Methods and compositions using NOP-derived cellulosic fibers as multifunctional adjuvants for broad spray coverage, drift control, and soil water-holding amendments

Abstract

A pesticidal composition includes a pesticidal active ingredient, nitro-oxidized cellulose fibers, and water. The nitro-oxidized cellulose fibers have a carboxylate content between about 0.8 mmol / g and about 3.0 mmol / g, and the pesticidal composition can be deployed through an agricultural spray nozzle under typical operating conditions.

Description

Attorney Docket No. 201291.12. PCTMETHODS AND COMPOSITIONS USING NOP-DERIVED CELLULOSIC FIBERS AS MULTIFUNCTIONAL ADJUVANTS FOR BROAD SPRAY COVERAGE, DRIFT CONTROL, AND SOIL WATER-HOLDING AMENDMENTSCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Patent Application No. 63 / 722,188 filed on November 19, 2024. The entire contents of this application are hereby incorporated by reference.BACKGROUND OF THE INVENTION1. Field of the Invention

[0002] The present invention relate to the use of nitro-oxidation process (NOP)-derived cellulosic fibers, including nitro-oxidized cellulose nanofibers (CNF) and / or nitro-oxidized cellulose microfibers (CMF) and derivatives thereof, as adjuvants, surfactants, soil and substrate amendments, drift control agents, and foliar surfactants.2. Description of the Related Art

[0003] Modern agricultural and industrial formulations rely heavily on synthetic chemicals and polymers, such as petroleum-derived adjuvants, surfactants, drift control agents, and water holding additives to improve delivery and efficacy of agricultural products. However, these products can contribute to environmental pollution, regulatory challenges, and microplastic contamination. Additionally, organic solvents used in surfactant applications pose significant hazards due to toxicity and cost. This is particularly relevant for widely used systemic herbicides such as glyphosate, where synthetic adjuvants are often used to modify droplet formation and spreading, which can increase the proportion of fine droplets and, if not properly controlled, reduce on-target delivery and raise off-target and regulatory concerns.SUMMARY OF THE INVENTION

[0004] To overcome the problems described above associated with synthetic chemical and polymer products for agricultural and industrial applications, example embodiments of the present invention provide NOP-produced carboxylated cellulosic fibers from lignocellulosic biomass that offer a sustainable, renewable, biodegradable, and environmentally friendlysolution. Functionalized via an NOP treatment, the resulting carboxylated cellulose fibers retain the cellulose backbone but possess additional properties including, for example, one or more of:1) tunable particle size and fiber aspect ratio,2) abundant functional groups on the fiber surface for customizable surface modification,3) highly hydrophilic surfaces that can provide to excellent water retention, interfacial compatibilization, and adhesive ability.

[0005] The overall features of NOP-derived carboxylated cellulose fibers yield superior performance in when used as fertilizers, pesticides, foliar sprays, and industrial coatings, where the utilization of these materials also reducing environmental impact. For example, in glyphosate formulations, carboxylated nitro-oxidized cellulose nanofibers (NOCNF) can act as multifunctional adjuvants that simultaneously modify spray droplet size distribution and reduce the drift tendency due to the enhance viscosity of NOCNF-containing suspension. The inclusion of NOCNFs can also enhance the foliar coverage and the adhesion between leaves and glyphosate, improving biological efficacy. In addition, carboxylated nitro-oxidized cellulose microfibers (NOCMF) and NOCNF-based materials can be produced in the form of hydrogel (e.g., Biogel), wet sponge structure (e.g., Hydrosponge), and aerated sponge structure (e.g., Aerosponge), which can be incorporated into growing substrates, including organic substrates such as coco coir, wood fiber, chips, sawdust, bark and rice hulls, as well as inorganic substrates such as perlite, vermiculite, rockwool, expanded clay pebbles, pumice and sand, to enhance water-holding capacity (WHC) by reducing evaporation and drainage rate and extend the irrigation intervals.

[0006] Example embodiments of the present invention provide materials and compositions based on a nitro-oxidization process (NOP) produced carboxylated cellulosic fibers at both micro- and nano-scale, as well as the derived products (in the form of gels and sponges) that can be used as adjuvants, surfactants, drift control agents, and soil amendments for varying agricultural and industrial applications. Example embodiments of the present invention provide carboxylated cellulose fibers, produced by a nitro-oxidation process (NOP), that can be used asmultifunctional, renewable adjuvants and soil amendments for diverse agricultural applications. In certain example embodiments, pesticidal compositions include at least one pesticidal active, such as glyphosate, and nitro-oxidized cellulose nanofibers (NOCNFs) and / or microfibers (NOCMF). In these formulations, NOCNFs impart shear-thinning behavior by forming an entangled fiber network that modifies spray breakup and provide a controlled, predominantly coarse droplet size distribution with a defined fraction of productive fine droplets (<50 pm), very low ultrafine fractions (<10 pm), and stable, repeatable spray performance, thereby improving foliar coverage and reducing off-target drift without reliance on conventional synthetic drift-control polymers. In other example embodiments, NOCNF / NOCMF-based hydrogels and sponges, including, for example, Biogels, Hydrosponge, and Aerosponge, are incorporated into agricultural substrates such as coco coir at loadings of about 0.1 wt%-about 5 wt%. These carboxylated cellulose fibers derived products form highly porous, water-retentive networks that increase water-holding capacity (WHC) by about 6%-about 20%, and about 18%- about 19% for optimized formulations, slowing evaporation and drainage and extending irrigation intervals. The example embodiments include methods of manufacturing and using the compositions of example embodiments of the present invention for improving drift control, foliar deposition, and moisture management using biodegradable, NOP-derived cellulosic fibers.

[0007] In certain example embodiments, the NOP-derived cellulosic fibers, including CNF, CMF, and CNF / CMF derivatives (e.g., hydrogel (such as a Biogel) and sponge structures (such as a Hydrosponge and a Aerosponge), are used as water-holding amendments in agricultural substrates and soil (e.g., coco coir), or as multifunctional adjuvants in glyphosate and other pesticidal formulations to provide drift control and enhanced foliar coverage. Additionally, the example embodiments of the present invention encompass industrial applications such as antifouling coatings, oil spill remediation materials, and industrial dispersants, leveraging these NOP-derived cellulosic fibers' unique physical and chemical properties. NOP-derived cellulosic fibers can be produced from any renewable lignocellulosic biomass sources, and the fibers of the example embodiments of the present invention provide a sustainable and high- performance alternative to synthetic polymeric products.

[0008] The nitro-oxidized cellulose fibers used in pesticidal compositions of example embodiments and the NOP-derived cellulosic additives used in the agricultural substrate compositions of example embodiments can be jointly effective to: (i) reduce spray drift and improve foliar coverage and retention of pesticidal active ingredients; and (ii) increase waterholding capacity of the substrate and extend irrigation intervals, thereby improving overall input efficiency and stress resilience in agricultural or agricultural production systems of example embodiments of the present invention.

[0009] The reduced water loss of the substrate of example embodiments enables longer intervals between irrigations, reduced total water consumption, more stable root-zone moisture conditions, and increased resilience of plants to missed irrigations, equipment malfunctions, labor shortages, or high-heat events.

[0010] According to an example embodiment of the present invention, a pesticidal composition includes a pesticidal active ingredient, nitro-oxidized cellulose fibers, and water. The nitro-oxidized cellulose fibers have a carboxylate content between about 0.5 mmol / g and about 3.0 mmol / g, and the pesticidal composition can be deployed through an agricultural spray nozzle under typical operating conditions.

[0011] The nitro-oxidized cellulose fibers can include nitro-oxidized cellulose nanofibers (NOCNFs) and / or nitro-oxidized cellulose microfibers (NOCMFs). The pesticidal composition can be deployed through a spray nozzle at a pressure of about 15 psi-about 60 psi, a flow rate of about 0.2 L / min-about 1.5 L / min per nozzle, and a nozzle-to-target distance of about 20 cm- about 60 cm. A spray droplet size distribution of the pesticidal composition satisfies at least one of the following conditions a volume median droplet diameter (Dv50) is between about 80 pm and about 200 pm; a percent spray volume of droplets smaller than 50 pm is less than about 25%; and a percent spray volume of droplets smaller than 10 pm is less than about 1%. The percent spray volume of droplets smaller than 50 pm can be between about 10% and about 20%. The percent spray volume of droplets smaller than 10 pm can be less than about 0.5%.

[0012] The pesticidal active ingredient can be a glyphosate active ingredient selected from glyphosate acid, agriculturally acceptable salts thereof, and a mixture thereof. The glyphosate active ingredient can be present in a range from about 0.8 wt%-about 20.0 wt% (acidequivalent) in the pesticidal composition. The pesticidal active ingredient can include isopropylamine, mono-ammonium, di-ammonium, potassium, sodium, dimethylammonium, trimesium salt, or a combination thereof.

[0013] The nitro-oxidized cellulose fibers can have diameters between about 3 nm and about 10 nm and lengths between about 0.2 pm and about 1 pm. The nitro-oxidized cellulose fibers can be present in an amount from about 0.01 wt% to about 5 wt% based on a total weight of the pesticidal composition. The nitro-oxidized cellulose fibers can be present in an amount from about 0.05 wt% to about 2 wt% based on a total weight of the pesticidal composition.

[0014] A viscosity of the pesticidal composition at a shear rate of about 0.1 s-1can be at least about 103times greater than the viscosity of the pesticidal composition at a shear rate of about 1000 s“1. A viscosity of the pesticidal composition at a shear rate of about 0.1 s“1can be at least about 104times greater than the viscosity of the pesticidal composition at a shear rate of about 1000 s-1.

[0015] The pesticidal composition can exhibits a volume-weighted mean diameter D[4,3] between about 130 pm and about 170 pm and / or a spray-to-spray coefficient of variation (Cv) in D[4,3] of about 60 ppm or less. The pesticidal composition can exhibit a spray-to-spray coefficient of variation (Cv) in D[4,3] of about 50 ppm or less. The pesticidal composition can include about 0.2 wt% NOCNF and about 0.16 wt% glyphosate, and spray droplet size parameters averaged over three independent spray events can be: DvlO is about 40.28 pm, Dv50 is about 118.53 pm, Dv90 is about 278.83 pm, D[4,3] is about 141.80 pm, D[3,2] is about 74.48 pm, Cv is about 44.42 ppm, Span is about 2.013, %V < 5 pm is bout 0.2516%, %V < 10 pm is about 0.4616%, and %V < 50 pm is about 15.15%. The pesticidal composition can have a percent volume of droplets smaller than 50 pm of about 15.15% and can have a percent volume of droplets smaller than 10 pm less than about 0.5% of a total spray volume.

[0016] The nitro-oxidized cellulose fibers function as at least one a drift-control agent, a rheology modifier, a spreader or surfactant-like component, and a film-forming agent that generates a microgel network on leaf surfaces.

[0017] According to an example embodiment of the present invention, a method of controlling pests providing the pesticidal composition of another example embodiment and spraying the pesticidal composition through an agricultural spray nozzle onto plant foliage, seeds, soil, or growth media.

[0018] The method can further include a step of diluting the pesticidal composition with water. The pesticidal composition can includes a glyphosate herbicidal formulation, and the nitro-oxidized cellulose fibers can increase droplet surface area and coverage on leaf surfaces while maintaining an ultrafine droplet volume fraction below about 0.5%.

[0019] According to an example embodiment of the present invention, a method of manufacturing a pesticidal composition includes (a) providing an aqueous dispersion of nitrooxidized, carboxylated cellulose fibers having a solids content between about 0.1 wt% and about 10 wt%; (b) mixing the aqueous dispersion with a pesticidal active ingredient under shear conditions sufficient to provide a mixture that is homogeneous and sprayable; and (c) adjusting a pH of the mixture to between about 2 and about 12 to provide a stable pesticidal composition. The stable pesticidal composition includes a homogeneous matrix of the nitrooxidized, carboxylated cellulose fibers and the pesticidal active ingredient, and the stable pesticidal composition exhibits shear-thinning behavior when sprayed.

[0020] The method can further include adding additional formulation components to the stable pesticidal composition and adjusting the stable pesticidal composition to a final volume.

[0021] According to an example embodiment of the present invention, an agricultural substrate composition includes a substrate and a nitro-oxidation-process-derived (NOP- derived) cellulosic additive included in a range of from about 0.1 wt% to about 5.0 wt%. The agricultural substrate composition increases a water-holding capacity by at least about 5% relative to an identical composition but without the NOP-derived cellulosic additive when evaluated by gravimetric water-loss measurements over an 18-day period.

[0022] The substrate can include soil and / or a soilless substrate. The soilless substrate can include an organic substrate selected from coco coir, wood fiber, chips, sawdust, bark, rice hulls, or a mixture thereof and / or can include an inorganic substrate selected from perlite, vermiculite, rockwool, expanded clay pebbles, pumice, sand, or a mixture thereof.

[0023] The NOP-derived cellulosic additive is selected from nitro-oxidized cellulose nanofibers (NOCNF), nitro-oxidized cellulose microfibers (NOCMF), a hydrogel, a wet sponge, an aerated sponge, or a mixture thereof.

[0024] The increase in water-holding capacity can be between about 6% and about 20%. The increase in water-holding capacity can be between about 18% and about 19%. The NOP- derived cellulosic additive can be selected from a hydrogel included in a range from about 0.25 w%-about 1.0 wt%, wet sponge granules included in a range from about 0.25 wt%-about 3.0 wt%, aerated sponge granules included in a range from about 0.25 wt%-about 1.0 wt%, or a combination thereof. The hyrdrogel can be included at about 0.5 wt% and can increase the water-holding capacity by about 18.20%; the wet sponge granules can be included at about 0.25 wt% and can increase the water-holding capacity by about 18.58%; or the aerated sponge granules can be included at about 0.25 wt% and can increase the water-holding capacity by about 18.74%. When evaluated by gravimetric water-loss measurements over an 18-day period using fully hydrated samples weighed at two-day intervals, a composition including about 0.5 wt% biogel can exhibit an average water loss of about 24.2 g per two-day interval; a composition including about 0.25 wt% wet sponge granules can exhibit an average water loss of about 24.0 g per two-day interval; or a composition including about 0.25 wt% aerated sponge granules can exhibit an average water loss of about 24.0 g per two-day interval.

[0025] The NOP-derived cellulosic additive can include a three-dimensional porous network having a total porosity of at least about 70% by volume and can be configured to act as a microreservoir network to slow water drainage and evaporation. The total porosity of the three- dimensional porous network can be at least about 90% by volume.

[0026] According to an example embodiment of the present invention, a method of increasing water-holding capacity of an agricultural substrate (a) providing a substrate, (b) mixing from about 0.1 wt% to about 5.0 wt% of a nitro-oxidation-process-derived (NOP- derived) cellulosic additive with the substrate to provide a mixture, and (c) hydrating the mixture to field capacity to provide an agricultural substrate. The agricultural substrate exhibits reduced average water loss per day and increased water-holding capacity of at least about 5%relative to an identical substrate but without the NOP-derived cellulosic additive as determined by gravimetric mass-loss measurements over about 18 days.

[0027] The substrate can include soil and / or a soilless substrate. The soilless substrate can include an organic substrate selected from coco coir, wood fiber, chips, sawdust, bark, rice hulls, or a mixture thereof and / or can include an inorganic substrate selected from perlite, vermiculite, rockwool, expanded clay pebbles, pumice, sand, or a mixture thereof.

[0028] The NOP-derived cellulosic additive can be selected from nitro-oxidized cellulose nanofibers (NOCNF), nitro-oxidized cellulose microfibers (NOCMF), a hydrogel, a wet sponge, an aerated sponge, or a mixture thereof. The agricultural substrate can exhibit increased waterholding capacity of at least about 10% relative to an identical substrate but without the NOP- derived cellulosic additive as determined by gravimetric mass-loss measurements over about 18 days. The agricultural substrate can exhibit increased water-holding capacity of at least about 15% relative to an identical substrate but without the NOP-derived cellulosic additive as determined by gravimetric mass-loss measurements over about 18 days. The NOP-derived cellulosic additive can be included in a range of about 0.25 wt%-about 0.5 wt%, and the increased water-holding capacity can be in a range from about 18%-about 19%.

[0029] According to an example embodiment of the present invention, an integrated agricultural system includes a pesticidal composition of another example embodiment configured for foliar or soil application and an agricultural substrate composition of another example embodiment configured for growing plants.

[0030] According to an example embodiment of the present invention, a composition comprising nitro-oxidized, carboxylated cellulose fibers, wherein a first portion of the nitro- oxidized, carboxylated cellulose fibers have a first cross-sectional dimension in a range from about 2 nm-about 100 nm, a second portion of the nitro-oxidized, carboxylated cellulose fibers have a second cross-sectional dimension in a range from about 100 nm-about 50 mm, and the composition is an agricultural adjuvant, a surfactant, a drift control agent, or a soil amendment.

[0031] 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

[0032] Fig. 1 shows concentration-dependent viscosity versus shear rate profiles for aqueous suspensions containing glyphosate and CNF-glyphosate mixtures. The results show the shear-thinning behavior of CNF-glyphosate mixtures and the substantially higher low-shear viscosity of these samples, where the glyphosate solution show a typical Newtonian behavior.

[0033] Fig. 2 shows water-sensitive papers sprayed with the CNF-glyphosate mixture suspension under the same conditions used for droplet size measurements. The results show a relatively uniform coverage with predominantly coarse droplets and limited fine misting.

[0034] Fig. 3 shows water-loss test results for the coco coir substrate amended with CNF / CMF-based Biogel (0.5 wt%), Hydrosponge (0.25 wt%), and Aerosponge (0. 25 w%) amendments at selected loadings over 0-19 days, compared to those of the coco coir substrate alone. The results show a reduced cumulative water loss or an increased water-holding capacity of the treated substrates.DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS

[0035] Example embodiments of the present invention include various compositions that can be used, for example, as a pesticide, an agricultural adjuvant, a surfactant, a drift control agent, or a soil amendment. The compositions can include nitro-oxidized, carboxylated cellulose fibers. The compositions can include nitro-oxidized, carboxylated cellulose fibers that are nano-scale and / or micro-scale. Nano-scale fibers have a cross-sectional dimension in a range from about 2 nm-about 100 nm, within manufacturing and / or measurement tolerances, and micro-scale fibers have a cross-sectional dimension in a range from about 100 nm-about 50 mm, within manufacturing and / or measurement tolerances. The compositions can exhibit non-Newtonian behavior and can be deployed through an agricultural spray nozzle under typical operating conditions. For example, the compositions can be sprayed using a nozzle at a pressure of about 15 psi-about 60 psi, a flow rate of about 0.2 L / min-about 1.5 L / min per nozzle, and a nozzle-to-target distance of about 20 cm-about 60 cm, within measurement tolerances. It is possible to apply the compositions using any suitable method, including spraying.

[0036] Example embodiments of the present invention also include agricultural substrate compositions that can be used, for example, to grow plants and / or crops. The agricultural substrate compositions can provide reduced average water loss per day and can provided increased water-holding capacity. The reduced water loss can allow for longer intervals between irrigations, reduced total water consumption, more stable root-zone moisture conditions, and increased resilience of plants to missed irrigations, equipment malfunctions, labor shortages, or high-heat events.

[0037] Example embodiments of the present invention also include integrated agricultural systems that include a pesticidal composition of another example embodiment and an agricultural substrate composition of another example embodiment. For example, the pesticidal composition can be configured for foliar or soil application, and the agricultural substrate composition can be configured for growing plants and / or crops.

[0038] "Pesticidal active ingredient" or "pesticidal active" can refer to any chemical or biological agent that exerts a controlling or killing effect on a target pest, including herbicides, fungicides, insecticides, acaricides, nematicides, bactericides, biological control agents, and mixtures thereof. As used herein, "glyphosate" refers to N-(phosphonomethyl)glycine and its agriculturally acceptable salts, complexes, and acid equivalents, including but not limited to isopropylamine, potassium, ammonium, dimethylamine, and trimesium salts.

[0039] "Carboxylated cellulose nanofibers" or "carboxylated NOCNF" can refer to NOP produced cellulose fibers in the nanoscale having at least one dimension in the nanometer range, typically with diameters from about 3 nm to about 100 nm and lengths from about 0.1 pm to about 50 pm, within manufacturing and / or measurement tolerances, wherein a portion of the hydroxyl groups of the cellulose backbone are oxidized or otherwise converted to carboxylate groups using one 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, 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 process biomass to make fibers. The NOP treatmentcan convert the hydroxyl groups to carboxylate groups at the C-6 position of the anhydroglucose repeating unit in cellulose chains, while simultaneously removing a portion of lignin and hemicellulose. Alternatively, the fibers can be derived using any other suitable process. The fibers can be derived from renewable, plant-based sources. For example, the carboxylated NOCMFs and / or NOCNFs can be obtained from any cellulose-containing feedstock, including but not limited to wood, agricultural residues, grasses, crop wastes, animal manures, food wastes and other natural organic materials.

[0040] "Drift" can refer to the off-target movement of sprayed droplets away from the intended treatment area, particularly fine droplets that remain suspended in the air and are transported by air currents. "Spray droplet size distribution" can refer to the statistical distribution of droplet diameters produced during spraying, measured using laser diffraction or other established techniques, and characterized by one or more of DvlO, Dv50, Dv90, and the percent volume of droplets below defined size thresholds (e.g., <10 pm, <50 pm, or <90 pm). As used herein, DvlO, Dv50, and Dv90 denote, respectively, the droplet diameters at which 10%, 50%, and 90% of the total spray volume is contained in droplets smaller than the stated value.

[0041] "Foliar coverage" can refer to the extent and uniformity of wetting and deposition of a spray on plant foliage, which may be quantified by droplet counts per unit area, fractional area coverage, or image-based measurements using tracers, dyes, or fluorescent markers.

[0042] "Shear-thinning" can refer to a rheological behavior in which viscosity decreases with increasing shear rate.

[0043] "Biogel" refers to a hydrated, gel-like composition comprising a continuous network of cellulose nano- and / or microfibers produced by NOP (NOCNF and / or NOCMF) dispersed in water. In certain example embodiments, Biogel is a kind of hydrogel containing natural polymeric scaffolds, having a water content greater than about 90 wt%-about 98 wt%, within manufacturing and / or measurement tolerances, and forms a soft, shape-stable structure that can be blended into varying agricultural substrates, including organic substrates such as coco coir, wood fiber, chips, sawdust, bark, and rice hulls, as well as inorganic substrates such as perlite, vermiculite, rockwool, expanded clay pebbles, pumice, and sand, to increase waterholding capacity by providing nano- and micro-capillary water reservoirs.

[0044] "Hydrosponge" refers to a sponge-like, highly porous solid or semi-solid material comprising cellulose nano- and / or microfibers (e.g., CNF and / or CMF) arranged in a three- dimensional network. Hydrosponges can be produced by the ice templating methods as disclosed in PCT Application No. PCT / US2025 / 041872, the entire contents of this application are hereby incorporated by reference. In some example embodiments, Hydrosponge can be a total porosity greater than about 70%-about 80% by volume, optionally greater than about 90% or about 95%, within manufacturing and / or measurement tolerances, and is capable of absorbing and retaining many times its dry weight in water. Hydrosponge may be used in a powder form, a granular form (which can be referred to as "Hydrosponge Ground"), or a bulk form to provide water-retentive voids and micro-reservoirs when incorporated into an agricultural substrate.

[0045] "Aerosponge" refers to a low-density, aerated or foam-like cellulose nano- and / or microfiber network with very high internal porosity. In certain example embodiments, Aerosponge includes interconnected macro-, micro-, and nano-pores, with total porosity greater than about 70%-about 90% by volume, within manufacturing and / or measurement tolerances, exhibiting rapid water uptake and release characteristics. Aerosponge may be used in a powder form, a granular form (which can be referred to as "Aerosponge Ground"), or a bulk form to increase the water-holding capacity and moisture-distribution uniformity of substrates, such as coco coir.

[0046] The terms Biogel, Hydrosponge, and Aerosponge encompass functionally equivalent CNF- and / or CMF-based hydrogels and sponge materials, regardless of their precise trade name or manufacturing route, that include a cellulose nano- / microfiber network that enhances water retention when added to an agricultural substrate. For example, Biogels can include hydrogels including nitro-oxidized cellulose fibers, Hyrdrosponges can include wet sponges including nitro-oxidized cellulose fibers, and Aerosponges can include aerated sponges including nitrooxidized cellulose fibers. The nitro-oxidized cellulose fibers can include, for example, nitro- oxidized cellulose nanofibers (NOCNFs) and / or nitro-oxidized cellulose microfibers (NOCMFs).

[0047] "Agricultural substrate" can refer to any medium used for growing plants, including but not limited to soil, soil-less substrates (such as organic substrates like coco coir, wood fiber,chips, sawdust, bark and rice hulls, as well as inorganic substrates like perlite, vermiculite, rockwool, expanded clay pebbles, pumice, sand), and mixtures thereof. The term "agricultural substrate" can further encompasses materials used as soil amendments or conditioners when blended into field soil, potting mixes, or other growth media to modify water-holding capacity, structure, aeration, or nutrient-retention properties.

[0048] The oxidized cellulose can be fibrillated mechanically by methods such as high- pressure homogenization, microfluidization, grinding, blending or ultrasonication, to yield carboxylated CNF from carboxylated CMF having to increase the aspect ratio and specific surface area. The nitro-oxidized cellulose fibers can include nitro-oxidized cellulose nanofibers (NOCNFs) and / or nitro-oxidized cellulose microfibers (NOCMFs). In some example embodiments, the carboxylated CNFs have a carboxylate content between about 0.5 mmol / g and about 3.0 mmol / g, including between about 0.8 mmol / g and about 2.0 mmol / g, as measured by potentiometric titration, within manufacturing and / or measurement tolerances. In particular example embodiments, the CNFs include fibrils with diameter between about 3 nm and about 10 nm and lengths between about 0.2 pm and about 1 pm, within manufacturing and / or measurement tolerances.

[0049] The nitro-oxidized cellulose fibers can function as at least one of a drift-control agent, a rheology modifier, a spreader or surfactant-like component, or a film-forming agent that generates a microgel network on leaf surfaces.

[0050] The carboxylated CMFs and / or CNFs can be supplied as an aqueous dispersion having a solids content between about 0.1 wt% and about 10 wt%, within manufacturing and / or measurement tolerances, or as a partially dried and dispersible material. In some example embodiments, the CNFs are maintained in dispersion to avoid hornification and preserve their high surface area, charge, and rheological functionality.

[0051] In addition to carboxylate groups, the CNFs may be further functionalized, for example with additional hydrophilic or ionic groups, to tailor interactions with formulation components (e.g., glyphosate). However, in many example embodiments the NOP-derived carboxylated CNF alone provides adequate performance without further modification.

[0052] The glyphosate component of example compositions can be present as a free acid or, more typically, as an agriculturally acceptable salt. Representative salts include isopropylamine, mono- or di-ammonium, potassium, sodium, dimethylammonium, or mixtures thereof. The terms "glyphosate active" and ""glyphosate active" can include any form that provides glyphosate acid equivalent upon dilution and application.

[0053] The compositions of example embodiment may further include one or more additional formulation ingredients, including but not limited to: additional surfactants (nonionic, anionic, or amphoteric); humectants (e.g., glycerol, glycols, sorbitol); defoamers; preservatives; pH modifiers or buffers; antifoaming agents; and other adjuvants.

[0054] The composition may be formulated as a concentrate (e.g., a soluble concentrate or aqueous salt concentrate) or as a ready-to-use spray solution. In certain example embodiments, the carboxylated CNFs are present in the concentrate and remain stably dispersed over commercially relevant storage periods, without significant sedimentation, gelation, or phase separation.

[0055] When diluted to a spray tank concentration, the composition can generally contains glyphosate actives at levels customary in practice (for example, about 0.1 wt%-about 5 wt%, within manufacturing and / or measurement tolerances) and carboxylated CNF at levels between about 0.01 wt% and about 0.5 wt%, within manufacturing and / or measurement tolerances. At these low loadings, the CNF can significantly modify spray droplet formation and droplet behavior on leaf surfaces without significantly increasing the viscosity to the point of clogging or operational difficulty.

[0056] The inclusion of carboxylated CNF can alter the breakup of the liquid sheet at the spray nozzle and the subsequent evolution of droplets in flight. This behavior can be explained by several possible mechanisms, discussed below.

[0057] Network formation: The CNFs form an entangled network in the CNF-glyphosate suspension, providing a continuous, viscoelastic matrix that resists uncontrolled fragmentation of the droplet.

[0058] Shear-thinning rheology: The CNF dispersion exhibits high viscosity at low shear rate(e.g., in the spray line and on the leaf) and lower viscosity at high shear rate (e.g., at the nozzle), facilitating the pumping and atomization processes while stabilizing the droplet size.

[0059] Surface modification: The high surface area and the weak interfacial activity of CNFs can modify the apparent surface tension and droplet coalescence behavior, impacting the distribution of droplet sizes and their spreading on target surfaces.

[0060] An example embodiment provides a glyphosate herbicidal composition comprising:1) from about 0.01 wt% to about 1 wt%, or from about 0.08 wt% to about 0.2 wt%, within manufacturing and / or measurement tolerances, glyphosate active (on an acid-equivalent basis);2) from about 0.01 wt% to about 5 wt%, or from about 0.05 wt% to about 2 wt%, within manufacturing and / or measurement tolerances, of carboxylated CNF (on a dry weight basis);3) water; and4) optionally additional formulation components.

[0061] In certain example embodiments, when the CNF-glyphosate suspension is sprayed through a nozzle under typical operating conditions, the droplet size distribution satisfies at least one of the following:1) a volume median droplet diameter (Dv50) between about 80 pm and about 200 pm, within manufacturing and / or measurement tolerances;2) a percent spray volume of droplets smaller than 50 pm less than about 25%, including between about 10% and about 20%, within manufacturing and / or measurement tolerances; and3) a percent spray volume of droplets smaller than 10 pm less than about 1%, including less than about 0.5%, within manufacturing and / or measurement tolerances.

[0062] In certain example embodiments, the inclusion of carboxylated CNF in glyphosate or other pesticidal formulations provides improved drift control, foliar coverage, and spray-to-spray consistency, due at least in part to the network formation, shear-thinning rheology, and surface-modification effects described above.

[0063] The carboxylated CNF can function as a multifunctional adjuvant in glyphosate formulations. Depending on concentration and formulation design, the CNFs can act as one or more of the following:1) a drift-control agent, modulating droplet size distribution and reducing off-target movement of fine droplets;2) a spreader and surfactant-like component, reducing effective contact angles;3) a rheology modifier, imparting shear-thinning behavior beneficial for both sprayability and storage stability; and4) a film-forming agent, generating a microgel network on the leaf surface that retains glyphosate during dew, light rain, or irrigation events.

[0064] Compared to conventional adjuvants such as drift -control polymers (e.g., polyacrylamide) or other non-ionic surfactants, the CNFs offer the advantage of biodegradability, biocompatibility and environmental friendliness.

[0065] For example, compositions can be pesticidal compositions that include a pesticidal active ingredient, nitro-oxidized cellulose fibers, and water. The nitro-oxidized cellulose fibers can have a carboxylate content between about 0.8 mmol / g and about 3.0 mmol / g, within manufacturing and / or measurement tolerances. The nitro-oxidized cellulose fibers can be present in an amount from about 0.01 wt% to about 5 wt% or from about 0.05 wt% to about 2 wt% based on a total weight of the pesticidal composition.

[0066] Pests can be controlled by spraying the pesticidal compositions through an agricultural spray nozzle onto, for example, plant foliage, seeds, soil, or growth media. In some applications, the pesticidal compositions can be diluted with water before spraying.

[0067] When the pesticidal compositions are used in spraying applications, the pesticidal compositions can be deployed through an agricultural spray nozzle under typical operating conditions and can exhibit non-Newtonian behavior, i.e., shear-thinning behavior. For example, the viscosity of the pesticidal composition at a shear rate of about 0.1 s-1is at least about 103or about 104times greater than the viscosity of the pesticidal composition at a shear rate of about1000 s’1, within manufacturing and / or measurement tolerances. In addition, the nitro-oxidized cellulose fibers can increase droplet surface area and coverage on, for example, leaf surfaces, while maintaining an ultrafine droplet volume fraction below about 0.5%, within manufacturing and / or measurement tolerances.

[0068] A spray droplet size distribution of the pesticidal composition can satisfy, for example, at least one of the following conditions:1) a volume median droplet diameter (Dv50) can be between about 80 pm and about 200 pm, within manufacturing and / or measurement tolerances;2) a percent spray volume of droplets smaller than 50 pm can be less than about 25% or can between about 10% and about 20%, within manufacturing and / or measurement tolerances; and3) a percent spray volume of droplets smaller than 10 pm can be less than about 1% or can be less than about 0.5%, within manufacturing and / or measurement tolerances.

[0069] The pesticidal composition can exhibit a stable and reproducible coarse droplet distribution. The pesticidal composition can, for example, exhibit:1) a volume-weighted mean diameter D[4,3] between about 130 pm and about 170 pm; and / or2) a spray-to-spray coefficient of variation (Cv) in D[4,3] of about 60 ppm or less or about 50 ppm or less.

[0070] If the pesticidal composition includes, for example, about 0.2 wt% NOCNF and about0.16 wt% glyphosate, within manufacturing and / or measurement tolerances, then spray droplet size parameters averaged over three independent spray events can be: DvlO is about 40.28 pm, Dv50 is about 118.53 pm, Dv90 is about 278.83 pm, D[4,3] is about 141.80 pm, D[3,2] is about 74.48 pm, Cv is about 44.42 ppm, Span is about 2.013, %V < 5 pm is about 0.2516%, %V < 10 pm is about 0.4616%, and %V < 50 pm is about 15.15%, within manufacturing and / or measurement tolerances. Other spray droplet size parameters are also possible.

[0071] The pesticidal composition can have a percent volume of droplets smaller than 50 pm of about 15.15% and has a percent volume of droplets smaller than 10 pm less than about 0.5% of a total spray volume, within manufacturing and / or measurement tolerances.

[0072] The pesticidal active ingredient can be a glyphosate active ingredient. The pesticidal composition can include, for example, a glyphosate herbicidal formulation. For example, the pesticidal active ingredient can be selected from glyphosate acid, agriculturally acceptable salts thereof, and a mixture thereof. The glyphosate active ingredient can be present in a range from about 0.8 wt%-about 20.0 wt% (acid equivalent), within manufacturing and / or measurement tolerances, in the pesticidal composition. The pesticidal active ingredient can include isopropylamine, mono-ammonium, di-ammonium, potassium, sodium, dimethylammonium, trimesium salt, or a combination thereof.

[0073] Pesticidal compositions can be manufactured by providing an aqueous dispersion of nitro-oxidized, carboxylated cellulose fibers. The aqueous dispersion can have a solids content, for example, between about 0.1 wt% and about 10 wt%, within manufacturing and / or measurement tolerances. The aqueous dispersion can have other solids content. A pesticidal active ingredient can then be mixed into the aqueous dispersion. The mixing can be performed using, for example, high-shear mixers, homogenizers, or microfluidizers. The mixing can be performed under conditions sufficient to obtain a homogeneous, sprayable mixture. The mixing can occur, for example, under shear conditions between about 500 s’1and about 10,000 s’1, within manufacturing and / or measurement tolerances, to provide the mixture. It is possible to mix under other conditions. The pH of the mixture can then be adjusted to between about 2 and about 12, within manufacturing and / or measurement tolerances, to provide a stable pesticidal composition. The resulting stable pesticidal composition can include a homogeneous matrix of the nitro-oxidized, carboxylated cellulose fibers and the pesticidal active ingredient, and the stable pesticidal composition can exhibit shear-thinning behavior when sprayed.

[0074] Optionally, additional formulation components can be added to the stable pesticidal composition, and the stable pesticidal composition can be adjusted to a final volume.

[0075] Agricultural substrate compositions of example embodiments of the present invention can include a substrate and a nitro-oxidation-process-derived (NOP-derived) cellulosicadditive. The NOP-derived cellulosic additive can be selected, for example, from nitro-oxidized cellulose nanofibers (NOCNF), nitro-oxidized cellulose microfibers (NOCMF), a hydrogel, a wet sponge, an aerated sponge, or a mixture thereof. For example, the NOP-derived cellulosic additive can be selected from:1) a hydrogel included in a range from about 0.25 w%-about 1.0 wt%;2) wet sponge granules included in a range from about 0.25 wt%-about 3.0 wt%;3) aerated sponge granules included in a range from about 0.25 wt%-about 1.0 wt%; or4) a combination thereof.The NOP-derived cellulosic additive can be included in a range of from about 0.1 wt% to about 5.0 wt%, within manufacturing and / or measurement tolerances. The NOP-derived cellulosic additive can include a three-dimensional porous network having a total porosity of at least about 70% by volume or of at least about 90% by volume, within manufacturing and / or measurement tolerances, and can act as a micro-reservoir network to slow water drainage and evaporation.

[0076] The agricultural substrate composition can increase a water-holding capacity by at least about 5% relative to an identical composition but without any NOP-derived cellulosic additive when evaluated by gravimetric water-loss measurements over an 18-day period, within manufacturing and / or measurement tolerances. The increase in water-holding capacity in some example embodiments can be between about 6% and about 20%, including between about 18% and about 19%, within manufacturing and / or measurement tolerances. If a hyrdrogel is included at about 0.5 wt%, then the water-holding capacity can be increased by about 18.20%, within manufacturing and / or measurement tolerances. If wet sponge granules are included at about 0.25 wt%, then the water-holding capacity can be increased by about 18.58%, within manufacturing and / or measurement tolerances. If aerated sponge granules are included at about 0.25 wt%, then the water-holding capacity can be increased by about 18.74%, within manufacturing and / or measurement tolerances. When evaluated by gravimetric waterloss measurements over an 18-day period using fully hydrated samples weighed at two-day intervals, a composition including about 0.5 wt% biogel can exhibit an average water loss ofabout 24.2 g per two-day interval; a composition including about 0.25 wt% wet sponge granules can exhibit an average water loss of about 24.0 g per two-day interval; or a composition including about 0.25 wt% aerated sponge granules can exhibit an average water loss of about 24.0 g per two-day interval.

[0077] The substrate can include soil and / or a soilless substrate. The soilless substrate can include an organic substrate selected from coco coir, wood fiber, chips, sawdust, bark, rice hulls, or a mixture thereof and / or can include an inorganic substrate selected from perlite, vermiculite, rockwool, expanded clay pebbles, pumice, sand, or a mixture thereof.

[0078] Method of increasing the water-holding capacity of an agricultural substrate according to example embodiments of the present invention include mixing a nitro-oxidation- process-derived (NOP-derived) cellulosic additive with a substrate to provide a mixture. The NOP-derived cellulosic additive can be included in an amount from about 0.1 wt% to about 5.0 wt% or from about 0.25 wt%-about 0.5 wt%, within manufacturing and / or measurement tolerances. The mixture can then be hydrated to provide an agricultural substrate. For example, the mixture can be hydrated to field capacity. Field capacity can refer to the water content of a soil or substrate after it has been fully saturated with water and then allowed to drain freely under gravity until drainage has stopped or essentially stopped. The resulting agricultural substrate can provide reduced average water loss per day and increased water-holding capacity of at least about 5%, at least about 10%, at least about 15%, or in a range from about 18%- about 19% relative to an identical substrate but without any NOP-derived cellulosic additive as determined by gravimetric mass-loss measurements over about 18 days, within manufacturing and / or measurement tolerances.Example Embodiment 1 (Viscosity and Droplet Size Behavior of CNF-Glyphosate Formulations for Drift Reduction)

[0079] A series of glyphosate formulations were prepared to evaluate the effect of carboxylated cellulose nanofiber (CNF) addition on rheological behavior. A control formulation included 0.16 wt% glyphosate in water was compared with CNF-glyphosate suspensions containing a fixed amount of glyphosate (0.16 wt%) and different concentrations of CNF suspensions as shown in Fig. 1.

[0080] NOP-derived carboxylated CNF was used to prepared aqueous CNF-glyphosate suspensions with varying concentrations: 0.05 wt%, 0.10 wt%, 0.20 wt%, 0.50 wt%, and 1.0 wt% (dry basis weight relative to the total formulation weight). All samples were gently mixed until visually homogeneous.

[0081] Steady-shear viscosity measurements were conducted using a rotational rheometer equipped with a plate-to-plate geometry over a shear rate range from 0.1 s’1to 1000 s’1at ambient temperature. Fig. 1 shows the concentration-dependent viscosity versus shear rate profiles for the glyphosate-only formulation and the CNF-glyphosate suspensions.

[0082] The glyphosate solution (control sample) exhibited typical Newtonian behavior, with the viscosity remaining essentially constant at approximately 1 mPa-s across the tested shear rate range, which is similar to pure water.

[0083] In contrast, all CNF-containing formulations exhibited pronounced shear-thinning behavior. At low shear rates (e.g., 0.1 s-1), the apparent viscosity increased strongly with CNF concentration. For example, the viscosity of the formulation containing 0.10 wt% CNF and 0.16 wt% glyphosate at 0.1 s’1was measured to be approximately 104times higher than that of the glyphosate-only control. As shear rate increased, the apparent viscosity of the CNF-glyphosate suspensions decreased, approaching values suitable for spray application at nozzle shear rates.

[0084] This behavior is attributed to the tendency of flexible, high-aspect-ratio cellulose nanofibers to form an entangled, three-dimensional network in suspension. At low shear rates, extensive fiber-fiber entanglements resist the fiber alignment and flow, yielding high apparent viscosity. As shear rate increases, these entanglements are progressively disrupted, and the fibers align more with the flow, leading to a decrease in viscosity. Thinner and longer fibers, possessing higher aspect ratios, strengthen the three-dimensional network and further enhance the low-shear viscosity.

[0085] The network formation in CNF-glyphosate suspensions is particularly beneficial for foliar applications. During the droplet deposition on the leaf surface, the high low-shear viscosity increases the dissipation of kinetic energy, thus increasing the contact line friction and decreasing the droplet splashing and splitting tendency. The cohesive effect of the CNF networkreduces the droplet mobility, raises the tensile strength within the droplet, and improves the adhesion of droplets to hydrophobic leaf surfaces.

[0086] Overall, these results demonstrate that CNF functions as an effective rheology modifier in glyphosate formulations. By providing a shear-thinning, entangled fiber network, CNFs enhance the drift control, promotes better droplet retention and adhesion on leaf surfaces, and thereby enhancing the effective availability and efficacy of glyphosate after spraying, while maintaining practical sprayability through standard agricultural equipment.Example Embodiment 2 (Drift-Control Using CNF-Glyphosate Suspensions)

[0087] A soluble concentrate was prepared by mixing 0.16 wt% glyphosate acid, 0.2 wt% carboxylated CNF. The CNF sample possessed a carboxylate content of about 1.8 mmol / g, with diameters of about 4 to about 10 nm, and lengths of about 0.2 to about 2 pm, within manufacturing and / or measurement tolerances.

[0088] The droplet size analysis was carried out as particle size measurements of sprays according to the ISO 13320-2020 standard using a Spraytec MALVERN instrument. The Spraytec MALVERN instrument uses laser diffraction for the measurement of the size of spray droplets. The laboratory is maintained at a controlled temperature of about 20°C and three repeatability measurements are performed on each sample. The particle size analyser, equipped with a 300 mm focal length lens, is set up in the environment of the test support (ventilated optical table). This measurement method, based on light diffraction, can characterize particle sizes between about 0.1 pm and about 900 pm (Dv50 ~ 0.5 pm -600 pm), using an acquisition frequency of 5 Hz to 5 kHz, extendable to 10 kHz, for analyzing phenomena in the order of hundreds of microseconds, such as the dynamics of atomization by spraying or by dispersion. The standard distance between the spray nozzle and the laser beam is about 15 cm, within measurement tolerances, and a Uline Chemical Resistant Spray Bottle (model S-16187) is used as the spray nozzle. The CNF-glyphosate formulation was sprayed under these identical conditions using the laser diffraction instrument to obtain volume-based droplet size parameters. For this formulation, three independent spray measurements were performed, and the mean and standard deviation (SD) were calculated.

[0089] Table 1 summarizes the results for the CNF-containing formulation, displaying the droplet size distribution parameters for the 0.2 wt% CNF suspension mixed with 0.16 wt% glyphosate (mean ± SD, n = 3). The CNF-glyphosate mixture suspension produced droplets with an average DvlO of about 40.28 pm (SD ~ 0.64 pm), Dv50 of about 118.53 pm (SD ~ 0.23 pm), and Dv90 of about 278.83 pm (SD = 4.83 pm), within measurement tolerances. The volume- weighted mean diameter D[4,3] was about 141.80 pm, and the surface-weighted mean diameter D[3,2] was about 74.48 pm, within measurement tolerances. The coefficient of variation (Cv) of D[4,3] between sprays was approximately 44.42 ppm, and the Span was about 2.013, within measurement tolerances, indicating a relatively consistent coarse droplet distribution.

[0090] The CNF mix also showed a low fraction of ultrafine droplets: the percent volume of droplets smaller than 5 pm was about 0.25%, and the percent volume of droplets smaller than 10 pm was about 0.46%, within measurement tolerances. The percent volume of droplets smaller than 50 pm was about 15.15%, within measurement tolerances, indicating a moderate proportion of fine droplets that contribute to coverage while the vast majority of spray volume remains in larger, less drift-prone droplets.Table 1: Droplet size distribution parameters for 0.2 wt% CNF mix with 0.16 wt% glyphosate (mean ± SD, n = 3)

[0091] These results demonstrate that a CNF-glyphosate suspension formulated with 0.2 wt% carboxylated CNF and 0.16 wt% glyphosate can provide a predominantly coarse dropletsize distribution with a controlled fraction of fine droplets and a very low ultrafine fraction, consistent with improved drift management and foliar coverage in agricultural spray applications.

[0092] Spray coverage was assessed qualitatively using water-sensitive papers in parallel with laser diffraction measurements of droplet size as shown in Fig. 2. The CNF-glyphosate formulations were applied with a spray bottle under the same operating conditions used for droplet sizing. Consistent with the laser diffraction data indicating a predominantly coarse droplet size distribution with a controlled fraction of fine droplets, the 0.2 wt% CNF + 0.16 wt% glyphosate formulation produced relatively uniform coverage on the water-sensitive papers across the treated area, with only minor local variations in droplet density.Example Embodiment 3 (Enhanced Water-Holding Capacity (WHC) of Coco Coir Substrate Amended with CNF, CMF, Biogel, Hydrosponge, and Aerosponge)

[0093] This example embodiment illustrates the effect of NOP-derived cellulose nano- and micro-fiber materials, including CNF, CMF, hydrogel (e.g., Biogel), wet sponge (e.g., Hydrosponge), and aerated sponge (e.g., Aerosponge), on the water-holding capacity of growing substrate such as coco coir. Coco coir without additive served as the control.

[0094] Agricultural substrate blends were prepared by combining dry coco coir with various CNF / CMF-based additives at different weight percentages, calculated on the total substrate weight. The applied treatments included the following formulations:1) CMF added at 0.25 wt%, 0.5 wt%, 1.0 wt%, 3.0 wt%, and 5.0 wt%;2) CNF added at 0.25 wt%, 0.5 wt%, 1.0 wt%, 3.0 wt%, and 5.0 wt%;3) Biogel added at 0.25 wt%, 0.5 wt%, 1.0 wt%, 3.0 wt%, and 5.0 wt%;4) Hydrosponge (aggregated form, "Ag") added at 0.25 wt%, 0.5 wt%, 1.0 wt%, 3.0 wt%, and 5.0 wt%;5) Hydrosponge Ground added at 0.25 wt%, 0.5 wt%, 1.0 wt%, and 3.0 wt%;6) Aerosponge (aggregated form, "Ag") added at 0.25 wt%, 0.5 wt%, 1.0 wt%, and 3.0 wt%;7) Aerosponge Ground added at 0.25 wt%, 0.5 wt%, 1.0 wt%, and 3.0 wt%;8) Coco coir alone (no additive) was designated "Coco Coir Only" and used as the reference (i.e., 0% increase in water-holding capacity).

[0095] Water-loss values were obtained gravimetrically at two-day intervals over an 18-day observation period. For each treatment, the substrate blend was fully hydrated to approximate field capacity and allowed to drain to a stable starting mass. The initial mass was recorded using a precision balance.

[0096] Samples were held under identical environmental conditions (temperature, airflow, and light). At every two-day interval, each sample was weighed, and the reduction in mass relative to the previous measurement was recorded. The mass loss in grams corresponds directly to milliliters of water lost, assuming a water density of approximately 1 g / mL, within measurement tolerances.

[0097] Each two-day interval represents a discrete period of water depletion under controlled conditions. An average water loss per two-day interval ("Avg Water Lost") and per day ("Avg Daily Loss") was calculated for each treatment across the 18-day test. Percent increase in water-holding capacity (% Increase in WHC) was determined from the reduction in water loss relative to the coco coir control.

[0098] A broader set of formulations were also evaluated, and percent increases in waterholding capacity relative to coco coir alone were calculated. Table 2 below summarizes the results (percent increase in water-holding capacity) for coco coir amended with CMF, CNF, hydrogels (e.g., Biogel), wet sponges (e.g., Hydrosponge), and aerated sponges (e.g., Aerosponge). The data show, for example, that:1) CMF treatments provided modest improvements, with % increase in WHC generally in the range of about 6%-about 12%, within measurement tolerances. For example, CMF 3.0% yielded approximately 11.79% increase in WHC, within measurement tolerances.2) CNF (2 wt%) treatments provided improvements in the range of about 8%-about 15%, within measurement tolerances, with peak performance near intermediate loadings (e.g., CNF 2 wt% and 0.5 wt% showed about 14.97% increase in WHC, within measurement tolerances).3) Biogel treatments showed strong improvements at low to moderate loadings (Biogel 0.5 wt% = 18.20%; Biogel 0.25 wt% = 15.03%; Biogel 1.0 wt% = 15.58% (,within measurement tolerances)), while higher loadings such as 5.0 wt % exhibited reduced marginal benefit (= 5.85% increase in WHC, within measurement tolerances), suggesting an optimal loading range.4) Hydrosponge (Ag) treatments showed increases generally between about 9%- about 15%, within measurement tolerances, across the 0.25 wt%-5.0 wt% range, with Hydrosponge Ag 5.0 wt% achieving approximately 14.51% increase in WHC, within measurement tolerances.5) Hydrosponge Ground treatments exhibited some of the highest increases, with Hydrosponge Ground 0.25 wt% = 18.58% and Hydrosponge Ground 3.0 wt% = 19.47% increase in WHC, within measurement tolerances.6) Aerosponge (Ag) treatments showed improvements between about 6%-about 14%, with Aerosponge Ag 0.5 wt%- 1.0 wt% giving approximately 13.94%- 14.37% increase in WHC, within measurement tolerances.7) Aerosponge Ground treatments showed strong performance at low loading (Aerosponge Ground 0.25 wt% = 18.74%, within measurement tolerances), with somewhat lower gains at higher loadings (e.g., 1.0 wt%-3.0 wt% giving approximately 6%- approximately 7% increase in WHC, within measurement tolerances).

[0099] Overall, nearly all CNF- and CMF-based treatments increased the water-holding capacity relative to coco coir alone, with several formulations (notably Biogel 0.5 wt%, Hydrosponge Ground 0.25-3.0 wt%, and Aerosponge Ground 0.25 wt%) delivering increases on the order of 18%-19%.Table 2: Percent increase in water-holding capacity (WHC) for coco coir amended with CMF, CNF, Biogels, Hydrosponge, and Aerosponge

[0100] An approximately 18%-approximately 19% increase in water-holding capacity has tangible operational and agronomic benefits, including, for example:1) longer intervals between irrigations;2) reduced total water consumption;3) more stable moisture conditions supporting improved root-zone health;4) reduced plant loss in retail and scan-to-pay operations where individual crops are not actively irrigated;5) reduced impact of missed or irregular irrigation schedules, particularly in greenhouses and retail environments; and6) increased resilience during equipment malfunctions, labor shortages, or high- heat events.

[0101] These benefits can be achieved at relatively low inclusion rates (e.g., 0.25 wt%-0.5 wt% for Biogel, Hydrosponge Ground, and Aerosponge Ground), which supports a favorable cost-to-performance ratio for commercial agricultural substrates.

[0102] Overall, gravimetric mass-loss data collected every two days over an 18-day period, together with the compiled percent increase in WHC for multiple CNF / CMF-based materials and loadings, demonstrate that CNF-derived and hydrospongic additives significantly enhance the water-holding capacity of coco coir substrates— typically by about 6-20%, and approximately 18-19% for several optimized formulations. These results validate the use of CNF, CMF, Biogel, Hydrosponge, and Aerosponge as effective moisture-retention enhancers for agricultural substrates and support their use in water-efficient, stress-resilient growing systems.

[0103] 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 the art 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 pesticidal composition comprising: a pesticidal active ingredient; nitro-oxidized cellulose fibers; and water; wherein the nitro-oxidized cellulose fibers have a carboxylate content between about 0.5 mmol / g and about 3.0 mmol / g.

2. The pesticidal composition of claim 1, wherein the nitro-oxidized cellulose fibers include nitro-oxidized cellulose nanofibers (NOCNFs) and / or nitro-oxidized cellulose microfibers (NOCMFs).

3. The pesticidal composition of claim 1 or 2, wherein the pesticidal composition can be deployed through a spray nozzle at a pressure of about 15 psi-about 60 psi, a flow rate of about 0.2 L / min-about 1.5 L / min per nozzle, and a nozzle-to-target distance of about 20 cm-about 60 cm.

4. The pesticidal composition of one of claims 1-3, wherein a spray droplet size distribution of the pesticidal composition satisfies at least one of the following conditions: a volume median droplet diameter (Dv50) is between about 80 pm and about 200 pm; a percent spray volume of droplets smaller than 50 pm is less than about 25%; and a percent spray volume of droplets smaller than 10 pm is less than about 1%.

5. The pesticidal composition of claim 4, wherein the percent spray volume of droplets smaller than 50 pm is between about 10% and about 20%.

6. The pesticidal composition of claim 5, wherein the percent spray volume of droplets smaller than 10 pm is less than about 0.5%7. The pesticidal composition of one of claims 1-6, wherein the pesticidal active ingredient is a glyphosate active ingredient selected from glyphosate acid, agriculturally acceptable salts thereof, and a mixture thereof.

8. The pesticidal composition of claim 7, wherein the glyphosate active ingredient is present in a range from about 0.8 wt%-about 20.0 wt% (acid equivalent) in the pesticidal composition.

9. The pesticidal composition of one of claims 1-6, wherein the pesticidal active ingredient includes isopropylamine, mono-ammonium, di-ammonium, potassium, sodium, dimethylammonium, trimesium salt, or a combination thereof.

10. The pesticidal composition of one of claims 1-9, wherein the nitro-oxidized cellulose fibers have diameters between about 3 nm and about 10 nm and lengths between about 0.2 pm and about 1 pm.

11. The pesticidal composition of one of claims 1-10, wherein the nitro-oxidized cellulose fibers are present in an amount from about 0.01 wt% to about 5 wt% based on a total weight of the pesticidal composition.

12. The pesticidal composition of one of claims 1-11, wherein the nitro-oxidized cellulose fibers are present in an amount from about 0.05 wt% to about 2 wt% based on a total weight of the pesticidal composition.

13. The pesticidal composition of one of claims 1-12, wherein a viscosity of the pesticidal composition at a shear rate of about 0.1 s“1is at least about 103times greater than the viscosity of the pesticidal composition at a shear rate of about 1000 s-1.

14. The pesticidal composition of one of claims 1-12, wherein a viscosity of the pesticidal composition at a shear rate of about 0.1 s-1is at least about 104times greater than the viscosity of the pesticidal composition at a shear rate of about 1000 s-1.

15. The pesticidal composition of one of claims 1-14, wherein the pesticidal composition exhibits: a volume-weighted mean diameter D[4,3] between about 130 pm and about 170 pm; and / or a spray-to-spray coefficient of variation (Cv) in D[4,3] of about 60 ppm or less.

16. The pesticidal composition of one of claims 1-15, wherein the pesticidal composition exhibits a spray-to-spray coefficient of variation (Cv) in D[4,3] of about 50 ppm or less.

17. The pesticidal composition of one of claims 1-16, wherein the pesticidal composition includes about 0.2 wt% NOCNF and about 0.16 wt% glyphosate, and spray droplet size parameters averaged over three independent spray events are: DvlO is about 40.28 pm, Dv50 is about 118.53 pm, Dv90 is about 278.83 pm, D[4,3] is about 141.80 pm, D[3,2] is about 74.48 pm, Cv is about 44.42 ppm, Span is about 2.013, %V < 5 pm is bout 0.2516%, %V < 10 pm is about 0.4616%, and %V < 50 pm is about 15.15%.

18. The pesticidal composition of one of claims 1-16, wherein the pesticidal composition has a percent volume of droplets smaller than 50 pm of about 15.15% and has a percent volume of droplets smaller than 10 pm less than about 0.5% of a total spray volume.

19. The pesticidal composition of one of claims 1-18, wherein the nitro-oxidized cellulose fibers function as at least one of the following: a drift -control agent; a rheology modifier;a spreader or surfactant-like component; and a film-forming agent that generates a microgel network on leaf surfaces.

20. A method of controlling pests comprising:(a) providing the pesticidal composition according to one of claims 1-19; and(b) spraying the pesticidal composition through an agricultural spray nozzle onto plant foliage, seeds, soil, or growth media.

21. The method of claim 20, further comprising a step (a') diluting the pesticidal composition with water.

22. The method of one of claim 20 or 21, wherein the pesticidal composition includes a glyphosate herbicidal formulation, and the nitro-oxidized cellulose fibers increase droplet surface area and coverage on leaf surfaces while maintaining an ultrafine droplet volume fraction below about 0.5%.

23. A method of manufacturing a pesticidal composition comprising:(a) providing an aqueous dispersion of nitro-oxidized, carboxylated cellulose fibers having a solids content between about 0.1 wt% and about 10 wt%;(b) mixing the aqueous dispersion with a pesticidal active ingredient under shear conditions sufficient to provide a mixture that is homogeneous and sprayable; and(c) adjusting a pH of the mixture to between about 2 and about 12 to provide a stable pesticidal composition; wherein the stable pesticidal composition includes a homogeneous matrix of the nitro-oxidized, carboxylated cellulose fibers and the pesticidal active ingredient, and the stable pesticidal composition exhibits shear-thinning behavior when sprayed.

24. The method of claim 23, further comprising adding additional formulation components to the stable pesticidal composition and adjusting the stable pesticidal composition to a final volume.

25. An agricultural substrate composition comprising: a substrate; and a nitro-oxidation-process-derived (NOP-derived) cellulosic additive included in a range of from about 0.1 wt% to about 5.0 wt%; wherein the agricultural substrate composition increases a water-holding capacity by at least about 5% relative to an identical composition but without the NOP-derived cellulosic additive when evaluated by gravimetric water-loss measurements over an 18-day period.

26. The agricultural substrate composition of claim 25, wherein the substrate includes soil and / or a soilless substrate.

27. The agricultural substrate composition of claim 26, wherein the soilless substrate includes an organic substrate selected from coco coir, wood fiber, chips, sawdust, bark, rice hulls, or a mixture thereof and / or an inorganic substrate selected from perlite, vermiculite, rockwool, expanded clay pebbles, pumice, sand, or a mixture thereof.

28. The agricultural substrate composition of one of claims 25-27, wherein the NOP- derived cellulosic additive is selected from nitro-oxidized cellulose nanofibers (NOCNF), nitrooxidized cellulose microfibers (NOCMF), a hydrogel, a wet sponge, an aerated sponge, or a mixture thereof.

29. The agricultural substrate composition of one of claims 25-28, wherein the increase in water-holding capacity is between about 6% and about 20%.

30. The agricultural substrate composition of one of claims 25-28, wherein the increase in water-holding capacity is between about 18% and about 19%.

31. The agricultural substrate composition of one of claims 25-30, wherein the NOP- derived cellulosic additive is selected from: a hydrogel included in a range from about 0.25 w%-about 1.0 wt%; wet sponge granules included in a range from about 0.25 wt%-about 3.0 wt%; aerated sponge granules included in a range from about 0.25 wt%-about 1.0 wt%; or a combination thereof.

32. The agricultural substrate composition of claim 31, wherein, when evaluated by gravimetric water-loss measurements over an 18-day period using fully hydrated samples weighed at two-day intervals: a composition including about 0.5 wt% biogel exhibits an average water loss of about 24.2 g per two-day interval; a composition including about 0.25 wt% wet sponge granules exhibits an average water loss of about 24.0 g per two-day interval; or a composition comprising about 0.25 wt% aerated sponge granules exhibits an average water loss of about 24.0 g per two-day interval.

33. The agricultural substrate composition of one of claims 25-32, wherein the NOP- derived cellulosic additive includes a three-dimensional porous network having a total porosity of at least about 70% by volume and is configured to act as a micro-reservoir network to slow water drainage and evaporation.

34. The agricultural substrate composition of claim 33, wherein the total porosity of the three-dimensional porous network is at least about 90% by volume.

35. The agricultural substrate composition of one of claims 25-34, wherein the shear conditions are between about 500 s’1and about 10,000 s’1.

36. A method of increasing water-holding capacity of an agricultural substrate, the method comprising:(a) providing a substrate;(b) mixing from about 0.1 wt% to about 5.0 wt% of a nitro-oxidation-process-derived (NOP- derived) cellulosic additive with the substrate to provide a mixture; and(c) hydrating the mixture to field capacity to provide an agricultural substrate; wherein the agricultural substrate exhibits increased water-holding capacity of at least about 5% relative to an identical substrate but without the NOP-derived cellulosic additive as determined by gravimetric mass-loss measurements over about 18 days.

37. The method of claim 36, wherein the substrate includes soil and / or a soilless substrate.

38. The method of claim 37, wherein the soilless substrate includes an organic substrate selected from coco coir, wood fiber, chips, sawdust, bark, rice hulls, or a mixture thereof and / or an inorganic substrate selected from perlite, vermiculite, rockwool, expanded clay pebbles, pumice, sand, or a mixture thereof.

39. The method of one of claims 36-38, wherein the NOP-derived cellulosic additive is selected from nitro-oxidized cellulose nanofibers (NOCNF), nitro-oxidized cellulose microfibers (NOCMF), a hydrogel, a wet sponge, an aerated sponge, or a mixture thereof.

40. The method of one of claims 35-39, wherein the agricultural substrate exhibits increased water-holding capacity of at least about 10% relative to an identical substrate but without the NOP-derived cellulosic additive as determined by gravimetric mass-loss measurements over about 18 days.

41. The method of one of claims 36-38, wherein the agricultural substrate exhibits increased water-holding capacity of at least about 15% relative to an identical substrate but without the NOP-derived cellulosic additive as determined by gravimetric mass-loss measurements over about 18 days.

42. The method of one of claims 36-41, wherein the NOP-derived cellulosic additive is included in a range of about 0.25 wt%-about 0.5 wt%, and the increased water-holding capacity is in a range from about 18%-about 19%.

43. An integrated agricultural system comprising: a pesticidal composition of one of claims 1-19 configured for foliar or soil application; and an agricultural substrate composition of one of claims 25-35 configured for growing plants.

44. A composition comprising nitro-oxidized, carboxylated cellulose fibers, wherein a first portion of the nitro-oxidized, carboxylated cellulose fibers have a first cross-sectional dimension in a range from about 2 nm-about 100 nm, a second portion of the nitro-oxidized, carboxylated cellulose fibers have a second cross-sectional dimension in a range from about 100 nm-about 50 mm, and the composition is an agricultural adjuvant, a surfactant, a drift control agent, or a soil amendment.

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