Composite materials and methods for expediting and improving the ecological impact of composting

Abstract

The present teachings describe composite materials that can improve and expedite composting and reduce harmful off¬ gassing. The present teachings provide composite materials that can provide fast, scalable solutions that can be optimized for application in various composting systems including residential waste, food waste, human waste, animal waste, and other forms of organic waste processing through fermentation. In one aspect, the present teachings generally provide a composite material including titanium dioxide; silver; copper; selenium; and chitosan in a stable, non-toxic solvent. The composite material can also include a polymer such as polyvinylpyrrolidone (PVP).

Description

[0001] COMPOSITE MATERIALS AND METHODS OF USING THE SAME FOR EXPEDITING AND IMPROVING THE ECOLOGICAL IMPACT OF COMPOSTING

[0002] CROSS REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the benefit of U.S. Application No. 63 / 695,999, filed on September 18, 2024, which is incorporated herein by reference in its entirety.

[0004] FIELD

[0005] The present teachings are related to methods of composting using a composite material to improve and expedite composting and reduce harmful off-gassing.

[0006] BACKGROUND

[0007] Composting is a natural process of recycling organic waste into valuable fertilizer that can enrich soil and enhance crop production. Composting involves combining green materials (like fruit and vegetable scraps, coffee grounds, and grass clippings) with brown materials (such as dead leaves, branches, and paper). These materials break down over time through the action of microorganisms and other decomposers. Composting is a natural process that generates heat, which kills off pathogens and weeds. The end product, called compost, is rich in nutrients and can be added to soil to improve soil structure, retain moisture, support biodiversity, enhance plant metabolism, and reduce the need for chemical fertilizers.

[0008] Composting reduces trash in landfills, is climate friendly, and supports healthy soil restoration. When organic materials like food scraps decompose in a landfill, lack of oxygen (anaerobic conditions) impedes efficient fermentation, releasing methane, a potent greenhouse gas. Municipal solid waste landfills are the third-largest source of human-related methane emissions in the U.S., accounting for approximately 14% of methane emissions in 2021. retrieved 1

[0009] September 2024) Traditional composting employs aerobic decomposition, lowering methane emissions and promoting carbon sequestration in soil, as methane-producing microbes are not dominant in the presence of sufficient oxygen, / >%ffe::keeping-gi^.;hh g:giping; retrieved 1 September 2024). Nevertheless, the vast majority of high organic content waste continues to find its way into landfills, as composting is still relatively costly and inefficient. This situation is unfortunate, as methane is particularly harmful, accounting for approximately 30% of near-term global heating.

[0010] 1

[0011] IPTS / 128677603.1 retrieved 1 September 2024) Reducing methane emissions is therefore a high impact approach to limiting climate change and improving air quality.

[0012] While composting is more environmentally friendly than landfill waste storage, current composting methods still produce significant methane, and other harmful and even odiferous compounds like ammonia, hydrogen sulfide, nitrous oxide, dimethyl sulfide and greenhouse gases such as carbon dioxide.

[0013] Public and legislative support is growing very fast, resulting in states like California and New York to introduce composting mandates. The relative benefits of composting, while significant, are undermined by time (40 to 90 days) and space inefficiencies, compounded by the nuisances of odors and poor air quality. Many composting facilities attract local scorn resulting in fines and even banishment

[0014] Thus, the industry desires improved systems and methods to compost organic carbon- containing materials (or compostable materials) back to their natural state, which systems and methods can further reduce the emission of unwanted gases such as methane, ammonia and carbon dioxide.

[0015] SUMMARY

[0016] The present teachings provide a revolutionary technology of products (i.e., composite materials) that expedite the breakdown of organic carbon matter thereby enhancing the composting process. The methods can promote aerobic activity, making the composting process faster while also reducing the emission of methane and ammonia. The present teachings provide composite materials that can provide fast, scalable solutions that can be optimized for application in various composting systems including residential waste, food waste, human waste, animal waste, and other forms of organic waste processing through fermentation.

[0017] In one aspect, the present teachings generally provide a composite material including titanium dioxide; silver; copper; selenium; and chitosan in a stable, non-toxic solvent. The composite material can also include a polymer such as polyvinylpyrrolidone (PVP). In addition, the composite material can include an acid such as acetic acid.

[0018] In various embodiments, a composite material comprises titanium dioxide (TiCh) coated silver (Ag) (“(TiChln / Ag”) particles, copper (Cu), and selenium (Se), where the TiCb / Ag particles, Cu and Se are combined with chitosan and a polymer in a solvent such as

[0019] 2

[0020] IPTS / 128677603.1 water. The water can contain an acid, for example, acetic acid. The composite material also includes a solvent so that the components can be combined with, for example, coated by or encapsulated by, chitosan and a (other) polymer as a dispersion or colloidal mixture.

[0021] More specifically, a composite material of the present teachings generally can

[0022] 5 include TiCh coated Ag (“(TiOzjn / Ag”) nanoparticles, copper and selenium along with chitosan or a chitosan substrate (CS), where the (TiChWAg particles are combined with the chitosan or CS, all in a solvent. (Here, although just meant for symbolism, n can be an integer greater than zero, for example, from about 5 to about 250.) The (TiOzjn / Ag particles can be further combined with a polymer. The solvent typically includes an acid.

[0023] In some embodiments, the composite material can include TiCh and Se coated Ag (“TiOz / Ag / Se”) particles. In various embodiments, Cu can be substituted for Se or be in addition to Se in these particles.

[0024] In another aspect, the present teachings provide a method of making a composite material, where the method generally includes mixing TiC in an acidic solution with salts of5 Ag, Cu and Se, and a polymer in a first solvent to form a first mixture; exposing the first mixture to a reducing agent until less than about 15% of the Ag is Ag+to form a reduced mixture; mixing chitosan and an acid in a second solvent to form a second mixture; and adding a portion of the second mixture to a portion of the reduced mixture thereby forming a composite material, where the portion of the second mixture can be between about 3% by0 weight to about 30% by weight of the total weight of the composite material, depending on the intended application.

[0025] In another aspect, the present teachings provide a method of reducing at least one of methane emission, ammonia emission and carbon dioxide emission during composting. In various embodiments, the methods comprise contacting and mixing a compostable material with the composite material of the present teachings; and composting the compostable material to cause at least one of methane emission, ammonia emission and carbon dioxide emission from the compostable material to be reduced compared to a control of composting compostable material without exposure to a composite material of the present teachings. 0 DETAILED DESCRIPTION

[0026] The present teachings describe products (i.e., composite materials) that can expedite the breakdown of organic carbon matter thereby enhancing the composting process. The

[0027] 3

[0028] IPTS / 128677603.1 methods can promote aerobic activity, which makes the composting process faster while also being able to reduce the emission of methane and ammonia in the process. Without wishing to be bound to any particular theory, it is believed that the emission of methane can be reduced due to the aerobic digestion promoted significantly by the composite materials of the

[0029] 5 present teachings and methods of their use as described herein. Further, it is believed that emission of ammonia can be reduced significantly due to proper aerobic activity, and rapid oxidation of ammonia due to the presence of the composite materials of the present teachings. Finally, the present teachings can provide reduced emission of carbon dioxide believed to be due to expedited fermentation of the composting process so that more of the organic carbon remains with the final compost rather than escaping into the air.

[0030] The components of the composite materials of the present teachings include TiO2 believed to be associated with silver (Ag) nanoparticles such that numerous TiCh particles associate themselves with the Ag particles ((TiC WAg), which are photocatalytic components. The components of the composite material also include Se, which can assist in5 electron transfer process as an electron acceptor to the electron donor, which can be Ag. The composite material also includes Cu. In addition, the composite materials of the present teachings include a naturally sourced polymer, chitosan, engineered to possess positively charged moieties (i.e., a polycation).

[0031] When the composite material is exposed to visible light and particularly, sunlight, it0 can produce ionic species and radicals necessary for decomposition of organic material, unwanted matter, and contaminant compounds in the compostable material.

[0032] More specifically, photocatalysis is an emerging technology for the removal of recalcitrant contaminant compounds, for example, in polluted water in need of remediation. Technically, the cascade of reactions involved in photocatalysis is initiated by the absorption of a photon, which excites an electron from the valence band to the conduction band of the semiconductor material thereby generating an electron-hole pair. The electron-hole pair can migrate to the material surface, where it reacts with oxygen to form reactive oxygen species (“ROS”). It is these ROS that effect the oxidation of recalcitrant contaminant compounds, leading to the breakdown of target contaminants into benign by-products. 0 A photocatalyst with a narrower band gap favors the capture of visible-light photons. Accordingly, narrowing the band gap of a photocatalytic material facilitates more photocatalytic activity with visible light.

[0033] 4

[0034] IPTS / 128677603.1 The present teachings can utilize this photocatalytic process to drive rapid oxidation of compostable materials - decreasing chemical oxygen demand (COD), which triggers ROS, accelerating the decomposition of heavy hydrocarbons, oils and other organic waste. Such processes can make oxygen attainable for aerobic bacteria, stimulating dormant microorganisms and / or driving efficiency of the natural biological decomposition process - all with minimal human intervention. The composite material additionally can remediate and can reduce ammonia and / or hydrogen sulfide components produced by composting.

[0035] Further, without wishing to be bound to any particular theory, it is believed that the composite material also acts as a biostimulant so that it is catalytically active even when not exposed to visible light. Biostimulation is a bioremediation technique that involves changing an environment to stimulate the activity of existing microorganisms capable of degrading contaminants and organic materials found in the compostable materials. Biostimulation can utilize electron acceptors (e.g., oxygen) and electron donors (e.g., organic substrates) to assist in the metabolic processes of the microorganisms present in the compostable material. Thus, the composite materials of the present teachings, which include electron acceptors, e.g., Se, and electron donors, e.g., Ag, are suitable for facilitating biostimulation to assist in the composting process.

[0036] More specifically, it is believed that TiCh provides support for the other catalysts. Cu and Se can enhance the redox reactions on the TiO? surface. In the dark, Cu and Se can continue to catalyze reactions independently, supporting aerobic processes and organic degradation. Ag can further amplify this effect by facilitating electron transfer, improving the overall efficiency of the catalytic process, as well as acting to suppress anaerobic bacteria in the dark.

[0037] It is believed that the combination of TiCh, Ag, Cu, and Se in this composite forms a synergistic catalytic system where TiO? acts as a support and photothermal catalyst, Ag and Cu facilitate redox reactions and electron transfer, and Se enhances the catalytic properties by lowering energy barriers and assisting in charge separation. These combined effects can result in improved catalytic activity both in light and dark environments, making the composite material effective in a range of applications, such as controlling anaerobic processes in agricultural settings and decomposing organic materials.

[0038] It is believed that using the composite material at appropriate levels likely produces enough oxidative stress to selectively inhibit anaerobic bacteria while allowing aerobic

[0039] 5

[0040] IPTS / 128677603.1 bacteria to thrive. This selective inhibition and promotion of aerobic activity can enhance the decomposition of organic matter and reduce the production of undesirable by-products like ammonia and methane, particularly in composting. That is, the composite material (e.g., TiCh- Ag-Cu-Se coated chitosan) is beneficial in promoting aerobic processes, especially in environments where the reduction of anaerobic activity is desired.

[0041] Definitions

[0042] To facilitate an understanding of the present invention, a number of terms and phrases are defined below.

[0043] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The abbreviations used herein have their conventional meaning within the chemical and biological arts. The chemical structures and formulae set forth herein are constructed according to the standard rules of chemical valency known in the chemical arts.

[0044] The terms “a’- and “an” as used herein mean “one or more” and include the plural unless the context is inappropriate.

[0045] In the application, where an element or component is said to be included in and / or selected from a list of recited elements or components, it should be understood that the element or component can be any one of the recited elements or components, or the element or component can be selected from a group consisting of two or more of the recited elements or components.

[0046] Further, it should be understood that elements and / or features of a composition or a method described herein can be combined in a variety of ways without departing from the spirit and scope of the present invention, whether explicit or implicit herein. For example, where reference is made to a particular compound, that compound can be used in various embodiments of compositions of the present invention and / or in methods of the present invention, unless otherwise understood from the context. In other words, within this application, embodiments have been described and depicted in a way that enables a clear and concise application to be written and drawn, but it is intended and will be appreciated that embodiments may be variously combined or separated without parting from the present teachings and invention(s). For example, it will be appreciated that all features described and depicted herein can be applicable to all aspects of the invention(s) described and depicted herein.

[0047] 6

[0048] IPTS / 128677603.1 It should be understood that the expression “at least one of’ includes individually each of the recited objects after the expression and the various combinations of two or more of the recited objects unless otherwise understood from the context and use. The expression “and / or” in connection with three or more recited objects should be understood to have the same meaning unless otherwise understood from the context.

[0049] The use of the term “include,” “includes,” “including,” “have,” “has,” “having,” “contain,” “contains,” or “containing,” including grammatical equivalents thereof, should be understood generally as open-ended and non-limiting, for example, not excluding additional unrecited elements or steps, unless otherwise specifically stated or understood from the context.

[0050] Where the use of the term “about” is before a quantitative value, the present invention also includes the specific quantitative value itself, unless specifically stated otherwise. As used herein, the term “about” refers to a ±10% variation from the nominal value unless otherwise indicated or inferred from the context.

[0051] At various places in the present specification, values are disclosed in groups or in ranges. It is specifically intended that the description include each and every individual subcombination of the members of such groups and ranges and their endpoints. For example, an integer in the range of 0 to 40 is specifically intended to individually disclose 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 32, 33, 34, 35, 36, 37, 38, 39, and 40, and an integer in the range of 1 to 20 is specifically intended to individually disclose 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.

[0052] The use of any and all examples, or exemplary language herein, for example, “such as” or “including,” is intended merely to illustrate better the present invention and does not pose a limitation on the scope of the invention unless claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the present invention.

[0053] As used herein, “compost” refers to decomposed organic material that can be used as a fertilizer and soil additive. Compost is a nutrient-rich, organic material that results from the decomposition of organic matter or biodegradable waste. Compost is created through the process of “composting,” where organic matter or biodegradable waste such as food scraps, yard waste, agricultural byproduct, livestock waste, and other biodegradable materials break down into a nutrient-rich substance or compost. More specifically, compost is created through a natural process where microorganisms, such as bacteria and fungi, break down this

[0054] 7

[0055] IPTS / 128677603.1 organic material in the presence of oxygen (aerobic decomposition). The process of composting converts this waste into a dark, crumbly, soil-like substance that can be used to enrich garden soil, improve plant growth, and reduce the need for chemical fertilizers.

[0056] As used herein, “compostable material(s)” refer to organic containing materials or

[0057] 5 matter that can be transformed into compost via composting.

[0058] Throughout the description, where compositions and kits are described as having, including, or comprising specific components, or where processes and methods are described as having, including, or comprising specific steps, it is contemplated that, additionally, there are compositions and kits of the present invention that consist essentially of, or consist of, the recited components, and that there are processes and methods according to the present invention that consist essentially of, or consist of, the recited processing steps.

[0059] As a general matter, compositions specifying a percentage are by weight unless otherwise specified.

[0060] Composite Materials 5 The effects described herein can be realized by introducing a composite material of the present teachings that includes titanium dioxide; silver, copper; selenium; and chitosan. The composite materials also can include a polymer, for example, polyvinylpyrrolidone (PVP); and an acid such as acetic acid. As described herein, the composite materials can include TiCh coated silver ((TiOz)n / Ag) nanocomposites or nanoparticles. The ((TiC>2)n / Ag)0 nanocomposites can be coated with chitosan.

[0061] In particular, the composite material according to the present teachings can include a TiCT / Ag nanocomposite having a doping structure with Se that provides visible light-reactive TiOz nanoparticles. It has a wide photocatalytic range from UV to visible light, for example, sunlight, and can promote decomposition of pollutants and contaminant compounds.

[0062] The composite material components can be combined with chitosan, and another polymer. The other polymer can be PVP and or polyethylene glycol (PEG). Without wishing to be bound by any particular theory, it is believed that the other polymer prevents agglomeration or aggregation of the TiOz-containing nanocomposites so that their surface area is maximized to the radiating visible light and / or sunlight, i.e., maintaining an increased0 surface area of the TiCh-containing nanocomposites to maximize photocatalytic activity.

[0063] With the inclusion of Se as a doping agent, the composite material has a wide photocatalytic activation range, UV to visible light, while possessing a high potential for

[0064] 8

[0065] IPTS / 128677603.1 electron transmission with electron acceptors that promote decomposition of pollutants and oxidation of heavy metals as well as assisting in biostimulation. In addition, the presence of silver affords the composite material antimicrobial properties.

[0066] More specifically, in certain embodiments, a composite material of the present teachings for composting generally includes TiCb, Ag, Cu, Se, chitosan, and a polymer such as polyvinylpyrrolidone (PVP). With these components, TiCL-Ag nanocomposites can be formed along with TiCL-Ag-Se nanocomposites, creating a doping structure in preparing a visible light-reactive TiO? photocatalyst composition.

[0067] Depending on the application, the composite material can further contain precious or noble metals such as Au and Pt or transition metal components such as Ni and Co in addition to Ag. It is believed that, like the TiCh-Ag nanocomposite containing Se, the additional metal component(s) can be in the form of a nanocomposite with a doping structure.

[0068] The TiCL generally is substantially anatase phase TiO (e.g., at least about 80%, at least about 85%, at least about 90%, or at least about 95% , or at least about 99% is this phase). The TiCh particles can have a mean diameter between about 0.5 nm and about 20 nm.

[0069] In some embodiments, the composite material has a concentration of TiC from about 25 mg / L to about 1000 mg / L, from about 35 mg / L to about 500 mg / L, or from about 50 mg / L to about 400 mg / L. In various embodiments, the composite material has a concentration of TiO2 from about 100 mg / L to about 500 mg / L, or from about 65 mg / L to about 400 mg / L, or from about 75 mg / L to about 350 mg / L. In some embodiments, the composite material has a concentration of TiCL from about 200 mg / L to about 350 mg / L. In particular embodiments, the composite material has a concentration of TiCb from about 250 mg / L to about 290 mg / L or to about 325 mg / L or to about 375 mg / L.

[0070] In certain embodiments, the concentration of Ag in the composite material is about 5 mg / L to about 35 mg / L, or about 10 mg / L to about 25 mg / L, or about 15 mg / L to about 20 mg / L. In particular embodiments, the concentration of Ag in the composite material is about 10 mg / L to about 15 mg / L or to about 20 mg / L.

[0071] In particular embodiments, a composite material of the present teachings can include between about 0.05 mg / L to about 5 mg / L of Cu, for example, about 1 mg / mL to about 3 mg / mL, about 1.5 mg / mL to about 2.5 mg / mL, or about 1 mg / mL, or about 2 mg / mL, or about 3 mg / L of Cu.

[0072] 9

[0073] IPTS / 128677603.1 In various embodiments, if TiOz / Cu particles are present, and the concentration of Cu in the composite material can be between about 0.5 mg / L to about 5 mg / L. In some embodiments, the amount of Cu in the composite material can be from about 0.5 mg / L to about 7 mg / L, or from about 0.5 mg / L to about 3 mg / L.

[0074] In some embodiments, the concentration of the Se in the composite material is about 0.1 mg / L to about 3 mg / L, or about 0.2 mg / L to about 1.5 mg / L, or about 1 mg / L to about 1.5 mg / L.

[0075] With respect to the photocatalytic components of the composite material, in some embodiments, about 70% to about 98% by weight of the photocatalytic components can be TiC with about 2% to about 30% being Ag, Cu and Se. In certain embodiments, about 90% to about 95% of the photocatalytic components can be TiCL with the remaining 5% to 10% being Ag, Cu and Se.

[0076] The Ag in the composite material typically includes less than about 10% of Ag+. In various embodiments, the Ag in the composite material includes less than about 20% or less than about 15% of Ag+. In some embodiments, the Ag in the composite material includes less than about 5% Ag+. Ag particles can have a mean diameter of between about 15 nm and about 75 nm.

[0077] In various embodiments, the composite material includes a cationic biopolymer, for example, chitosan. In some embodiments, it is believed that the (TiO WAg particles are coated by or encapsulated by chitosan and another polymer, when present. For example, the coating can be chitosan and another polymer such as PVP and / or PEG. Chitosan does not dissolve in water and typically is prepared in a solvent by diluting with an organic or inorganic acid during manufacture.

[0078] In various embodiments, the composite material has a concentration of chitosan from about 0.3 g / L to about 20 g / L, or about 1 g / L to about 15 g / L or to about 10 g / L, or about 1 g / L to about 5 g / L, or about 2 g / L to about 6 g / L. In certain embodiments, the concentration of chitosan in the composite material is between about 2 g / L to about 10 g / L, or 0.5 g / L to about 5 g / L, or about 1 g / L to about 3 g / L.

[0079] In particular embodiments, the concentration of the (other) polymer, for example, PVP, in the composite material is about 0.001 g / L to about 20 g / L. In various embodiments, the concentration of the other polymer is about 0.005 g / L to about 15 g / L. In certain embodiments, the concentration of the other polymer is about 0.1 g / L to about 3 g / L. In

[0080] 10

[0081] IPTS / 128677603.1 particular embodiments, the concentration of the other polymer is about 0.2 g / L to about I g / L.

[0082] In various embodiments, the composite material includes about 0.0005% to about 5% by weight of chitosan based on the total weight of the composite material. In some embodiments, the composite material can include about 0.01 % to about 3% by weight of chitosan based on the total weight of the composite material. In certain embodiments, the composite material includes about 0.5% to about 2% by weight of chitosan based on the total weight of the composite material. In some embodiments, the composite material includes about 0.0005% to about 1% by weight of chitosan based on the total weight of the composite material.

[0083] More specifically, chitosan is a biopolymer ((CeHnNC lm) (here, m is meant for symbolism of a polymeric structure) extracted from chitin (the main structural component of crustacean shells). Chitosan material is a polycationic polymer replaced with an amino group through a chemical deacetylation reaction in chitin.

[0084] An acid such as aqueous acetic acid can be used as a solvent for chitosan and also can act as a dispersant on compostable materials, to provide a localized pH suitable for the formation and efficient growth of naturally occurring microorganisms.

[0085] In various embodiments, the solvent(s) include water, ethylene glycol, methylene glycol, diethylene glycol, an acid, and combinations thereof. In some embodiments, the acid is acetic acid. In certain embodiments, the acid can be hydrochloric acid, for example, in addition to another acid such as acetic acid. The hydrochloric acid often is sourced from the TiC solution in the formation of the composite material.

[0086] In certain embodiments, the composite material includes about 0.001% to about 3% by weight of the acid based on the total weight of the composite material. In some embodiments, composite material includes about 0.01% to about 2% by weight of the acid based on the total weight of the composite material. In particular embodiments, the composite material includes about 0.02% to about 0.5% by weight of the acid based on the total weight of the composite material. In some embodiments, the acid includes or is acetic acid.

[0087] The pH of the composite material typically is in the range of about 3 to about 6. In some embodiments the pH of the composite material is in the range of about 4 to about 5.

[0088] 11

[0089] IPTS / 128677603.1 The total amount of the solvent (e.g., including a “first solvent” and a “second solvent”) in the composite material for water remediation can be between about 50% to about 99.9% by weight based on the total weight of the composite material. In various embodiments, the composite material includes about 70 to about 99.9% by weight of the

[0090] 5 solvent based on the total weight of the composite material. In some embodiments, the composite material includes about 80 to about 99.9% by weight of the solvent based on the total weight of the composite material.

[0091] In some embodiments, the weight ratio of chitosan to nanocomposite materials (i.e., metals and metal oxides) is from about 5-50: 1, or about 15-35: 1, or about 8-20: 1. In certain0 embodiments, the weight ratio of chitosan to the other polymer (e.g., chitosan to PVP) is about 1-20:1, about 3-12: 1, or about 5-10:1.

[0092] In certain embodiments, the composite material can include Ag (e.g., from about 6 mg / L to about 40 mg / L such as about 10 mg / L to about 30 mg / L), TiO2 (e.g., from about 100 mg / L to about 400 mg / L such as about 200 mg / L to about 375 mg / L, or about 250 mg / L to about 350 mg / L), Se (e.g., from about 0.01 mg / L to about 3 mg / L such as about 1 mg / L to about 2 mg / mL, or about 1 mg / mL to about 1.5 mg / mL), and chitosan (e.g., from about 0.1 g / L to about 20 g / L such as about 1 g / L to about 10 g / L or about 2 g / L to about 10 g / L). In particular embodiments, the composite material can include PVP (e.g., from about 0.01 g / L to about 2.5 g / L such as about 0. 1 g / L to about 5 g / L or about 0. 1 g / L to about 1 g / L). 0 In various embodiments, the composite material can include Ag (e.g., from about 6 mg / L to about 30 mg / L such as about 10 mg / L to about 20 mg / L), TiCb (e.g., from about 200 mg / L to about 400 mg / L such as about 200 mg / L to about 350 mg / L, or about 250 mg / L to about 350 mg / L), Se (e.g., from about 0.01 mg / L to about 4 mg / L such as from about 1 mg / L or about 1.5 mg / mL), Cu (e.g., from about 0.1 mg / L to about 4 mg / L such as about 1.5 mg / L to about 2.5 mg / L), and chitosan (e.g., from about 0.1 g / L to about 15 g / L such as about 1 g / L to about 10 g / L or about 2 g / L to about 8 g / L). In particular embodiments, the composite material can include PVP (e.g., from about 200 mg / L to about 750 mg / L such as about 350 mg / L to about 650 mg / L).

[0093] In some embodiments, the composite material can include Ag (e.g., from about 100 mg / L to about 15 mg / L), TiCL / e.g., from about 275 mg / L to about 350 mg / L), Se (e.g., from about 1 mg / L to about 1.5 mg / L), Cu (e.g., from about 1.5 mg / L to about 2.5 mg / L), chitosan

[0094] 12

[0095] IPTS / 128677603.1 (e.g., from about 2 g / L to about 7 g / L); and PVP (e.g., from about 450 mg / L to about 600 mg / L).

[0096] In some embodiments, the present teachings provide a composite material including silver, titanium dioxide, selenium, copper, chitosan, and a (another) polymer, and optionally

[0097] 5 silver chloride and an acid. In certain embodiments, the present teachings provide a composite material including silver, titanium dioxide, selenium, copper, chitosan, an acid and a polymer, and optionally silver chloride. In particular embodiments, the present teachings provide a composite material including silver, titanium dioxide, selenium, copper, chitosan, an acid, a (another) polymer, and silver chloride. In these embodiments, the above amounts described herein of the various components apply equally here as well as elsewhere in the application.

[0098] Methods of Making the Composite Materials

[0099] In another aspect, the present teachings provide a method of making a composite material. The methods can generally comprise mixing TiO (in an acidic solution) and salts5 of Ag (e.g., AgNC ), Cu (e.g., Cu(NO3)2*3H2O) and Se (e.g., Na2SeO4), and a polymer in a water to form a first mixture; exposing the first mixture to a reducing agent until less than about 15% of the Ag is Ag+to form a reduced mixture; mixing chitosan and an acid in a second solvent to form a second mixture; and adding a portion of the second mixture to a portion of the reduced mixture thereby forming a composite material, wherein the portion of0 the second mixture is between about 3% by weight to about 30% by weight of the total weight of the composite material. In some embodiments, the portion of the second mixture is between about 10% by weight to about 20% by weight of the total weight of the composite material

[0100] In certain embodiments, the methods for making a composite material of the present teachings can include mixing a polymer such as polyvinylpyrrolidone (PVP) with water to create a first mixture. The first mixture can contain from 0.3 mg / mL to about 2 mg / mL of the polymer in water depending on the final concentration of polymer, e.g., PVP, in the composite material.

[0101] A second mixture, which can be a concentrated solution, can be prepared by mixing0 TiCL in an acidic solution (e.g., 10% hydrochloric acid (HC1) solution) and salts of Ag (e.g., silver nitrate (AgNCh)), Cu (e.g., cupric nitrate trihydrate (Cu(NO3)2*3H2O)) and Se (e.g., sodium selenate (Na2SeO4)) in water. Again, the amounts of these components added to the

[0102] 13

[0103] IPTS / 128677603.1 second mixture will depend on the desired final concentration in the composite material. The amounts added should also take into consideration the dilution that occurs during making of the composite materials.

[0104] The first mixture can be added to the second mixture to provide another (third) mixture, which becomes a reduced mixture. More specifically, the third mixture is exposed to ultraviolet (UV) radiation such as UVC radiation (e.g., about 200 nm) until the amount of Ag present is less than about 20% Ag+, or less than about 15% Ag+, or less than about 10% Ag+, or less than about 5% Ag+. The amount of Ag+ present can be determined by using UV spectrometry, for example, at a wavelength of about 415 nm to about 430 nm.

[0105] In a separate, fourth mixture, chitosan is mixed with water usually containing an acid such as acetic acid. The chitosan can be present in amount between about 10 mg / mL to about 50 mg / mL. The acid can be present in an amount between about 0.5% to about 3% by weight of the total weight of the fourth mixture, for example, between about 0.5% to about 2%, or about 1% by weight of the total weight of the fourth mixture.

[0106] A portion of the third mixture (i.e., the reduced mixture) is mixed with a portion of the fourth mixture to provide the final product composite material. The portion of the third mixture (i.e., the mixture containing the reduced silver) relative to the portion of the fourth mixture (i.e., the mixture containing the reduced chitosan) can be from 2:1 to 20:1 depending on the desired composition of the final product composite material.

[0107] Water or other solvents used herein can contain one or more of monoethylene glycol (MEG), diethylene glycol (DEG), and combinations thereof.

[0108] The total amount of solvents in the composite material can be between about 50% to about 99.9% by weight based on the total weight of the composite material. In various embodiments, the composite material includes about 80% to about 99.9% by weight of solvents based on the total weight of the composite material. In some embodiments, the composite material includes about 90% to about 99.9% by weight of the solvents based on the total weight of the composite material.

[0109] The present teachings can describe the amount of “effective material” in a formulation, which is the total concentration of active metal species present in the formulation. For example, in Example 1 below, the total amount of effective material is about 307.8 mg / mL of composite TiCL-Ag-Cu-Se (i.e., 292 mg / L TiO2 + 12.76 mg / mL Ag + 1.9 mg / mL Cu + 1.15 mg / mL Se). The amount of effective material in a formulation

[0110] 14

[0111] IPTS / 128677603.1 typically is between about 100 mg / L and about 550 mg / L, or between about 100 mg / L to about 450 mg / L, or about 125 mg / L to about 375 mg / L, or about 200 mg / L to about 350 mg / L.

[0112] The amounts of the components that contribute to the effective material can be within their ranges as described herein. For example, TiCL is the predominant species or component contributing to the effective material, e.g., greater than 75%, 80%, 85%, 90%, or 95% of the total effective material. Silver, copper and selenium can also be included in the effective material where their amounts are greatly reduced. For example, silver can be present in an amount of about 3% to about 8% of the amount of TiCF; copper can be present in an amount of about 0.1% to about 1% of the amount of TiCF; and selenium present in an amount of about 0.01% to about 1% of the amount of TiCF.

[0113] Methods of Using the Composite Materials

[0114] In another aspect, the present teachings provide a method of composting comprising contacting a composite material as described herein with compostable materials in need of composting; and composting the compostable material to compost. The methods can further include remixing the compostable material. The remixing can occur at regular intervals, for example, weekly, every other day, daily, twice a day, or more frequently. During the remixing, the compostable material containing a composite material of the present teachings can be exposed to visible light and / or sunlight for a suitable time and under conditions suitable for the composite material to become “activated,” for example, producing ROS that can reduce noxious compounds and contaminants. Moreover, depending on the type of composting, the surface of the treated compostable materials can be exposed to visible light such, e.g., daylight, during daylight hours such that the photocatalytic properties of the composite material can be activated, assisting in the decomposition process.

[0115] Prior to applying the composite material onto the compostable materials, the composite material is usually diluted with water. Depending on the amount of composite material and the amount of compostable material, the composite material can be diluted with a solvent, typically water, about 10 to about 100 times, for example, 500 mL composite material is diluted about 20 times with 10 L water. Any means of contacting the composite material with the compostable material can be used. However, spraying the composite material onto the compostable material while it is being mixed or rotated is an effective way to disperse the composite material on and in the compostable material.

[0116] 15

[0117] IPTS / 128677603.1 In various embodiments, the composting is conducted in a compost tumbler, a compost bin, a compost pile, an in-ground trench or hole, or a windrow composting line, trench or tunnel. In some embodiments, the remixing is by hand, or with a shovel or a pitch folk or similar device. In certain embodiments, the remixing is accomplished by rotating a compost tumbler a certain number of times. In particular embodiments, the remixing is done by a compost windrow.

[0118] Using a compost windrow along with a windrow composting line, trench or tunnel, a continuous composting process can be realized where fresh or newly treated compostable materials are added to the start of the windrow composting line, trench or tunnel, and the compost windrow mixes and moves the compostable materials along the line, trench or tunnel such that at the other end, compost results. The specific design, e.g., length of the line, trench or tunnel and speed of the compost windrow, would need to be determined based on how long it takes for the composting process to be completed.

[0119] The results of the composting process can be measured by a variety of parameters. For example, the amounts of the following parameters can be measured during the composting process to monitor its progress: temperature, methane (CH4) emissions, ammonia (NH3) emissions, and / or carbon dioxide (CO2) emissions. These parameters are typically measured using industry standard analytical techniques, which can include portable equipment for measurements in the field. For example, temperature can be measured using a Digital Industrial K-type Thermocouple Thermometer HVAC 2x Stainless Steel Probe, where the probe can be about 100 cm. Methane released from the compostable material can be measured in ppm (or mg / L) at its surface using a “Smart Sensor AS8800C.” Carbon dioxide released from the compostable material can be measured in ppm (or mg / L) at its surface using a “Smart Sensor AS8200.” Ammonia released from the compostable material can be measured in ppm (or mg / L) at its surface using a “Smart Sensor AR8500.”

[0120] Measurements of the above parameters and remixing of the compostable materials should usually be done at about the same time each day or at whatever interval those activities are undertaken.

[0121] For context, the measurements from composting compostable materials treated with a composite material of the present teachings is usually compared to composting compostable materials that were not treated with a composite material (a “control”) (where preferably each

[0122] 16

[0123] IPTS / 128677603.1 has the same composition of compostable materials). The control is usually sprayed with an equal amount of water as the diluted composite material mixture that was used.

[0124] For example, a decrease in methane emissions from composting material compared to a control of about 45% can be realized in about two and one half weeks with just one

[0125] 5 treatment of the composite material. A decrease in ammonia emissions from composting material compared to a control of about 85% can be realized in about two and one half weeks with just one treatment. Over nearly three weeks, the overall daily average of methane emission and of ammonia emission can be reduced about 90%, Over nearly three weeks, the daily average of carbon dioxide can be reduced about 25%. 0 The temperature of the compostable materials can be a good indicator of the amount of composting that is occurring where a higher temperature indicates that a more efficient and effective composting, i.e., changing the compostable materials into compost in a quicker process. A higher temperature also can show more aerobic activity. However, an increased temperature usually coincides with more carbon dioxide production, which usually occurs much earlier in the process with treated compostable material than with control compostable material. Although the overall amount of carbon dioxide produced can be greater over about two weeks, usually over that time, for example, three or four weeks, less carbon dioxide tends to be produced by the treated compostable material. The earlier production of carbon dioxide and the increased temperature earlier in the composting process evidences the expedited and0 more efficient composting process.

[0126] Examples

[0127] Example 1. Production of Composite Material #1

[0128] One liter (1 L) of composite material was made by preparing a first mixture of polyvinylpyrrolidone (PVP) (640 mg) in about 987.5 mL water at ambient temperature.

[0129] A second mixture was prepared by mixing 3.65 mL of a titanium dioxide (TiO2) solution (100 g / L TiO2 in 10% HC1 aqueous solution) (contains 365 mg of TiO2), silver nitrate ( AgNCh) (25.12 mg dissolved in 4.975 mL of distilled water), cupric nitrate trihydrate (CU(NO3)2*3H2O) (8.98 mg dissolved in 4.991 mL of distilled water) and sodium selenate (Na2SeOr) (3.5 mg dissolved in 4.997 mL distilled water) for 24 hours. The first mixture is0 mixed with the second mixture to provide a third mixture of about 1 L. The third mixture was mixed and exposed to UV radiation until the conversion of Ag+ to Ag became about 90% (i.e., less than about 10 % by weight of Ag+remains in the third mixture).

[0130] 17

[0131] IPTS / 128677603.1 Separately, 28 g chitosan was mixed with 11 mL of acetic acid in 989 mL distilled water to form a fourth mixture.

[0132] Next, 800 mL of the third mixture was added to 200 mL of forth mixture to form 1 L of final mixture, i.e., a composite material.

[0133] The amount of effective material considered for this formulation’s concentration is about 307.8 mg / mL of composite TiCb-Ag-Cu-Se (i.e., 292 mg / L TiCh + 12.76 mg / mL Ag + 1.89 mg / mL Cu + 1.15 mg / mL Se).

[0134] Example 2. Composting Test # 1

[0135] Two one cubic meter sized holes in the ground were filled with compostable material, where one cubic meter of compostable material weighs about 650 kg. The compostable material included 65% cow manure, 15% rice husk, 5% saw dust, and 15% waste food. Before putting in the ground, one of the cubic meters of compostable material was treated with the composite material of Example 1.

[0136] More specifically, for the treated compostable material, prior to application to the compostable material, about 100 mL of the composite material of Example 1 was diluted 50 times with water, here, about 5 L of water. The resulting diluted solution was sprayed on the compostable material while it was being mixed for composting. Subsequently, the treated compostable material was placed in a hole in the ground.

[0137] The other cubic meter of compostable material was not treated but sprayed with about 5 L of water while mixing for composting, then placed in another hole in the ground. This untreated compostable material was used as a control. The compostable materials were exposed to the daylight at their surfaces during the testing time.

[0138] On the seventh day after the first treatment, the compostable material was mixed well with a shovel. The control compostable material also was mixed in the same manner at this time. On the tenth day after the first treatment, the compostable material was again mixed well with a shovel. The control compostable material also was mixed in the same manner at this time.

[0139] The following results in Table 1 were recorded daily at approximately the same time each day, where T is treatment and C is the control. All measurements were made with handheld devices for field measurements. Tern is the temperature of the compostable material as measured using a Digital Industrial K-type Thermocouple Thermometer HVAC 2x Stainless

[0140] 18

[0141] IPTS / 128677603.1 Steel Probe, where the probe was 100 cm, which is stuck into the compostable material. CH4 is the amount its methane in ppm (or mg / L) released from the compostable material as measured at its surface using a “Smart Sensor AS8800C.” CO2 is the amount of carbon dioxide in ppm (or mg / L) released from the compostable material as measured at its surface using a “Smart Sensor AS8200.” NH3 is the amount of ammonia in ppm (or mg / L) released from the compostable material as measured at its surface using a “Smart Sensor AR8500.”

[0142] The results of these measurements are shown in Table 1.

[0143] Table 1

[0144] As can be seen in Table 1, methane emission was reduced about 46% in 16 days in the treated compostable material, and ammonia emission was reduced about 85% over that same time period in the treated compostable material. The higher temperature shows more aerobic activity and thus, more carbon dioxide production earlier in the time period. The rapid increase in temperature earlier in the time period also shows expedition of the composting.

[0145] Example 3. Production of Composite Material # 2

[0146] One liter (1 L) of composite material was made by preparing a first mixture of polyvinylpyrrolidone (PVP) (640 mg) in about 987.5 mL water at ambient temperature.

[0147] A second mixture was prepared by mixing 3.65 mL of a TiCL solution (100 g / L TiO2 in 10% HC1 aqueous solution) (contains 365 mg of TiO2), AgNCL (25.12 mg dissolved in 4.975 mL of distilled water), cupric nitrate trihydrate (Cu(NO3)2*3H2O) (8.98 mg dissolved in 4.991 mL of distilled water) and sodium selenate (Na2SeC>4) (3.5 mg dissolved in 4.997 mL distilled water) for 24 hours. The first mixture is mixed with the second mixture to provide a third mixture of about 1 L. The third mixture was mixed and exposed to UV radiation until

[0148] 19

[0149] IPTS / 128677603.1 the conversion of Ag+ to Ag became about 90% (i.e., less than about 10 % by weight of Ag+remains in the third mixture).

[0150] Separately, 28 g chitosan was mixed with 11 mL of acetic acid in 989 mL distilled water to form a fourth mixture.

[0151] Next, 900 mL of the third mixture was added to 100 mL of forth mixture to form 1 L of final mixture, i.e., a composite material.

[0152] The amount of effective material considered for this formulation’s concentration is about 346.28 mg / mL of composite TiO2-Ag-Cu-Se (i.e., 328.5 mg / L TiCh + 14.36 mg / mL Ag + 2.12 mg / mL Cu + 1.30 mg / mL Se).

[0153] Example 4 - Composting Test # 2

[0154] The raw compostable material was about 35% dry seaweed and about 65% horse manure.

[0155] For treating the raw compostable material, about 19 times of an amount of water is added to the composite material of Example 3. More specifically, 500 mL of the composite material of Example 3 was mixed with 9.5 L tap water. The resulting mixture was sprayed onto 50 kg of the raw compostable material while mixing it for composting. The material was then moved to a compost tumbler for 20 days of testing. This procedure was repeated three more times for four compost tumblers total containing treated compostable material.

[0156] As a control, four other compost tumblers were filled with 50 kg of the raw compostable material, where only 10 L tap water was sprayed onto the mixing compostable material while mixing before adding it to a compost tumbler.

[0157] Each compost tumbler was rotated 20 times once per day to aerate and remix the compostable material and compost after each measurement had been completed. The measurements were taken between about 12:30 pm- 1:30 pm each day, measuring temperature of the compostable material, and the emission of methane (CH4), carbon dioxide (CO2), and ammonia (NH3) from the compost tumbler. All measurements were taken with hand-held devices for field measurements. Temperature was measured using a Digital Industrial K-type Thermocouple Thermometer HVAC 2x Stainless Steel Probe, where the probe was 100 cm. Methane was measured using a “Smart Sensor AS8800C,” carbon dioxide was measured using a “Smart Sensor AS8200,” and ammonia was measured using a “Smart Sensor AR8500.” All of the measurements in the following tables are in ppm.

[0158] 20

[0159] IPTS / 128677603.1 The results of the measurements from each of the compost tumblers are shown in Tables 2-5 below. It should be noted that no measurements were taken on Days 11-14 and no CH4 measurements were taken on Day 9 (ND = not determined).

[0160] 21

[0161] IPTS / 128677603.1 Table 2

[0162] Temperature (°C)

[0163] Tumbler ID Day l: Day 2: Day 3: Day 4: Day 5: Day 6: Day 7: Day 8: Day 9:

[0164] Experiment 1 34 40 34 35.2 32 37.7 34 30 27

[0165] Experiment 2 33 38 33 35.3 32 34 33 28 T1

[0166] Experiment 3 33 40 35.5 32 37 32 33 27 26

[0167] Experiment 4 33 41 35.5 35.2 32 33 34 27 27

[0168] Control 1 32 41.6 36.6 34 30 31 33 33 30

[0169] Control 2 34 41 34 32 29 31 33 26 25

[0170] Control 3 32 46.6 34 32 29 28 32 26 25

[0171] Control 4 32 42.7 36.6 31.6 30 30 34 26 26

[0172] Temperature Day Day Day: Day: Day: Day: Average Total Tumbler ID 10: 15: 16 17 18 19 per day Average

[0173] Experiment 1 1 26 26 24 23 23 30.19 Experiment 2 25 25 25 24 23 23 29.22 Experiment 3 25 24 24 24 23 24 29.30 Experiment 4 26 24 25 24 23 23 29.51 29.56 Control 1 25 23 24 25 27 27 30.15 Control 2 24 24 22 23 22 22 28.13 Control 3 23 23 21 21 21 21 27.64

[0174] Control 4 24 24 20 20 20 20 27.79 28.43

[0175] 22

[0176] IPTS / 128677603.1 Table 3

[0177] CH4 Day Day Day Day Day Day Day Day Day

[0178] Tumbler ID 1: 2: 3: 4: 5: 6: 7: 8: 9:

[0179] Exper. 1 0.6 0.16 0 0 0 13 127 0 ND

[0180] Exper. 2 0.2 0.04 0 0 0 0 10 0 ND

[0181] Exper. 3 0.12 0.24 0 0 0 52 3 0 ND

[0182] Exper. 4 0.38 0.06 0 0 0 18 36 0 ND

[0183] Control 1 0.44 0 0 244 244 170 660 562 ND

[0184] Control 2 0.35 0 0 35 37 50 79 83 ND

[0185] Control s 0.11 0 0 80 53 52 165 147 ND

[0186] Control 4 0.97 0.41 0 241 149 261 625 523 ND

[0187] Control 5 0.04 0 0 9 10 0 93 20 ND

[0188] CH4 Day Day Day: Day: Day: Day: Ave / Total

[0189] Tumbler ID 10: 15: 16 17 18 19 day Average

[0190] Exper. 1 0 0 0 0 0 0 10.05

[0191] Exper. 2 0 0 0 0 0 0 0.73

[0192] Exper. 3 0 50 0 0 0 0 7.53

[0193] Exper. 4 0 16 93 37 0 0 14.32 8.16

[0194] Control 1 0 361 186 83 56 10 184.03

[0195] Control 2 0 146 10 32 10 10 35.17

[0196] Control 3 0 176 182 136 150 103 88.87

[0197] Control 4 219 507 490 424 390 340 297.88

[0198] Control 5 0 0 101 106 92 101 38.00 114.98

[0199] 23

[0200] IPTS / 128677603.1 Table 4

[0201] CO2

[0202] Day Day Day Day Day Day Day Day Day

[0203] Tumbler ID 1: 2: 3: 4: 5: 6: 7: 8: 9:

[0204] Exper. 1 981 841 774 451 606 692 570 578 823

[0205] Exper. 2 1544 1082 1169 470 622 783 1349 785 1153

[0206] Exper. 3 3993 1629 3083 808 1100 1356 1201 952 1310

[0207] Exper. 4 2740 1168 1473 760 770 1110 1215 1271 1111

[0208] Control 1 3991 3031 2229 460 2374 4656 1951 2399 1142

[0209] Control 2 3795 998 1161 772 1081 1079 1257 1024 1240

[0210] Control 3 2437 1085 1754 673 1082 1219 1045 1257 1480

[0211] Control 4 2591 2166 1615 914 1106 1023 1064 806 1656

[0212] Day Day Day: Day: Day: Day: Ave / Total

[0213] Tumbler ID 10: 15: 16 17 18 19 day Average

[0214] Exper. 1 400 552 746 718 671.69

[0215] Exper. 2 505 584 650 680 660 650 845.73

[0216] Exper. 3 852 1495 1370 1400 1260 1557.79

[0217] Exper. 4 522 762 821 821 1118.77 1048.50

[0218] Control 1 952 1119 984 984 2020.92

[0219] Control 2 661 1031 1203 1203 1269.62

[0220] Control 3 740 997 980 994 1017 1010 1184.67

[0221] Control 4 537 1207 1060 1060 1292.69 1441.97

[0222] 24

[0223] IPTS / 128677603.1 Table 5

[0224] NH3 Day Day Day Day Day Day Day Day

[0225] Tumbler ID 1: Day 2: 3: 4: 5: 6: 7: 8: 9:

[0226] Experimental

[0227] 1 0 3.4 9.0 0 0 0 0 0 0

[0228] Experimental

[0229] 2 0 0 0.0 0 0 0 0 0 0

[0230] Experimental

[0231] 3 0 0 0.0 0 0 0 0 0 0

[0232] Experimental

[0233] 4 0 0 0.0 0 0 0 0 0 0

[0234] Control 1 0 0 0.0 0 19 0.8 0 5.8 0

[0235] Control 2 0 0 0.0 0 5.6 15.4 0 3.6 0.8

[0236] Control 3 0 0 0.0 0 10.5 0 0 10.9 1.8

[0237] Control 4 0 0 0.0 0 22.1 15 0 35.2 0

[0238] Day Day Day Day Day Day Ave / Total

[0239] Tumbler ID 10 15 16 17 18 19 day Average

[0240] Exper. 1 0 0 0 0 0 0.89

[0241] Exper. 2 0 5.4 1.8 2.1 1.5 I.1 0.79

[0242] Exper. 3 0 5.4 0 0 0 0 0.36

[0243] Exper. 4 0 11.3 10.9 10.3 9.5 7.6 3.31 1.34

[0244] Control 1 78.3 29.9 29.3 26.9 23.4 20.4 15.59

[0245] Control 2 0 17.2 17.2 15.6 14 II.3 6.71

[0246] Control 3 0 16.8 14 15.6 15.2 14 6.59

[0247] Control 4 37.7 55.7 46.7 38.4 34.5 29.5 20.99 12.47

[0248] As can be seen in the above, the overall daily average of methane emission was

[0249] 5 reduced by about 93% over 19 days, and the overall daily average of ammonia emission was reduced by about 90% over 19 days. Further, the overall daily average of carbon dioxide emission was reduced by about 27% over 19 days.

[0250] Example 5 - Composting Test # 3

[0251] For treating the raw compostable material, about 19 times of an amount of water is0 added to the composite material of Example 3. More specifically, 30 L of the composite material of Example 3 was mixed with 570 L tap water. The resulting mixture was sprayed onto 30 tons of the raw compostable material (about 50 cubic meters) while mixing it for composting.

[0252] The treated compostable material was then moved to the front end (start) of a compost 5 trench for daily mixing and movement with a compost windrow installed on top of the trench

[0253] 25

[0254] IPTS / 128677603.1 that moved from one end to the other end of the trench, mixing the compostable material. The compost trench was 60 meters in length, 5 meters wide and 2.5 meters in height with an open top side for placement of the compost windrow. The 30 tons of newly treated compostable material was added at one end of the compost trench and was mixed and moved towards the other end of the compost trench where about 30 tons of compost was removed daily. The time in the compost trench was about 15 days as the compost windrower moved at a speed of about 12 meters per hour and worked about 10 hours per day so that each compost trench was mixed twice each day and moved compostable material / compost about 4 meters towards the exit of the compost trench every day.

[0255] As a control, another compost trench was filled with 30 tons of the same raw compostable material each day, where only 600 L tap water (no composite material) was sprayed onto the compostable material while mixing before adding it into a compost trench. The compost windrow and the addition and removal of composting materials and compost was the same as discussed above for the compost windrow trench having the treated compostable material. Initially, each compost trench is filled with untreated compostable material, with the 30 tons of treated compostable material added each day to the testing compost trench (compost trench 1) and 30 tons of untreated compostable material added to the control compost trench (compost trench 2).

[0256] Measurements were taken between about 10:00 am- 12:00 pm each day, measuring temperature of the compostable material, and the emission of ammonia (NH3) from the compost trench. Three measurement points selected from each compost trench line at about 10 meters from the start (where fresh compostable material was introduced to the compost trench) (“Pl” in the below tables), about 30 meters from the start (“P2”), and about 59 meters from the start (“P3”). The temperature of the compostable material and emission of ammonia was reported on the measurement days in the tables below. All measurements were taken with hand-held devices for field measurements. Temperature was measured using a Digital Industrial K-type Thermocouple Thermometer HVAC 2x Stainless Steel Probe, where the probe was 100 cm. Ammonia was measured using a “Smart Sensor AR8500.” All of the measurements in the following tables are in ppm.

[0257] The results of the measurements from each of the compost trenches are shown in Tables 6 and 7 below. It should be noted that measurements were not taken every day and that compost trench 1 is for the treated compostable material and compost trench 2 was for the untreated compostable material. Further, the 4-day average is the average of the

[0258] 26

[0259] IPTS / 128677603.1 measurements taken on days 16, 18, 19 and 21 because it took 15 days for the compostable material to enter and then exit their respective trenches.

[0260] Table 6

[0261] Temperature (°C)

[0262] Day Day Day

[0263] Point Day 1: Day 3: Day 5: Day 6: Day 8: 10 Day 11 13 15

[0264] Trench 1 Pl 33.9 47.5 48.3 49.2 49.1 49.5 49.3 49.3 49.2

[0265] Trench 1_P2 42.3 42.2 42.4 42.6 47.2 55.3 59.2 62.1 62.5

[0266] Trench 1_P3 48.5 47.6 48.0 45.8 44.5 42.3 40.9 40.3 38.0

[0267] Trench 2_P1 33.1 33.2 33.5 33.3 33.5 34.0 33.8 33.8 34.0

[0268] Trench 2_P2 42.3 42.2 42.5 42.5 40.2 42.1 42.3 42.7 42.0

[0269] Trench 2_P3 55.2 54.8 55.0 55.4 55.3 55.1 55.4 55.2 55.2

[0270] Temperature (°C)

[0271] Day Day Day 4-day

[0272] Point Dayl6 18 19 21 Average

[0273] Trench 1 Pl 49.7 49.9 50.5 49.7 49.95

[0274] Trench 1_P2 62.1 62.8 62.5 62.4 62.45

[0275] Trench 1 P3 37.1 36.2 35.5 35.3 36.02

[0276] Trench 2_P1 33.7 33.5 33.5 33.2 33.47

[0277] Trench 2_P2 42.1 42.3 42.7 42,5 42.36

[0278] Trench 2_P3 55.2 55.1 55.0 55.1 55.1

[0279] The average temperatures at points 1 and 2, which typically are higher than at point 3, are in the composting “zones” and show more aerobic bacteria activity and faster decomposition of the raw compostable material than when at a lower temperature. The 4-day average temperature of the treated compostable material (Trench 1) shows that the process is completed and gradually the compost is in the curing phase and ready to be used (e.g., packaged and shipped). And as noted in Table 7, at point 3, the ammonia emissions are significantly reduced for the final product.

[0280] In general, for the treated compostable material, the temperature at point 1 shows that that start of the composting process is sooner; at point 2, the decomposition rate is higher; and at point 3, the compostable material has reached its curing phase and completion of the composting in a shorter time than in the untreated (control) trench.

[0281] For the untreated (control) trench, the 4-day average temperature shows a higher temperature at point 3 than at point 2, which is higher than at point 1. Such a trend indicates that the compostable material needs more composting time in the trench, which could be accomplished by lowering the speed of movement of the compostable material through the

[0282] 27

[0283] IPTS / 128677603.1 trench, e.g., 2 meters per day of movement rather than the 4 meters per day that was sufficient for the treated compostable material.

[0284] Table 7

[0285] NH3

[0286] Day Day Day Day

[0287] Point Day 1: Day 3: Day 5: Day 6: Day 8: 10 11 13 15

[0288] Trench 1_P1 100 100 100 100 100 100 100 100 100

[0289] Trench 1_P2 100 100 100 100 100 76.8 54.2 44.0 43.8

[0290] Trench 1_P3 44.0 42.5 43.3 44.1 43.9 44.4 44.2 21.7 13.5

[0291] Trench 2_P1 100 100 100 100 100 100 100 100 100

[0292] Trench 2_P2 100 100 100 100 100 100 100 100 100

[0293] Trench 2_P3 44.0 42.5 43.3 44.1 43.9 44.4 44.2 44.0 43.8

[0294] NH3

[0295] Day Day Day Day 4-day

[0296] Point 16 18 19 21 Average

[0297] Trench 1_P1 100 100 100 100 100

[0298] Trench 1_P2 44.4 44.2 44.0 43.8 44.1

[0299] Trench 1_P3 13.3 13.2 13.0 13.1 13.15

[0300] Trench 2_P1 100 100 100 100 100

[0301] Trench 2_P2 100 100 100 100 100

[0302] Trench 2_P3 42.5 43.3 44.1 43.9 43.95

[0303] After the 15 -day composing period, the ammonia reduction is reduced on average over 86% per day based on the 4-day average compared to about a 56% reduction on average per day based on the 4-day average.

[0304] INCORPORATION BY REFERENCE

[0305] This application refers to various issued patents, published patent applications, journal articles, and other publications, all of which are incorporated herein by reference. If there is a conflict between any of the incorporated references and the instant specification, the specification shall control. In addition, any particular embodiment of the present disclosure that falls within the prior art may be explicitly excluded from any one or more of the claims. Because such embodiments are deemed to be known to one of ordinary skill in the art, they may be excluded even if the exclusion is not set forth explicitly herein. Any particular embodiment of the disclosure can be excluded from any claim, for any reason, whether or not related to the existence of prior art.

[0306] 28

[0307] IPTS / 128677603.1 EQUIVALENTS

[0308] The disclosure may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The foregoing embodiments are therefore to be 5 considered in all respects illustrative rather than limiting the disclosure described herein.

[0309] Scope of the disclosure is thus indicated by the appended claims rather than by the foregoing description, and all changes that come within the meaning and range of equivalency of the claims are intended to be embraced therein.

[0310] 29

[0311] IPTS / 128677603.1

Claims

1. CLAIMSWhat is claimed is:

1. A composite material comprising: titanium dioxide;5 silver; copper; selenium; and chitosan.

2. The composite material of claim 1 , further comprising polyvinylpyrrolidone.

3. The composite material of claim 1, comprising titanium dioxide (TiCL ) coated silver (Ag) (“(TiChln / Ag") particles, copper (Cu), and selenium (Se), wherein the TiCh / Ag particles, Cu and Se are associated with chitosan and a polymer in a solvent.

4. The composite material of claim 3, wherein the polymer is polyvinylpyrrolidone.

5. The composite material of claim 3 or 4, wherein the solvent is water.

6. The composite material of any one of claims 1-5, wherein the TiCb comprises substantially anatase phase TiCh.

7. The composite material of any one of claims 1-6, wherein the Ag comprises less than about 10% of Ag+.

8. The composite material of any one of claims 3-7, wherein the (TiChln / Ag particles are coated by and / or encapsulated by the chitosan and the polymer.

9. The composite material of any one of claims 1-8, wherein the Ag is in the form of particles having a mean diameter of between about 15 nm and about 75 nm.

10. The composite material of any one of claims 1-9, wherein the TiO? is in the form of particles having a mean diameter between about 0.5 nm and about 20 nm. 5 1 1. The composite material of any one of claims 3-10, wherein the solvent comprises one or more of water, ethylene glycol, methylene glycol, diethylene glycol, and an acid.

12. The composite material of claim 11, wherein the acid is acetic acid.30IPTS / 128677603.

113. The composite material of any one of claims 3-12, comprising about 50% to about 99.8% by weight of the solvent based on the total weight of the composite material.

14. The composite material of any one of claims 11-13, comprising about 0.001% to about 3% of the acid based on the total weight of the composite material.5 15. The composite material of any one of claims 1-14, wherein the concentration of the chitosan is about 0.5 g / L to about 10 g / L.

16. The composite material of any one of claims 1-15, wherein the concentration of the TiCh is about 50 mg / L to about 1000 mg / L.

17. The composite material of any one of claims 1-16, wherein the concentration of the0 Ag is about 5 mg / L to about 35 mg / L.

18. The composite material of any one of claims 1-17, wherein the concentration of the Cu is about 0.5 mg / L to about 5 mg / L.

19. The composite material of any one of claims 1-18, wherein the concentration of the Se is about 0.05 mg / L to about 3 mg / L.

20. The composite material of any one of claims 3-19, wherein the concentration of the polymer is about 0.01 g / L to about 5 g / L.

21. The composite material of any one of claims 1-20, wherein the composite material is diluted with about 5 times to about 100 times with water before application to a compostable material. 0 22. A method of making a composite material comprising: mixing TiCL, and salts of Ag, Cu and Se, and a polymer in a first solvent to form a first mixture; exposing the first mixture to a reducing agent until less than about 15% of the Ag is Ag+to form a reduced mixture; 5 mixing chitosan and an acid in a second solvent to form a second mixture; and adding a portion of the second mixture to a portion of the reduced mixture thereby forming a composite material, wherein the portion of the second mixture is between about 3% by weight to about 30% by weight of the total weight of the composite material.31IPTS / 128677603.

123. The method of claim 22, wherein the reducing agent comprises ultraviolet radiation, micro waves, or a combination thereof.

24. The method of claim 22 or 23, wherein the portion of the second mixture is between about 10% by weight to about 20% by weight of the total weight of the composite material.5 25. A method of reducing at least one of methane emission, ammonia emission and carbon dioxide emission during composting comprising: contacting and mixing a compostable material with the composite material of any one of claims 1-21 ; and composting the compostable material to cause at least one of methane emission,0 ammonia emission and carbon dioxide emission from the compostable material to be reduced compared to a control of compostable material without exposure to the composite material of any one of claims 1-21.

26. The method of claim 25, wherein the method comprises remixing the compostable material. 5 27. The method of claim 26, wherein the remixing occurs daily.

28. The method of any one of claims 25 to 27, wherein the composting is conducted in a compost tumbler, a compost bin, a compost pile, an in-ground trench or hole, or a windrow composting line, tunnel or trench.32IPTS / 128677603.1

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