medium, or turf grass.

[0033] The above and other features, elements, characteristics, steps, and advantages of the present invention will become more apparent from the following detailed description of example embodiments of the present invention with reference to the attached drawings.BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Fig. 1 shows Fourier transform infrared (FTIR) spectra comparing the dry residue of a commercial fertilizer with lyophilized residues of nitro-oxidation process (NOP) fertilizers derived from palm waste, horse manure, food waste, and spent grain.

[0035] Fig. 2 is a bar graph showing lettuce shoot biomass yield in response to application of different NOP fertilizers and a control treatment. The bars represent mean values with standard deviation (n = 5); bars labeled with different letters indicate treatments that are statistically different at p = 0.05.

[0036] Figs. 3A-3C are bar graphs showing cumulative nitrogen (A), phosphorus (B), and potassium (C) leached from soil (mg / kg) over a five-week period of weekly leaching events for soil treated with NOP fertilizers and control treatments. The bars represent mean values with standard deviation (n = 5); within each nutrient panel, bars labeled with different letters indicate treatments that are statistically different at p = 0.05.

[0037] Figs. 4A-4C are line graphs showing temporal patterns of nitrogen (A), phosphorus (B), and potassium (C) losses from control and NOP-fertilizer-treated soils (mg / kg) during a five-week series of weekly leaching events.DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS

[0038] The following examples are provided to illustrate particular example embodiments of the present invention and are not intended to limit its scope. Unless otherwise indicated, percentages are by weight and concentrations are given on a mass-per-volume basis.

[0039] Example embodiments provide a liquid fertilizer composition that includes a nitrooxidized effluent (also referred to as NOP-derived effluent). The liquid fertilizer composition includes an aqueous phase, which can at least be partially provided by the nitro-oxidized effluent. Cellulosic fibers can be dispersed in the aqueous phase. In addition, nitrogen, phosphorus, and potassium can be dissolved in the aqueous phase. It is possible that the liquidfertilizer composition is substantially free of heavy metals selected from the group including arsenic, cadmium, lead, mercury, and a combination thereof, within manufacturing and / or measurement tolerances. It is also possible that the liquid fertilizer composition is free of synthetic polymeric slow-release coatings.

[0040] The N: P: K values of the liquid fertilizer can be tuned to the particular application. The liquid fertilizer composition can, for example, have an N:P:K ratio by weight in a range of about 1:0.1:0.5 to about 10:5:10, within manufacturing and / or measurement tolerances. Or the liquid fertilizer composition can have an N:P:K ratio of about 3:1:2, about 3:0:3, about 24:0:0, about 13:0:0, about 7:0:7, about 17:0:0, about 3:0:0, or about 7:0:0, within manufacturing and / or measurement tolerances. In an example embodiment, the liquid fertilizer composition can have an N: K ratio of about 3:3, within manufacturing and / or measurement tolerances, and can contain substantially no phosphorus other than the phosphorus included in the nitrooxidized effluent. The total nitrogen concentration in the liquid fertilizer composition can be from about 0.01 wt%-about 10 wt%, within manufacturing and / or measurement tolerances, and a total potassium concentration in the liquid fertilizer composition can be from about 0.01 wt%-about 15 wt%, within manufacturing and / or measurement tolerances.

[0041] Optionally, the liquid fertilizer can include secondary nutrients and / or micronutrients, including for example, one or more selected from the group including calcium, magnesium, sulfur, iron, manganese, zinc, copper, boron, molybdenum, chlorine, and a combination thereof. For some applications, the liquid fertilizer can include iron and / or manganese. Iron and / or manganese can be included in amounts effective to enhance leaf greenness of turf grass relative to an identical liquid fertilizer composition without iron and / or manganese.

[0042] The dispersed cellulosic fibers can present at a concentration of about 0.01 wt%-about 5 wt% of the liquid fertilizer composition, within manufacturing and / or measurement tolerances. The dispersed cellulosic fibers can include nitro-oxidized cellulosic fibers, but the dispersed cellulosic fibers do not have to be nitro-oxidized cellulosic fibers. For example, the dispersed cellulosic fibers can be a mix of nitro-oxidized cellulosic fibers and cellulosic fibers from other sources. The nitro-oxidized cellulosic fibers can be obtained using any of the nitro-oxidation processes (NOPs) disclosed in U. S. Patent No. 10,894,838, PCT Application No.PCT / US2015 / 060261, PCT Application No. PCT / US2024 / 026949, PCT Application No.PCT / US2024 / 055838, and PCT Application No. PCT / IB2025 / 053319, the entire contents of this patent and these applications are hereby incorporated by reference. PCT Application No.PCT / IB2025 / 053319 discloses a pressure-assisted NOP (PANOP) that can be used to make nitrooxidized or NOP-derived cellulosic fibers. As an example, the dispersed cellulosic fibers can be obtained by contacting a lignocellulosic material with an aqueous nitric acid solution and optionally nitrite salt under conditions sufficient to partially depolymerize cellulose and introduce carboxyl groups on the cellulose backbone.

[0043] The cellulosic fibers can include carboxylated cellulose microfibers (carboxylated CMFs) and / or carboxylated cellulose nanofibers (carboxylated CNFs). The carboxylated cellulose nanofibers have a diameter in a range of about 5 nm–about 500 nm, within manufacturing and / or measurement tolerances, and a carboxyl content of at least about 0.1 mmol / g, within manufacturing and / or measurement tolerances. The carboxylated cellulose nanofibers can be present in the liquid fertilizer composition at a concentration of about 0.01 wt% to about 1 wt% of the liquid fertilizer composition.

[0044] Examples of dissolved nitrogen include proteins, organic nitrogen-containing compounds, nitrate, ammonium, and mixtures thereof. Examples of dissolved phosphorus includes ortho-phosphates, phosphate esters, phosphonates, and mixtures thereof. The liquid fertilizer compositions can include an oxidized organic carbon compound. Examples of oxidized organic carbon compounds include hemi-cellulose, lignin, acid hydrolyzed derivatives of hemicellulose (such as monomers, dimers, oligomers, and oxidized versions), acid hydrolyzed derivatives of lignin (such as monomers, dimers, oligomers, and oxidized versions), and mixtures thereof. The oxidized organic carbon compounds can include one or more of a low molecular weight carboxylic acid, a polycarboxylate, a humic-like substance, a lignin-derived aromatic, and a hemicellulose-derived oligosaccharide.

[0045] The nitro-oxidized effluent can provide at least a portion of one or more of the dispersed cellulosic fibers, the dissolved nitrogen, the dissolved phosphorus, the dissolved potassium, and the oxidized organic carbon compounds. Alternatively or in addition to thenitro-oxidized effluent providing these components, one or more of dispersed cellulosic fibers, dissolved nitrogen, dissolved phosphorus, dissolved potassium, and oxidized organic carbon compound can be added separately from the nitro-oxidized effluent. For example, the nitrooxidized effluent can include at least about 30 wt% to about 40 wt% of a total of the dissolved nitrogen, at least about 10 wt% of a total of the dissolved phosphorus, and at least about 10 wt% of a total of the dissolved potassium, within manufacturing and / or measurement tolerances.

[0046] The nitro-oxidized effluent can be obtained by nitro-oxidation of an organic waste feedstock with nitric acid. The organic waste feedstock by treated with any of nitro-oxidation processes (NOPs) disclosed in U. S. Patent No. 10,894,838, PCT Application No.PCT / US2015 / 060261, PCT Application No. PCT / US2024 / 026949, PCT Application No.PCT / US2024 / 055838, and PCT Application No. PCT / IB2025 / 053319. PCT Application No.PCT / IB2025 / 053319 discloses a pressure-assisted NOP (PANOP) that can be used to process organic waste feedstock to make nitro-oxidized or NOP-derived effluent. The organic waste feedstock can be selected, for example, from the group including food waste, brewery spent grain, distillery spent grain, coffee grounds, animal manures, agricultural residues, crop vines, fruit rinds and / or peels, vegetable rinds and / or peels, palm residues, sugarcane bagasse, hardwood residues, softwood residues, aquatic biomass, or a combination thereof. An NOP-derived effluent typically includes a characteristic mix of sugar-derived oligomers from, for example, cellulose and hemicellulose, and of oxidized / acid-solubilized lignin derivatives from, for example, the specific biomass. These carbon species, the carboxylated cellulosic fibers, and the high nitrate can create a compositional "fingerprint" that is consistent with NOP treatment.

[0047] The liquid fertilizer compositions can be pumpable. For example, the liquid fertilizer composition can be a pumpable liquid with a total solids content in range of about 0.1 wt%-about 20 wt%, within manufacturing and / or measurement tolerances.

[0048] The liquid fertilizer compositions can reduce leaching compared to conventional fertilizers. Specifically, the liquid fertilizer compositions can nitrogen, phosphorus, and potassium leaching when applied to soil.

[0049] For example, when the liquid fertilizer composition is applied to soil at a given nitrogen application rate and evaluated using the five-week weekly leaching protocol discussed below, the cumulative nitrogen leaching loss from the soil is at least about 10%, within manufacturing and / or measurement tolerances, lower than a cumulative nitrogen leaching loss obtained with a reference fertilizer consisting essentially of water-soluble urea applied at the given nitrogen application rate and evaluated using the same five-week weekly leaching protocol. For example, when the liquid fertilizer composition is applied to soil at a given phosphorus application rate and evaluated using the five-week weekly leaching protocol discussed below, the cumulative phosphorus leaching loss from the soil is at least about 5%, within manufacturing and / or measurement tolerances, lower than the cumulative phosphorus leaching loss obtained with a reference fertilizer consisting essentially of water-soluble urea applied at the given phosphorus application rate and evaluated using the same five-week weekly leaching protocol. For example, when the liquid fertilizer composition is applied to soil at a given potassium application rate and evaluated using the five-week weekly leaching protocol discussed below, a cumulative potassium leaching loss from the soil is at least about 5%, within manufacturing and / or measurement tolerances, lower than a cumulative potassium leaching loss obtained with a reference fertilizer consisting essentially of water-soluble urea applied at the given potassium application rate and evaluated using the same five-week weekly leaching protocol.

[0050] The liquid fertilizer compositions of example embodiments can be used to fertilize plants. For example, the liquid fertilizer composition can be applied to soil or a growth medium. As examples, the plants can include a leafy vegetable crop, such as lettuce, or turf grass. But the liquid fertilizer compositions can be applied to other plants as well. The liquid fertilizer composition can be a turf fertilizer composition comprising iron and / or manganese and can be applied to turf grass to improve turf coloration and coverage. The turf fertilizer composition can further include carboxylated cellulose nanofibers and can provide improved turf coverage relative to an identical composition without carboxylated cellulose nanofibers. The liquid fertilizer composition can be applied by any suitable method, including, for example, by at least one of soil drench, fertigation, in-furrow application, side-dressing, or surface spraying. Anagriculturally effective amount of liquid fertilizer composition can be applied, including, for example, form 0 ppm N per single plant-200 ppm N per single plant, within manufacturing and / or measurement tolerances. Alternatively, the liquid fertilizer composition can be applied at a rate corresponding to about 10 kg of nitrogen per hectare-about 400 kg of nitrogen per hectare, within manufacturing and / or measurement tolerances.

[0051] The liquid fertilizer compositions of example embodiments can be used to improve nutrient use efficiency. For example, the liquid fertilizer compositions can be applied to soil such that plant-available nitrogen in the soil is maintained at levels sufficient for plant growth and such that leaching losses of at least one of nitrogen, phosphorus, or potassium from the soil is reduced relative to an equivalent application of a reference fertilizer consisting essentially of water-soluble urea. In addition, application of the liquid fertilizer compositions can result in plant biomass yields that are at least equal to or greater than the plant biomass yield obtained with a conventional fully water-soluble fertilizer applied at the same nitrogen rate.

[0052] Example embodiments of the present invention include methods of producing liquid fertilizer compositions. The methods include using a single-step NOP-treatment of organic waste feedstock to make an effluent and cellulosic fibers that can be used in the liquid fertilizer compositions. That is, the resultant cellulosic fibers do not have to be isolated and then purified as a separate material before being incorporated into the liquid fertilizer compositions, while also using the full nutrient content of the resultant effluent.

[0053] The methods include providing a suitable organic waste feedstock and contacting the organic waste feedstock with an aqueous nitric acid solution, optionally in the presence of a nitrite salt (e.g., potassium nitrite), under conditions sufficient to nitro-oxidize the organic waste feedstock and to produce a reaction mixture including an acidic aqueous phase and a suspended cellulosic-solid phase. Suitable organic waste feedstock can include, for example, at least one of food waste, brewery spent grain, palm waste, or horse manure. This step be carried out, for example, with nitric acid at a concentration in the range of about 1 wt% to about 70 wt%, at a temperature of about 10°C-about 120°C, and for a time of about 0.25 hours-about 24 hours, within manufacturing and / or measurement tolerances. It is possible to conduct this step under other conditions. At least a portion of suspended cellulosic-solid phase can beseparated from the reaction mixture to obtain a nitro-oxidized effluent and isolated cellulose nanofibers. The nitro-oxidized effluent can be neutralized with a base to obtain a neutralized effluent. The base can be any suitable base, including, for example, a based selected from the group including an ammonium hydroxide, a potassium hydroxide, a sodium hydroxide, a calcium hydroxide, and a combination thereof. The neutralized effluent can be adjusted to any desirable pH, including, for example, a pH in the range of about 5.0–about 8.5, within manufacturing and / or measurement tolerances. Optionally, to adjust the nutrient analysis of the liquid fertilizer composition, one or more nutrient salts can be added to the neutralized effluent. The nutrient salts can be selected from the group including a nitrogen salt, a phosphorus salt, a potassium salt, a secondary micronutrient salt, a combination thereof. The neutralized effluent can then be formulated into a liquid fertilizer composition.

[0054] Before the neutralized effluent is formulated into the liquid fertilizer composition, isolated cellulose nanofibers can be dispersed into the neutralized effluent.

[0055] During these methods all or substantially all, within manufacturing and / or measurement tolerances, of the neutralized effluent can be formulated into the liquid fertilizer composition without discharge of a separate liquid waste stream. The methods also include concentrating or diluting the neutralized effluent to obtain a total nitrogen concentration suitable for direct agricultural application. The resultant liquid fertilizer composition can have an N:P:K ratio of about 3:1:2, about 3:0:3, about 24:0:0, about 13:0:0, about 7:0:7, about 17:0:0, about 3:0:0, or about 7:0:0.

[0056] Example embodiments of the present invention provide methods of upcycling organic waste by converting suitable organic waste feedstock into a liquid fertilizer composition according to another example embodiment by a method according to another example embodiment and then applying the liquid fertilizer composition to soil, a growth medium, or turf grass.Example 1: Nutrient Profile of NOP Effluents and Respective Biomasses

[0057] This example demonstrates that the nitro-oxidation process (NOP) solubilizes macro-and micronutrients from a wide range of organic feedstocks into a liquid phase and that theresulting nitro-oxidized effluents (also referred to as NOP-derived effluents) possess nutrient profiles suitable for use as liquid fertilizers.1.1 Instrumentation and Materials

[0058] Macronutrients (P, K, Ca, S, Na, Mg) and micronutrients (including Fe, Mn, Zn, Si and others) in biomass digests and nitro-oxidized effluents were quantified by ICP-OES using a Thermo Scientific iCAP 6500 instrument. Nitrate, nitrite, and ammonium were quantified colorimetrically on a POLARstar Omega plate reader using 300-µL wells of a 96-well microplate.

[0059] All biomass feedstocks (including palm tree foliage, sugarcane bagasse, brewery and distillery spent grains, coffee grounds, grape pomace, tomato vine, hemp vine, azolla, manures, hardwood, various fruit and vegetable rinds and peels, sorghum, cruciferous vegetables, and pistachio shells) were dried at 60°C and ground or blended to a fine granular consistency prior to use.1.2 Nitro-Oxidation Process (NOP)

[0060] For each biomass, NOP was carried out in 100-mL digestion tubes equipped with PVDF-coated stir bars. Dry biomass (3.0 g) was combined with 42 mL of 50 % (w / w) HNO3, and 0.50 g KNO3was added as an oxidizing agent. Tubes were sealed and heated at 50°C with stirring (~230 rpm) for 9 h. After cooling, tubes were vented in a fume hood, and the suspensions were filtered through glass microfiber filters to separate the cellulose-rich solids from the NOP effluent. The effluent volume and mass were recorded, and solid cellulose was washed with deionized water until the supernatant pH exceeded 2.5.1.3 Acid Digestion of Raw Biomasses

[0061] For comparison, 0.50 g of each dry biomass was digested with 5.0 mL of 70 % HNO3at 115°C for 20 min. After cooling, 1.0 mL of 30 % H2O2was added, and heating was continued for an additional 20 min at 115°C. Digests were diluted to 50 mL with deionized water and weighed prior to analysis.1.4 Macronutrient and Micronutrient Contents of Raw Biomasses

[0062] Macronutrient concentrations in the raw biomasses, expressed as mg of nutrient per g of dry biomass, are summarized in Table 1. High-P feedstocks included brewery and distillery spent grains, hemp vine, azolla, tomato vine, and gourd and cantaloupe rinds, with P values generally above 5 mg / g and up to about 6.8 mg / g (Table 1). Potassium was particularlyenriched in food-waste-type biomasses such as banana peel, broccoli, sorghum, and fruit rinds and peels, with K contents up to about 72.8 mg / g in banana peel (Table 1). Sulfur and calcium contents varied widely, with cruciferous vegetables and vine residues showing elevated levels (Table 1).Table 1: Total P, K, S, Ca, and Na Concentrations of Raw BiomassBiomass P[a]K[a]S[a]Ca[a]Na[a]Palm Tree 0.642± 0.048 6.268± 0.615 2.295± 0.280 11.669+ 2.396 0.261± 0.069 Bagasse 0.267± 0.018 1.404 ± 0.055 0.394± 0.031 1.098± 0.105 0.126± 0.008 SpentGrains 5.796 ± 0.066 1.165 ± 0.016 2.430± 0.066 1.759 ± 0.094 0.097 ± 0.001 (Brewery)SpentGrains 6.542 ± 0.147 4.492 ± 0.538 28.782 ± 0.903 2.198 ± 1.117 0.725 ± 0.0226 (Distillery)Coffee1.617 ± 0.074 7.134 ± 0.142 1.253± 0.021 1.416± 0.023 0.039± 0.010 GroundsPomace 3.336± 0.258 23.014± 7.455 1.488± 0.087 3.445± 0.528 0.120± 0.025 Tomato5.181± 0.459 41.253± 1.247 2.907± 0.170 25.894± 1.458 0.725± 0.138 VineHemp Vine 6.271± 0.093 45.136± 0.894 2.794± 0.114 22.234± 0.512 0.601± 0.009 Azolla 5.031± 0.053 18.564± 0.577 4.550± 0.134 22.803± 0.191 9.143± 0.066 Cow4.758 ± 0.225 3.379 ± 0.122 1.540± 0.107 12.931 ± 0.302 0.874 ± 0.048 ManureHorse3.753± 1.686 5.750± 1.043 1.216± 0.210 15.477± 7.078 1.301± 0.063 ManureHardwood 0.641± 0.031 1.135± 0.040 4.619± 0.172 7.190± 0.146 5.111± 0.115 Banana3.309± 0.031 72.837 ± 1.291 1.195± 0.033 3.864± 0.118 0.279± 0.028 (Peel)Pistachio0.290± 0.073 1.535± 0.147 0.099± 0.011 0.262± 0.028 3.336± 0.663 ShellSorghum 0.586± 0.085 31.328± 1.311 0.764± 0.009 3.847± 0.139 0.269± 0.004 Broccoli 4.980± 0.140 56.839± 0.242 9.398± 0.070 3.967± 0.046 0.373± 0.012 Cabbage 3.509± 0.072 26.154± 0.244 2.562± 0.136 4.932± 0.066 1.502± 0.017 Onion 4.586± 0.061 17.005± 0.144 5.299± 0.080 12.898± 0.407 0.429± 0.066 Gourd6.529± 0.179 33.092± 0.662 1.690± 0.049 3.349± 0.060 0.134 ± 0.001 (Rind)Cantaloupe6.827 ± 0.348 30.987± 1.304 2.681± 0.111 4.163 ± 0.181 1.364 ± 0.065 (Rind)Watermelon 2.198± 0.067 18.648± 0.892 1.283± 0.054 1.965± 0.067 0.120± 0.016, 2.198 ± 0.094 18.648± 0.150 1.283± 0.058 1.965 ± 0.004 0.120 ± 0.007 (Skin / Leaf)Values indicated are averages of 3 replicates ± standard deviation. Element concentrations were determined by ICP-OES analysis.[a]Total element concentrations expressed as mg of nutrient per g of biomass.

[0063] Micronutrient contents (Fe, Mg, Mn, Zn, Si) in the same biomasses are shown in Table 2. Manures, bagasse, hardwood, and certain residues exhibited relatively high Fe and Mg, whereas many food-waste materials had modest but agronomically relevant levels of Mn and Zn as shown in Table 2. Heavy metals such as Ag, As, Cd, Co, Li, Pb, Ni, Sb, Se, Ti, and Mo were below the ICP-OES detection limit (0.100 ppm) for all biomasses as shown in Table 2.Table 2: Total Fe, Mg, Mn, Zn, and Si Concentrations of Raw BiomassBiomass Fe[a]Mg[a]Mn[a]Zn[a]Si[a]Palm Tree 0.430 ± 0.099 2.249 ± 0.213 0.053 ± 0.008 0.018 ± 0.003 0.761 ± 0.276 Bagasse 1.315 ± 0.327 0.519 ± 0.091 0.023 ± 0.003 0.018 ± 0.004 0.289 ± 0.008 Spent Grains0.155 ± 0.038 2.007 ± 0.076 0.040 ± 0.003 0.078 ± 0.007 1.396 ± 0.096 (Brewery)Spent Grains1.106 ± 0.093 2.239 ± 1.293 0.416 ± 0.012 0.904± 0.0914 5.087 ± 1.212 (Distillery)Coffee0.045 ± 0.001 1.710 ± 0.039 0.037 ± 0.000 0.008 ± 0.000 0.015 ± 0.002 GroundsPomace 0.032 ± 0.001 0.955 ± 0.023 0.010 ± 0.000 0.016 ± 0.002 0.041 ± 0.008 Tomato Vine 0.107 ± 0.038 4.427 ± 0.305 0.073 ± 0.004 0.076 ± 0.037 0.116 ± 0.059 Hemp Vine 0.142 ± 0.036 7.066 ± 0.107 0.141 ± 0.001 0.065 ± 0.000 0.097 ± 0.006 Azolla 0.152 ± 0.024 2.077 ± 0.012 0.034 ± 0.001 0.303 ± 0.065 1.443 ± 0.112 Cow Manure 0.509 ± 0.040 4.178 ± 0.217 0.159 ± 0.009 0.050± 0.002 1.839 ± 0.031 Horse Manure 3.192 ± 0.505 2.689 ± 0.609 0.153 ± 0.032 0.108± 0.070 3.715 ± 1.090 Hardwood 0.886 ± 0.057 0.525 ± 0.303 0.386 ± 0.222 0.279± 0.021 0.293 ± 0.021 Banana (Peel) 0.029 ± 0.001 1.853 ± 0.021 0.066 ± 0.002 0.026± 0.001 1.093 ± 0.259 Pistachio Shell 0.000 ± 0.000 0.038 ± 0.008 0.010 ± 0.015 0.015 ± 0.021 0.061 ± 0.071 Sorghum 0.048 ± 0.014 2.321 ± 0.051 0.143 ± 0.001 0.015 ± 0.002 6.456 ± 3.721 Broccoli 0.032 ± 0.001 2.485 ± 0.046 0.014 ± 0.000 0.027 ± 0.0001 0.016 ± 0.004 Cabbage 0.035 ± 0.001 2.672 ± 1.036 0.022 ± 0.0001 0.018 ± 0.001 0.102 ± 0.049 Onion 0.077 ± 0.017 1.508 ± 0.050 0.019 ± 0.001 0.023 ± 0.017 0.054 ± 0.031 Gourd (Rind) 0.057 ± 0.002 2.303 ± 0.054 0.011 ± 0.0001 0.032 ± 0.0001 0.421 ± 0.059Cantaloupe0.051 ± 0.002 4.469 ± 0.187 0.021 ± 0.001 0.030± 0.001 0.343 ± 0.030 (Rind)Watermelon 0.025 ± 0.001 1.036 ± 0.018 0.094 ±0.0002 0.023 ± 0.001 0.251 ± 0.013 Pineapple0.025 ±0.0004 1.036 ± 0.010 0.094 ± 0.001 0.023 ± 0.001 0.251 ± 0.009 (Skin / Leaf)Values indicated are averages of 3 replicates ± standard deviation. Element concentrations were determined by ICP-OES analysis.[a]Total element concentrations expressed as mg of nutrient per g of biomass.1.5 Macronutrient and Micronutrient Contents of NOP Effluents

[0064] Macronutrient concentrations solubilized into the nitric acid during NOP are summarized in Table 3. Feedstocks that were nutrient-rich in the raw state (e.g., azolla, vine residues, manures, fruit rinds and peels) yielded NOP effluents enriched in P, K, S, Ca, and Na as shown in Table 3.

[0065] Micronutrient concentrations in the NOP effluents are presented in Table 4. For most metals, the majority of the biomass-borne content was transferred to the effluent phase. This confirms that NOP can upcycle both macro- and micronutrients into a liquid fraction that can be directly used as a fertilizer base as shown in Tables 3 and 4.Table 3: Total P, K, S, Ca, and Na Concentrations of Biomass via NOPBiomass P[a]K[a]S[alCa[a]Na[a]Palm 0.686 ± 0.077 88.274± 7.587 2.482± 0.280 10.539 ± 1.320 1.363 ± 0.179 Bagasse 0.346 ± 0.032 88.110 ± 16.725 0.577 ± 0.049 1.833 ± 0.433 1.149 ± 0.070 Spent Grains6.327 ± 1.108 82.930± 7.969 2.676± 0.405 2.118± 0.348 1.053± 0.108 (Brewery)Coffee 1.752± 0.136 98.272±4.379 1.679± 0.113 2.055± 0.147 1.092± 0.062 Pomace 3.693 ± 0.711 105.937± 11.837 1.627 ± 0.280 4.089± 1.259 1.050± 0.140 Tomato Vine 4.445 ± 0.672 116.969± 11.595 2.833 ± 0.437 24.059 ± 3.480 1.459 ± 0.123 Hemp Vine 6.024± 1.634 105.514± 15.398 2.996± 0.781 22.806± 6.130 1.384± 0.307 Azolla (High P) 9.391± 0.504 110.269 ± 5.473 7.438± 0.377 2.186± 0.123 1.158± 0.019 Azolla (Low P) 4.134 ± 0.941 96.085 ± 8.314 7.097 ± 1.444 2.175 ± 0.454 1.658 ± 0.307 Cow Manure 5.205 ± 1.479 78.610± 1.731 2.001± 0.563 15.864± 4.631 1.607 ± 0.051 Horse Manure 3.110 ± 0.068 94.025 ± 7.824 1.265 ± 0.057 16.122 ± 1.905 1.823 ± 0.160 Hardwood 0.074 ± 0.007 64.280 ± 7.148 0.455 ± 0.044 1.446 ± 0.174 1.136 ± 0.124 Banana (Peel) 3.400± 0.644 134.423 ± 3.498 1.474 ± 0.300 4.520± 0.785 1.180± 0.310 Pistachio Shell 0.119± 0.013 67.968± 6.984 0.119± 0.012 0.558± 0.053 4.628± 1.482Sorghum 0.633 ± 0.036 87.736± 1.568 0.913 ± 0.053 3.970± 0.838 0.990± 0.171 Broccoli 3.840 ± 0.300 102.974 ± 4.545 7.793 ± 0.519 3.535 ± 0.291 1.221 ± 0.094 Cabbage 3.291 ± 0.323 91.451 ± 7.244 2.636± 0.237 5.170± 0.493 2.525 ± 0.159 Onion 4.289 ± 0.944 88.967 ± 14.425 5.429 ± 1.182 14.645 ± 3.035 1.678 ± 0.286 Gourd (Rind) 5.211 ± 1.388 78.610 ± 12.012 1.650± 0.429 3.135 ± 0.843 0.911 ± 0.162 Cantaloupe7.005 ± 0.850 98.892 ± 6.677 2.878± 0.314 4.693 ± 0.567 2.058 ± 0.167 (Rind)Watermelon 4.816 ± 1.042 97.182 ± 12.773 1.498 ± 0.303 3.473 ± 0.744 1.304 ± 0.281 Pineapple1.755 ± 0.228 74.915 ± 6.906 1.231± 0.142 1.944± 0.223 0.772 ± 0.073 (Skin / Leaf)Values indicated are averages of 3-5 replicates ± standard deviation. Element concentrations were determined by ICP-OES analysis.[a]Total element concentrations in mg per g of biomass.Table 4: Total Fe, Mg, Mn, Zn, and Si Concentrations of Biomass via NOP Biomass Fe[a]Mg[a]Mn[a]Zn[a]Si[a]Palm 0.249 ± 0.034 2.363 ± 0.282 0.066 ± 0.010 0.042 ±0.007 0.704 ± 0.077 Bagasse 1.803 ± 0.632 0.634± 0.059 0.029 ± 0.003 0.044± 0.010 0.351 ± 0.026 Spent Grains0.141± 0.012 2.276 ± 0.402 0.046 ± 0.004 0.109± 0.013 0.221 ± 0.015 (Brewery)Coffee 0.060± 0.006 2.115 ± 0.152 0.048 ± 0.007 0.021± 0.006 0.014± 0.002 Pomace 0.044± 0.005 1.131 ± 0.245 0.014 ± 0.002 0.041± 0.012 0.043 ± 0.004 Tomato Vine 0.116 ± 0.015 4.286 ± 0.612 0.075 ± 0.011 0.145 ± 0.018 0.064 ± 0.006 Hemp Vine 0.140± 0.016 7.204±1.950 0.161 ± 0.021 0.092± 0.011 0.075 ± 0.009 Azolla (High P) 0.173 ± 0.022 2.440 ± 0.132 0.052 ± 0.007 0.082 ± 0.012 0.010 ± 0.002 Azolla (Low P) 0.235 ± 0.027 2.879 ± 0.634 0.052 ± 0.005 0.061 ± 0.006 0.022 ± 0.001 Cow Manure 0.452± 0.061 5.130± 1.513 0.180± 0.023 0.071± 0.006 0.475 ± 0.073 Horse Manure 3.222± 0.425 2.890± 0.365 0.175 ± 0.012 0.135 ± 0.019 0.185 ± 0.014 Hardwood 0.087 ± 0.014 0.171 ± 0.015 0.038 ± 0.004 0.038 ± 0.005 0.048 ± 0.005 Banana (Peel) 0.032 ± 0.005 2.090 ± 0.395 0.072 ± 0.017 0.044 ± 0.009 0.757 ± 0.130 Pistachio Shell 0.000± 0.000 0.096 ± 0.009 0.000± 0.000 0.014 ± 0.006 0.026 ± 0.001 Sorghum 0.077 ± 0.005 2.263 ± 0.481 0.170 ± 0.011 0.032 ± 0.008 0.735 ± 0.046 Broccoli 0.034 ±0.010 2.075 ± 0.174 0.013 ± 0.002 0.038 ± 0.006 0.024 ± 0.001 Cabbage 0.031 ± 0.002 2.055 ± 0.198 0.020 ± 0.002 0.029 ± 0.011 0.056 ± 0.009 Onion 0.125 ± 0.016 1.684 ± 0.353 0.025 ± 0.003 0.052 ± 0.006 0.050 ± 0.005 Gourd (Rind) 0.057 ± 0.014 2.017 ± 0.543 0.010 ± 0.002 0.046 ± 0.008 0.324 ± 0.074 Cantaloupe0.069 ± 0.026 4.735 ± 0.596 0.026 ± 0.004 0.050 ± 0.006 0.326 ± 0.046 (Rind)Watermelon 0.027 ± 0.005 1.720 ± 0.395 0.018 ± 0.003 0.034 ± 0.011 0.207 ± 0.017Pineapple0.027 ± 0.001 0.927 ± 0.118 0.092± 0.004 0.038± 0.013 0.198± 0.012 (Skin / Leaf)Values indicated are averages of 3-5 replicates ± standard deviation. Element concentrations were determined by ICP-OES analysis.[a]Total element concentrations in mg per g of biomass.1.6 Nitrate, Nitrite, and Total Nitrogen in NOP Effluents

[0066] Final nitrate, nitrite, and calculated total nitrogen concentrations for selected NOP effluents and a nitric acid control (no biomass) are given in Table 5. The nitric acid control exhibited a nitrate concentration of about 10.9 M, while biomass-containing effluents showed slightly lower nitrate values (approximately 8.2-10.4 M) and elevated nitrite levels relative to the control as shown in Table 5. Calculated total nitrogen ranged from about 1.15 x 105to 1.53 x 105ppm, as shown in Table 5, indicating that NOP effluents are intrinsically rich in nitrate-N with minor nitrite.Table 5: Average Nitrate and Nitrite Concentrations of NOP EffluentsTotal N Biomass [NO₃⁻] M[a][NO₂⁻] M[b]ppm[c]Palm 9.883 ± 0.340 2.8xl03± 2.2xl0’41.385xl05Coffee 8.185 ± 0.638 2.6x10-3± 2.3x10-41.146xl05Cow Manure 8.989 ± 0.573 4.0xl03± 4.3xl0’41.259xl05Tomato (Vine) 10.201 ± 0.182 2.7xl03± 1.7xl0’41.429xl05Horse Manure 10.100 ± 0.187 2.4xl03± 1.7xl0‘41.413xl05Azolla (High P) 10.142 ± 0.272 3.1xl0’3± 1.5xl0’41.421x105Azolla (Low P) 9.936 ± 0.745 3.5x10-3± 2.6x10-41.392xl05Banana (Peel) 10.387 ± 0.240 3.5xl03± S. OxlO’41.455xl05Control[d]10.923 ± 0.130 2.5x10-4± 2.1x10-41.530xl05Broccoli 10.623 ± 0.292 2.9xl0’3± 1.8xl0’41.487xl05Cabbage 10.733 ± 0.670 2.5xl0’4± 1.3xl0’41.503xl05Pomace 9.824 ± 0.270 4.0xl0’3± 3.7xl0’41.376xl05Spent Grains (Brewery) 9.497 ± 0.521 3.5x10-3± 2.4x10-41.330xl05Onion 9.524 ± 0.558 4.1x10-3± 2.6x10-41.334xl05Hemp (Vine) 10.355 ± 0.342 4.0xl03± 3.8xl0’41.451xl05Gourd (Rind) 9.948 ± 0.183 4.2xl03± 8.3xl0’41.394xl05Hardwood 9.432 ± 0.501 3.6xl03± 5.3xl0’41.321x105Corn 10.026 ± 0.559 2.1x10-3± 3.7x10-41.404xl05Pistachio 10.653 ± 0.463 2.0x10-3± 2.9x10-41.492xl05Bagasse 9.858 ± 0.539 3.1xl03l 2.4xl0’41.381xl05Cantaloupe (Rind) 10.202 ± 0.276 3.0x10-3± 1.6x10-31.429xl05Sorghum 10.753 ± 0.304 4.0x10-3± 1.2x10-31.506xl05Watermelon (Rind) 10.84210.234 2.3xlQ-3i 1.3xl0’31.519xl05Pineapple (Skin / Leaf) 10.10610.165 4.3xlQ-3i 3.3xl0’41.415xl05Values indicated are averages of 3-5 replicates ± standard deviation.[a]The concentration of nitrate was determined by subtracting the nitrite concentration from the concentration of total nitrite after the reduction of nitrate by VCI3.[b]The concentration was determined by colorimetric detection by UV / Vis spectroscopy.[c]Total nitrogen values are representative of the sum of the mean concentrations of nitrate and nitrite, converted into stoichiometric elemental nitrogen.1.7 Nutrient Recovery Comparison: NOP vs. Acid Digestion

[0067] The percentage of each nutrient recovered in NOP effluents relative to the corresponding acid digests of raw biomasses is summarized in Table 6. Percentage recoveries were calculated as:(Average NOP effluent concentration / average acid digestion concentration) x 100 %. For most nutrients and feedstocks, recoveries approached or exceeded 100%, reflecting high solubilization efficiency and, in the case of K, additional potassium introduced via KNO3as shown in Table 6. This example shows that NOP effluents retain essentially all plant-essential macro- and micro-nutrients present in the feedstocks and therefore constitute nutrient-dense liquid fertilizer bases.Table 6: Nutrient % Recovery Comparison of Acid Digestion vs NOP Treated BiomassesBiomass P% K% S% Ca% Na% Fe% Mg% Mn% Zn% Si% Palm Tree 106.9 1408.3 108.1 90.3 522.2 57.9 105.1 124.5 233.3 92.5 Bagasse 129.6 6275.6 146.4 166.9 911.9 137.1 122.2 126.1 244.4 121.5 SpentGrains 109.2 7118.5 110.1 120.4 1085.6 91.0 113.4 115.0 139.7 15.8 (Brewery)Coffee108.3 1377.5 134.0 145.1 2800.0 133.3 123.7 129.7 262.5 93.3 GroundsPomace 110.7 460.3 109.3 118.7 875.0 137.5 118.4 140.0 256.3 104.9 Tomato85.8 283.5 97.5 92.9 201.2 108.4 96.8 102.7 190.8 55.2 VineHemp Vine 96.1 233.8 107.2 102.6 230.3 98.6 102.0 114.2 141.5 77.3 Cow109.4 2326.4 129.9 122.7 183.9 88.8 122.8 113.2 142.0 25.8 ManureHorse82.9 1635.2 104.0 104.2 140.1 100.9 107.5 114.4 125.0 5.0 ManureHardwood 11.5 5663.4 9.9 20.1 22.2 9.8 32.6 9.8 13.6 16.4 Banana102.8 184.6 123.3 117.0 422.9 110.3 112.8 109.1 169.2 69.3 (Peel)Pistachio41.0 4427.9 120.2 213.0 138.7 100.0 252.6 100.0 93.3 42.6 ShellSorghum 108.0 280.1 119.5 103.2 368.0 160.4 97.5 118.9 213.3 11.4 Broccoli 77.1 181.2 82.9 89.1 327.3 106.3 83.5 92.9 140.7 150.0 Cabbage 93.8 349.7 102.9 104.8 168.1 88.6 76.9 90.9 161.1 54.9 Onion 93.5 523.2 102.5 113.5 391.1 162.3 111.7 131.6 226.1 92.6 Gourd79.8 237.5 97.6 93.6 679.9 100.0 87.6 90.9 143.8 77.0 (Rind)Cantaloupe102.6 319.1 107.3 112.7 150.9 135.3 106.0 123.8 166.7 95.0 (Rind)Watermelon 219.1 521.1 116.8 176.7 1086.7 108.0 166.0 19.1 147.8 82.5 Pineapple79.8 401.7 95.9 98.9 643.3 108.0 89.5 97.9 165.2 78.9 (Skin / Leaf)The percentage values were calculated by: (Average NOP Effluent Values / Average Acid Digestion Values) *100%. Values greater than 100% indicate 1) that NOP treatment extracted more nutrients than the acid digestion method, 2) different elements were added to NOP than acid digestion (i.e. KNO2), or 3) error is present.Example 2: NOP Effluent Fertilizers for Lettuce Grow Trial

[0068] This example illustrates (i) the formulation of NOP effluent-derived fertilizers to achieve a target NPK ratio suitable for lettuce production and (ii) the performance of these fertilizers in terms of lettuce biomass yield and mitigation of N, P, and K leaching relative to a conventional fertilizer.2.1 NOP Effluent Fertilizer Preparation

[0069] NOP effluents produced from food waste, spent grains, palm waste, and horse manure were filtered and analyzed by UV-Vis spectroscopy and ICP-OES to determine existing NPK levels. Each effluent was neutralized with NH4OH and supplemented with potassium phosphate salts to obtain liquid fertilizers with an approximate N-P-K ratio of 3-1-2 (on a weight basis).

[0070] The final nutrient compositions of the neutralized NOP fertilizers are reported in Table 7. Total nitrogen concentrations ranged from about 835 ppm to about 899 ppm, with nitrate and ammonium present at roughly comparable molar concentrations, as shown in Table 7. Phosphorus concentrations were about 297 ppm-about 329 ppm, and potassium about 516 ppm-about 575 ppm, yielding N-P-K ratios close to 3-1-2 for all four formulations as shown in Table 7.Table 7: NPK of Neutralized NOP EffluentsFertilizer N ppm[a]NOg" M NH4+M P ppm[b]K ppm[b]N-P-K[c]Food Waste 835.497 0.0319 0.0277 326.170 560.589 3-1.17-2.01 Spent Grains 894.058 0.0291 0.0312 296.673 515.706 3-1.05-1.88 Palm Tree 898.567 0.0329 0.0310 327.971 568.180 3-1.10-1.91 Horse844.196 0.0338 0.0304 329.024 574.692 3-1.10-1.92 Manure[a]Total nitrogen was determined by colorimetric determination of nitrate, nitrite, and ammonium.[b]Total P and K were determined by ICP-OES analysis.[c]NPK ratio was comparison of P and K concentrations to N.

[0071] Dry residues of the fertilizers of example embodiments and of a commercial fertilizer were analyzed by FT-IR, confirming the presence of lignin- and hemicellulose-derived organic functional groups in the NOP fertilizers that are absent in the commercial product, as shown in Figure 1.2.2 Grow Trial Methods

[0072] Cheshire fine sandy loam soil from the Lockwood Farm (Connecticut Agricultural Experiment Station, Hamden, CT) was sieved (<2 mm) and placed into pots (approximately 500 g soil per pot). Lettuce (Lactuca sativa L.) seedlings were transplanted and allowed to acclimate for five days.

[0073] Treatments consisted of four NOP fertilizers (food waste, spent grains, palm waste, horse manure), a commercial fertilizer, and an unfertilized control. For each fertilized treatment, fertilizers were diluted such that 20 mL of solution delivered approximately 25.0 ppm N, 8.3 ppm P, and 16.7 ppm K per pot. This application was repeated once after one week, giving total inputs of about 50 ppm N, 16.7 ppm P, and 33.4 ppm K per pot.

[0074] Plants were grown under controlled conditions until harvest, and shoot biomass was recorded at the end of the growth cycle as shown in Fig. 2.2.3 Lettuce Biomass Yield

[0075] Lettuce shoot biomass was strongly influenced by fertilization as shown in Fig. 2. The commercial fertilizer increased shoot biomass relative to the unfertilized control, and the horse-manure-derived NOP fertilizer produced the highest biomass yield, significantly exceeding (P < 0.05) yields from both the commercial fertilizer and the other NOP fertilizers, as shown in Fig. 1. Biomass yields among the other NOP fertilizers (food waste, palm waste, spent grains) were not significantly different from each other; however, the spent-grain NOP fertilizer did not significantly increase yield relative to the control, as shown in Fig. 2.2.4 Leaching Study and Nutrient Retention

[0076] One week after the second fertilizer application, leaching was initiated by applying 200 mL of water to each pot. Leachates were collected through perforations in the pot bottoms, volumes were recorded, and samples were analyzed for N, P, and K. A five-week weekly leaching protocol includes conducting weekly leaching events were conducted for five weeks.2.4.1 Nitrogen

[0077] Cumulative nitrogen losses during the five-week weekly leaching protocol showed that the commercial fertilizer caused the highest total N leaching, as shown in Fig. 3A. Relative to this, nitro-oxidized or NOP-derived fertilizers from food waste, horse manure, palm waste, and spent grain reduced cumulative N leaching by approximately 39%, 28%, 20%, and 10%, respectively, in that order, as shown in Fig. 3A. The NOP-derived fertilizers differed significantly among themselves in N-leaching mitigation efficiency (P < 0.05).2.4.2 Phosphorus

[0078] Cumulative P losses are presented in Fig. 3B. The unfertilized control had significantly lower P leaching than the commercial fertilizer (P < 0.05). Among the NOP-derived fertilizers, the horse-manure formulation reduced P leaching by about 17.5 % relative to the commercial fertilizer, while the spent-grain, food-waste, and palm-waste formulations reduced P losses by approximately 12%, 7%, and 1.5%, respectively, as shown in Fig. 3B.2.4.3 Potassium

[0079] Cumulative K losses are shown in Fig. 3C. Commercial fertilizer produced significantly higher cumulative K loss than the unfertilized control (P < 0.05). In contrast, all NOP-derived fertilizers, except the palm-waste formulation, significantly mitigated K leaching relative to the commercial fertilizer, as shown in Fig. 3C. Notably, the NOP-derived fertilizers from food waste and horse manure reduced K leaching to levels similar to the unfertilized control, with overall K retention (reduced loss) ranging between about 7% and 32% relative to the commercial fertilizer, as shown in Fig. 3C.2.4.4 Temporal Patterns

[0080] Weekly patterns of N, P, and K concentrations in soil receiving commercial versus NOP-derived fertilizers are depicted in Fig. 4. Commercial fertilizer produced early, sharp peaks in nutrient loss, whereas NOP-derived fertilizers produced more moderate and sustained nutrient release profiles, consistent with enhanced retention and slower release.2.5 Summary of Example 2

[0081] This example shows that NOP effluent-derived fertilizers can be formulated to agronomically relevant NPK ratios as shown in Table 7 and, when applied at modest rates, can sustain or enhance lettuce growth, as shown in Fig. 2, while substantially reducing N, P, and K leaching compared with a conventional soluble fertilizer, as shown in Figs. 3 and 4.Example 3: NOP Effluent Fertilizers for Turf Grass Grow Trial

[0082] This example describes the preparation of industrial-scale NOP effluents, their formulation into turf grass fertilizers with and without cellulose nanofibers (CNF), and the evaluation of these formulations on turf growth, coverage, and tissue elemental composition.3.1 Industrial-Scale NOP Procedure

[0083] Jute fibers were ground and added to a large stainless-steel reactor. Approximately 2000 L of 50% (w / w) HNO3were added at a solvent-to-fiber ratio of 10 mL / g. The mixture wasT1heated to 50°C for 7 h-9 h. Cellulose microfibers (CMFs) were removed by filtration, and the NOP-derived effluent was neutralized to about pH 3 with either solid KOH or 50 % (w / w) NH4OH. This procedure was repeated as necessary to generate twenty-five one-ton totes of NOP-derived effluent. CNFs were prepared by neutralizing CMF with NH4OH followed by high-pressure homogenization (400 bar).3.2 NOP Fertilizer Formulations

[0084] Industrial NOP-derived effluents served as the base for fertilizer formulations.Additives were used to make concentrated 7-0-7 or 24-0-0 solutions, which were subsequently diluted to produce application-ready formulations containing 3% N with either 0% or 3% K2O.

[0085] Fifteen fertilizer formulations were prepared, including twelve NOP-based formulations and three controls (urea-based with or without CNF and a water-only control). The compositions of these formulations in terms of N, P, K, Fe, Mn, CNF content, and pH are summarized in Table 8. Formulations differed in the presence or absence of CNF and in Fe and Mn levels to allow evaluation of structural and micronutrient effects, as shown in Table 8.Table 8: NOP Effluent Fertilizer Formulations for Turf Grass Grow Trial Fertilizer Fe, Mn, CNF,Formulation N, % P, % K, % % % % pH1[a]3.0 0.0 0.0 0.0 0.0 0.0 5.82[a]3.0 0.0 0.0 0.0 0.0 0.5 5.83[a]3.0 0.0 0.0 0.1 0.2 0.0 5.54[a]3.0 0.0 0.0 0.1 0.2 0.5 5.35[a]3.0 0.0 0.0 0.5 1.0 0.0 5.06[a]3.0 0.0 0.0 0.5 1.0 0.5 5.07[b]3.0 0.0 3.0 0.0 0.0 0.0 6.18[b]3.0 0.0 3.0 0.0 0.0 0.5 6.09[b]3.0 0.0 3.0 0.3 0.6 0.0 6.210[b]3.0 0.0 3.0 0.3 0.6 0.5 6.111[b]3.0 0.0 3.0 0.2 0.3 0.0 5.712[b]3.0 0.0 3.0 0.2 0.3 0.5 5.713[c]3.0 0.0 0.0 0.0 0.0 0.0 7.914[c]3.0 0.0 0.0 0.0 0.0 0.5 7.015[d]0.0 0.0 0.0 0.0 0.0 0.0 7.0CNF was prepared by neutralization of CMF with NH4OH and high-pressure homogenization at 400 bar.[a]NOP-derived effluent was neutralized with NH4OH, and the NPK ratio was adjusted to 24-0-0 by addition of urea, prior to dilution to an NPK ratio of 3-0-0.[b]NOP-derived effluent was neutralized with KOH and NH4OH, and the NPK ratio was adjusted to 7-0-7, prior to dilution to an NPK ratio of 3-0-0.[c]Commercially sourced urea was source of nitrogen.[d]Water only.3.3 Turf Grass Grow Trial Methods

[0086] Commercial turf grass seedlings were established in 1 ft x 1 ft soil trays. After two weeks of growth, fertilizers were applied with a backpack sprayer at a rate equivalent to 1 lb N per 1000 ft2. Trays were maintained in an indoor growth tent at approximately 21°C, 60% relative humidity, with 18 h of artificial light per day, and irrigated daily as needed.

[0087] Turf height and ground coverage were monitored by imaging each tray every 2-3 days. At days 1, 6, 10, and 15, turf was trimmed and allowed to regrow. After two weeks, clippings were collected, dried at 70°C for 3 days, acid-digested, and analyzed by ICP-OES.3.4 Turf Growth and Coverage

[0088] Average turf height over time for each formulation is presented in Table 9. Across the trial, certain NOP formulations, particularly formulations 1, 3, 9, and 10, produced among the tallest turf stands at multiple time points, as shown in Table 9.Table 9: Average turf grass height over time after repeated trimming of leaves Average GrassHeight, inchesFertilizer Day Day Day Day Day Day Day Day Day Day Formulation 1 3 6 8 10 13 15 17 20 271 4.2 2.7 3.4 2.7 3.8 2.8 2.9 2.4 3.0 3.3 2 4.1 2.5 3.3 2.7 3.4 3.0 2.9 2.7 3.2 3.1 3 3.7 2.5 3.8 2.6 2.9 2.9 2.8 2.8 3.1 3.6 4 3.4 2.9 3.1 2.8 3.0 3.1 2.8 3.0 2.8 3.3 5 4.1 2.6 3.3 2.7 2.7 3.1 3.2 2.7 2.9 3.7 6 3.8 2.3 3.1 2.9 3.2 2.5 3.1 2.7 2.9 3.6 7 3.7 2.5 3.5 2.5 3.4 3.3 2.7 2.7 3.3 3.8 8 3.8 2.2 3.2 3.1 3.9 2.8 3.4 2.4 3.2 3.9 9 3.8 2.5 4.2 2.9 3.6 3.0 3.4 2.8 3.4 4.0 10 4.4 2.4 3.6 2.8 3.4 2.7 3.3 2.7 2.9 3.9 11 3.9 2.6 3.8 3.1 3.1 3.0 2.8 2.9 2.8 3.712 3.5 2.8 3.3 2.9 3.3 3.1 3.0 2.8 3.4 3.4 13 4.3 2.4 3.5 2.9 3.2 2.9 3.1 2.6 3.0 3.1 14 4.2 2.2 2.8 3.0 2.8 3.1 3.1 2.7 3.4 2.9 15 4.6 2.1 2.8 2.7 2.7 2.7 3.1 2.5 2.4 3.4Values indicated are averages of 3 replicate grow trials per formulation. Day 1 represents 24 h after initial fertilizer was added to turf grass. At days 1, 6, 10, and 15, the grass was cut and allowed to continue growing.

[0089] Height increments between trimming intervals (growth gains) are summarized in Table 10. The data show that several NOP formulations supported robust regrowth after cutting, with growth increments comparable to or greater than those achieved with urea-based controls, as shown in Table 10.Table 10: Average turf grass height change at different trimming intervals Fertilizer Growth Growth Growth Formulation 1 2 31 0.8 1.1 3.32 0.8 0.7 0.33 1.3 0.3 0.84 0.2 0.2 0.45 0.7 0.0 1.06 0.9 0.3 0.87 1.0 0.9 1.18 1.0 0.8 1.49 1.8 0.7 1.210 1.3 0.6 1.211 1.2 0.0 0.712 0.6 0.4 0.613 1.1 0.3 0.514 0.6 -0.1 0.215 0.6 0.0 0.9Values indicated are averages of 3 replicate grow trials per formulation. Growth values, in inches, were calculated by subtracting the initial average cut height from the average grass height after desired time.

[0090] Ground coverage, quantified via image analysis, is shown in Table 11. Formulations containing 0.5% CNF generally increased percent coverage relative to their CNF-freecounterparts, with some CNF-containing formulations achieving coverages greater than 60% by the end of the trial, compared with about 31% coverage in the water-only control, as shown in Table 11.

[0091] Formulations that included Fe and Mn produced turf with darker green coloration than formulations lacking these micronutrients, consistent with improved chlorophyll status.Table 11: Average coverage by grass growth over timeFertilizer Day Day Day Day Day DayFormulation 1 3 6 8 10 131 39.9 41.7 36.9 46.2 48.8 48.32 43.8 43.1 39.7 51.4 60.1 57.43 29.6 25.4 26.8 38.8 42.1 42.44 34.0 36.9 34.8 44.5 49.4 43.75 41.2 44.7 44.7 51.0 60.4 57.26 45.3 49.1 50.5 58.3 63.4 64.47 40.6 44.6 43.9 52.0 59.5 62.18 39.7 43.2 47.6 56.3 64.1 61.29 41.8 45.4 48.0 53.0 59.1 64.010 40.7 40.5 41.4 48.9 56.7 57.611 39.6 42.4 44.3 52.7 55.5 58.612 45.0 46.3 45.2 56.6 62.0 61.113 37.5 37.6 38.7 49.0 54.5 52.314 29.6 25.5 24.6 38.8 42.2 44.115 28.3 22.8 20.6 27.0 29.2 31.0Values indicated are averages of 3 replicate grow trials per formulation. Images of turf grass were taken and Chat-GPT was used to analyze the space of the soil plot occupied by grass grown.3.5 Elemental Composition of Turf Grass

[0092] Elemental compositions of grass leaves harvested at the end of the trial are reported in Table 12. Concentrations (mg / g dry weight) of P, S, Zn, Fe, Mn, Mg, Ca, Na, and K were generally similar across treatments, indicating adequate nutrition and absence of toxicity. Formulations 3-6, which contained higher Fe and Mn levels, produced the highest Fe and Mn concentrations in leaf tissue, as shown in Table 12, consistent with their formulation design.Table 12: Elemental analysis of turf grass leaves after grow trialFertilizerFormulation P S Zn Fe Mn Mg Ca Na K1 3.963 3.545 0.095 0.265 0.038 3.877 0.621 0.575 44.912 2 4.150 3.619 0.051 0.228 0.072 3.328 0.577 0.463 41.232 3 4.396 3.792 0.533 1.907 0.079 3.364 0.550 0.624 42.438 4 4.042 3.621 0.069 0.263 0.053 2.995 0.454 0.385 42.206 5 4.687 4.074 0.042 0.297 0.125 3.258 0.528 0.381 41.048 6 4.245 3.428 0.042 0.413 0.103 3.185 0.522 0.563 39.393 7 4.281 3.883 0.048 0.114 0.046 3.401 0.453 0.501 40.550 8 4.238 5.001 0.050 0.128 0.048 3.592 0.491 0.345 42.190 9 4.686 4.621 0.047 0.150 0.055 3.323 0.490 0.326 44.553 10 4.772 4.423 0.047 0.125 0.067 3.424 0.481 0.558 44.813 11 4.716 5.912 0.058 0.130 0.077 3.522 0.452 0.366 46.109 12 4.394 3.460 0.045 0.133 0.070 3.155 0.451 0.504 41.147 13 5.246 4.732 0.058 0.125 0.054 3.663 0.530 0.403 42.842 14 3.948 3.982 0.043 0.105 0.043 3.030 0.442 0.410 40.234 15 3.695 2.201 0.038 0.143 0.035 3.575 0.646 0.580 37.680 Values indicated are averages of 3-5 replicates of acid digested grass leaves. Element concentrations were determined by ICP-OES analysis. Total element concentrations in mg per g of biomass.Large Scale Fertilizer Preparation

[0093] NOP-derived fertilizers were prepared from 25 tons of NOP-derived effluent, produced by the NOP of jute fibers, as shown in Table 13. After filtration, the pH of the effluent is approximately -1. Water soluble fertilizers can be made at large scale by the addition of a variety of bases to the nitric acid effluent. By addition of only KOH and water, soluble liquid fertilizers of NPK weight percents of 7:0:7 were produced, with pH 5-7. For NPK fertilizers where the concentration of K < N, NH4OH, NH4SO4, or urea can be added to increase the N value to as high as 32 w / w%. For the 25 tons of NOP-derived effluent, half was neutralized first with solid KOH, and the other half was neutralized with 50 w / w% NH4OH, until a pH of 3 was achieved. The NPK values of the NH4OH neutralized samples were on average, 17:0:0. To increase the nitrogen content, additional NH4OH was added to increase the pH to 5, then urea was added to a desired N concentration. The most common fertilizer produced had an NPK value of 24:0:0, which utilized urea and NH4OH. After neutralization, fertilizers with NPK valuesof 13:0:0, 7:0:0, and 3:0:0 were produced by dilution with water. Additionally, other fertilizer additives are compatible with the 24:0:0 or 7:0:7 NOP-derived fertilizers, such as Fe(SO4) and Mn(SO4), at concentrations less than 0.5 w / w% respectively. CNF from the large scale jute NOP can be added at concentrations of 0.1 w / w%-2.0 w / w%, via high pressure homogenization at 400 bar-600 bar.Table 13: Elemental analysis of industrial scale jute NOP effluentsTotal N, N%from N% from Total P2O5, Total K2O,Effluents wt% Nitrate Ammonium wt% wt% NPK pH1 17.038 8.214 8.824 0.00443 0.0436 17 - 0 - 0 3.15 2 17.13 7.721 9.409 0.0042 0.0028 17.1 -0 - 0 2.93 3 17.488 8.053 9.435 0.00442 0.041 17.5 -0 - 0 3.3 4 17.667 8.02 9.647 0.00465 0.0423 17.7 -0 - 0 3.27 5 14.53 7.123 7.407 0.00418 0.0022 14.5 -0 - 0 3.16 6 15.613 7.792 7.822 0.00422 0.0077 15.6 -0 - 0 3.17 7 19.206 8.912 10.294 0.00451 0.0046 19.2 -0 - 0 3.09 8 14.181 7.665 6.516 0.00455 0.0046 14.2 -0 - 0 3.24 9 14.866 7.616 7.25 0.00432 0.0434 14.9 -0 - 0 3.25 10 15.974 9.816 6.157 0.00475 0.0032 16 - 0 - 0 3.18 11 16.289 7.825 8.464 0.00427 0.047 16.3 -0 - 0 2.67 12 14.911 6.649 8.262 0.00452 0.049 14.9 -0 - 0 3.37 All effluents above were filtered to remove cellulose and neutralized with 50 w / w% NH4OH until pH ~3. The total N values were determined by ion colorimetry methods described above. The total P and K values were determined by ICP-OES. pH was determined by a pH meter.3.6 Summary of Example 3

[0094] This example shows that industrial-scale NOP effluents can be formulated into flexible turf fertilizers, as shown in Table 8, that support strong turf growth, as shown in Tables 9 and 10, enhance ground coverage particularly when CNF is included, as shown in Table 11, and supply micronutrients such as Fe and Mn effectively to turf grass, as shown in Table 12, while performing at least as well as, and in some respects better than, conventional urea-based fertilizers.

[0095] It should be understood that the foregoing description is only illustrative of the present invention. Various alternatives and modifications can be devised by those skilled in theart without departing from the present invention. Accordingly, the present invention is intended to embrace all such alternatives, modifications, and variances that fall within the scope of the appended claims.

Claims

WHAT IS CLAIMED IS:

1. A liquid fertilizer composition comprising:an aqueous phase;dispersed cellulosic fibers including carboxylated cellulose microfibers and / or carboxylated cellulose nanofibers;dissolved nitrogen;dissolved phosphorus;dissolved potassium;an oxidized organic carbon compound; anda nitro-oxidized effluent.

2. The liquid fertilizer composition of claim 1, wherein the dispersed cellulosic fibers include nitro-oxidized cellulosic fibers.

3. The liquid fertilizer composition of claim 1 or 2, wherein the carboxylated cellulose nanofibers have a diameter in a range of about 5 nm–about 500 nm and a carboxyl content of at least about 0.1 mmol / g.

4. The liquid fertilizer composition of one of claims 1-3, wherein the nitro-oxidized effluent includes at least about 30 wt% to about 40 wt% of a total of the dissolved nitrogen, at least about 10 wt% of a total of the dissolved phosphorus, and at least about 10 wt% of a total of the dissolved potassium.

5. The liquid fertilizer composition of one of claims 1-4, whereinthe nitro-oxidized effluent is obtained by nitro-oxidation of an organic waste feedstock with nitric acid; andthe organic waste feedstock is selected from the group including food waste, brewery spent grain, distillery spent grain, coffee grounds, animal manures, agricultural residues, cropvines, fruit rinds and / or peels, vegetable rinds and / or peels, palm residues, sugarcane bagasse, hardwood residues, softwood residues, aquatic biomass, or a combination thereof.

6. The liquid fertilizer composition of one of claims 1-5, wherein the liquid fertilizer composition has an N:P:K ratio by weight in a range of about 1:0.1:0.5 to about 10:5:10.

7. The liquid fertilizer composition of one of claims 1-6, wherein the liquid fertilizer composition has an N:P:K ratio of about 3:1:2, about 3:0:3, about 24:0:0, about 13:0:0, about 7:0:7, about 17:0:0, about 3:0:0, or about 7:0:0.

8. The liquid fertilizer composition of one of claims 1-6, wherein the liquid fertilizer composition has an N: K ratio of about 3:3 and contains substantially no phosphorus other than phosphorus included in the nitro-oxidized effluent.

9. The liquid fertilizer composition of one of claims 1-8, wherein a total nitrogen concentration is from about 0.01 wt%-about 10 wt%, and a total potassium concentration is from about 0.01 wt%-about 15 wt%.

10. The liquid fertilizer composition of one of claims 1-9, wherein the dispersed cellulosic fibers are present at a concentration of about 0.01 wt%-about 5 wt% of the liquid fertilizer composition.

11. The liquid fertilizer composition of one of claims 1-10, wherein the oxidized organic carbon compounds include one or more of a low molecular weight carboxylic acid, a polycarboxylate, a humic-like substance, a lignin-derived aromatic, and a hemicellulose-derived oligosaccharide.

12. The liquid fertilizer composition of one of claims 1-11, further comprising one or more selected from the group including calcium, magnesium, sulfur, iron, manganese, zinc, copper, boron, molybdenum, chlorine, and a combination thereof.

13. The liquid fertilizer composition of one of claims 1-12, further comprising iron and / or manganese in amounts effective to enhance leaf greenness of turf grass relative to an identical liquid fertilizer composition without iron and / or manganese.

14. The liquid fertilizer composition of one of claims 1-13, wherein the carboxylated cellulose nanofibers are present in the liquid fertilizer composition at a concentration of about 0.01 wt% to about 1 wt% of the liquid fertilizer composition.

15. The liquid fertilizer composition of one of claims 1-14, wherein the liquid fertilizer composition is substantially free of heavy metals selected from the group including arsenic, cadmium, lead, mercury, and a combination thereof.

16. The liquid fertilizer composition of one of claims 1-15, wherein, when the liquid fertilizer composition is applied to soil at a given nitrogen application rate and evaluated using a five-week weekly leaching protocol, the cumulative nitrogen leaching loss from the soil is at least about 10% lower than a cumulative nitrogen leaching loss obtained with a reference fertilizer consisting essentially of water-soluble urea applied at the given nitrogen application rate and evaluated using the five-week weekly leaching protocol.

17. The liquid fertilizer composition of one of claims 1-16, wherein the liquid fertilizer composition is a pumpable liquid with a total solids content in range of about 0.1 wt%-about 20 wt%.

18. The liquid fertilizer composition of one of claims 1-17, wherein the liquid fertilizer composition is free of synthetic polymeric slow-release coatings.

19. The liquid fertilizer composition of one of claims 1-18, wherein the dissolved nitrogen includes proteins, organic nitrogen-containing compounds, nitrate, ammonium, or a mixture thereof.

20. The liquid fertilizer composition of one of claims 1-19, wherein the dissolved phosphorus includes ortho-phosphate, phosphate esters, phosphonates, or a mixture thereof.

21. The liquid fertilizer composition of one of claims 1-20, wherein the oxidized organic carbon compounds includes hemi-cellulose, lignin, acid hydrolyzed derivative of hemi-cellulose, acid hydrolyzed derivative of lignin, or a mixture thereof.

22. The liquid fertilizer composition of one of claims 1-21, wherein the nitro-oxidized effluent includes at least a portion of each of the dispersed cellulosic fibers, the dissolved nitrogen, the dissolved phosphorus, the dissolved potassium, and the oxidized organic carbon compounds.

23. A method of fertilizing plants comprising applying to soil or a growth medium with an agriculturally effective amount of the liquid fertilizer composition of one of claims 1–22.

24. The method of claim 23, wherein the plants include a leafy vegetable crop.

25. The method of claim 24, wherein the leafy vegetable crop is lettuce.

26. The method of claim 23, wherein the plants include turf grass.

27. The method of one of claims 23-26, wherein the liquid fertilizer composition is applied by at least one of soil drench, fertigation, in-furrow application, side-dressing, or surface spraying.

28. The method of one of claims 23-27, wherein the liquid fertilizer composition is applied at a rate corresponding to about 10 kg of nitrogen per hectare-about 400 kg of nitrogen per hectare.

29. The method of one of claims 23-28, wherein, when the liquid fertilizer composition is applied to soil at a given nitrogen application rate and evaluated using a five-week weekly leaching protocol, a cumulative nitrogen leaching loss from the soil is at least about 10% lower than a cumulative nitrogen leaching loss obtained with a reference fertilizer consisting essentially of water-soluble urea applied at the given nitrogen application rate and evaluated using the five-week weekly leaching protocol.

30. The method of one of claims 23-28, wherein, when the liquid fertilizer composition is applied to soil at a given phosphorus application rate and evaluated using a five-week weekly leaching protocol, a cumulative phosphorus leaching loss from the soil is at least about 5% lower than a cumulative phosphorus leaching loss obtained with a reference fertilizer consisting essentially of water-soluble urea applied at the given phosphorus application rate and evaluated using the five-week weekly leaching protocol.

31. The method of one of claims 23-28, wherein, when the liquid fertilizer composition is applied to soil at a given potassium application rate and evaluated using a five-week weekly leaching protocol, a cumulative potassium leaching loss from the soil is at least about 5% lower than a cumulative potassium leaching loss obtained with a reference fertilizer consisting essentially of water-soluble urea applied at the given potassium application rate and evaluated using the five-week weekly leaching protocol.

32. The method of one of claims 23-31, wherein the liquid fertilizer composition is a turf fertilizer composition including iron and / or manganese and is applied to turf grass to improve turf coloration and coverage.

33. The method of claim 32, wherein the turf fertilizer composition further includes carboxylated cellulose nanofibers and provides improved turf coverage relative to an identical composition without carboxylated cellulose nanofibers.

34. A method of improving nutrient use efficiency in soil comprising applying to the soil the liquid fertilizer composition of one of claims 1–22 such that:(i) plant-available nitrogen in the soil is maintained at levels sufficient for plant growth; and(ii) at least one of nitrogen, phosphorus, or potassium leaching losses from the soil is reduced relative to an equivalent application of a reference fertilizer consisting essentially of water-soluble urea.

35. A method of producing a liquid fertilizer composition, the method comprising: (a) providing an organic waste feedstock;(b) contacting the organic waste feedstock with an aqueous nitric acid solution under conditions sufficient to nitro-oxidize the organic waste feedstock and to produce a reaction mixture including an acidic aqueous phase and a suspended cellulosic-solid phase;(c) separating at least a portion of the suspended cellulosic-solid phase from the reaction mixture to obtain a nitro-oxidized effluent and isolated cellulose nanofibers;(d) neutralizing the nitro-oxidized effluent with a base to obtain a neutralized effluent; and(e) formulating the neutralized effluent into the liquid fertilizer composition.

36. The method of claim 35, wherein the step (b) is carried out with nitric acid at a concentration in the range of about 1 wt% to about 70 wt%, at a temperature of about 10°C-about 120°C, and for a time of about 0.25 hours-about 24 hours.

37. The method of claim 35 or 36, wherein the step (b) includes contacting the organic waste feedstock with a nitrite salt.

38. The method of one of claims 35–37, wherein the nitrite salt in step (b) includes potassium nitrite.

39. The method of one of claims 35–38, wherein the base in step (d) is selected from the group including an ammonium hydroxide, a potassium hydroxide, a sodium hydroxide, a calcium hydroxide, and a combination thereof.

40. The method of one of claims 35–39, wherein the neutralized effluent is adjusted to a pH in the range of about 5.0–about 8.5.

41. The method of one of claims 35–40, further comprising, after step (d), adding one or more nutrient salts selected from the group including a nitrogen salt, a phosphorus salt, a potassium salt, a secondary salt, and a micronutrient salt.

42. The method of one of claims 35–41, further comprising dispersing the isolated cellulose nanofibers into the neutralized effluent prior to or during step (e).

43. The method of one of claims 35–42, wherein all or substantially all of the neutralized effluent is formulated into the liquid fertilizer composition without discharge of a separate liquid waste stream.

44. The method of one of claims 35–43, wherein the organic waste feedstock includes at least one of food waste, brewery spent grain, palm waste, or horse manure.

45. The method of one of claims 35–44, further comprising concentrating or diluting the neutralized effluent to obtain a total nitrogen concentration suitable for direct agricultural application.

46. The method of one of claims 35–45, wherein the liquid fertilizer composition has an N:P:K ratio of about 3:1:2, about 3:0:3, about 24:0:0, about 13:0:0, about 7:0:7, about 17:0:0, about 3:0:0, or about 7:0:0.

47. A method of upcycling organic waste comprising converting the organic waste feedstock into the liquid fertilizer composition of one of claims 1–22 by the method of one of claims 35–46 and then applying the liquid fertilizer composition to soil, a growth medium, or turf grass.

Images