CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application is related to, and claims priority to, Provisional Patent Application No. 62/788,806, entitled “OCEAN REMEDIATION AND C02 SEQUESTRATION NANOBIOCOMPOSITE AND PEACEKEEPING METHODS OF USE,” filed January 5, 2019, the entire contents of which is incorporated herein in its entirety.

BACKGROUND

1. FIELD OF INVENTION

[0002] The present invention relates to treatment of oceanic near-surface waters to remediate waste products, and more particularly, to a means of capturing carbon dioxide from the atmosphere and the ocean.

2. BACKGROUND ART

[0003] The cleanup of oil spills have obtained localized and limited success by setting out floatation snakes containing oil-swelling media, such as fibrillated plastics, protein containing materials such as human hair, organophilic clay particulates, and various combinations intended to minimize visible ecosystem collateral damage while procuring or transporting petroleum primarily for maintaining the economic gain obtainable by burning processed petrochemicals as the most inexpensive source of hydrocarbons for energy and plastic feedstocks.

[0004] The idea to fertilize the oceans to create enhanced biomass is fundamentally different concept than visible oceanic waste management. One potential biomass objective discussed in the literature has been geared to reversing increasing trends in atmospheric carbon dioxide content with little or no effort, or progress made, in enhancing the robustness of oceanic ecosystems. Present day state of the art efforts at ocean fertilization have reached a technological plateau, because methods to retain the fertilization compounds at approximately the top 12 inches of the ocean surface and indeed better aimed at about the top inch of high carbon dioxide containing surface waters, have met with limited or no success. Further improvement of materials, technologies, and the sociopolitical drivers of their development, remain to be identified and tested before any serious further progress in ocean ecological administration can begin. The future creation and development of geopolitical international oceanic water fishing and aquaculture rights located far from national borders are as important as the development of any technical concepts to restrict the rapid migration of ocean applied surface fertilizer into deeper ocean waters. Both the technical challenges and the political basis for any ecological cooperation on international levels have met with little or no conceptual success. This restricts fertilization efforts to shallow ocean regions within national borders where semipermeable nets, pure commercial gain, and the presence of shallow water to constrain fertilizer movement, drive the present ocean aquaculture ecology efforts. Such enterprises presently remain transient and short sighted with respect to immediate shallow ocean aquaculture profiteering such as the development of privately owned oyster or shrimp farms, and leave the regions well offshore open to unconstrained exploitation without a hierarchy of mechanisms in place to maintain or to restore biodiversity after rampant over-fishing and over-harvesting have taken place.

[0005] Methods to remediate plastic waste in the deep ocean also suffer from several technological and political setbacks, because the undefined ownership of international waters continues to allow these regions to be used as an international waste dumping ground. In one approach, the ability to sweep up local concentrations of floating plastic waste which has concentrated at the known oceanic gyres, has met with limited or no success, because the nets used to sweep up these materials have insufficiently small pores or are not sufficiently deep, or are not sufficiently tall, to prevent plastic waste from simply migrating around these manmade barriers. This results in a loss of a profit motive for capture and recycling of oceanic waste plastics. Attempts at international regulations to prevent such waste dumping have proven unenforceable.

[0006] In another approach, the shift to bioplastics capable of biodegradation has met with limited success on the land where microbes associated with surface soils are able to digest some of these materials. However, there are no such known microbes that can digest such biodegradable plastics in the saltwater ocean environment, because they are not water soluble, or because the technology to degrade them has not been adequately envisioned for oceanic environments. In this case, it is quite clear that biodegradable does not mean ocean degradable or ocean-specific degradable. Also, the concept of biodegradation is substantially misleading to the public with respect to the fate of such plastics with respect to eventual oceanic pollution. The nearest semi-soluble plastic candidates of biopolymers identified to date, are obtained by processing harvested algae. Such products are being studied, but they are not presently available commercially. The focus for such materials development has been to reduce the reliance on fossil petroleum hydrocarbon feedstocks for plastics, which may limit eventual release into the atmosphere as carbon dioxide.

[0007] Non-ocean based global cooling concepts have been discussed in the literature, with limited studies. One such concept has focused attention on the deployment of finely divided solids made into atmospheric aerosols using such materials as calcium carbonate or sulfur dioxide. These ideas are to reflect solar radiation into outer space and away from planet earth by micron sized particulate injection into the earth’s stratosphere. While extremely limited testing has already begun on this technology, it is quite controversial, and has met with justifiable critique, including that of removing a necessary energy source from the oceans, or causing further acidification of the oceans. The oceans are already suffering from carbonic acid acidity arising from excess carbon dioxide content, and there is a significant trend in increased biodiversity loss from such acidity. Adding to acid rain by sulfur injection to the atmosphere not otherwise counterbalanced with cation species, eventually produces sulfuric acid. Environmentalists are therefore justifiably opposed to any further manmade lowering of oceanic pH, as the ability of the oceans to contain life and provide foodstuffs is already significantly compromised, as oceanic resources continue to plummet and ocean temperatures rise, while oceanic dissolved oxygen content continues to decrease.

[0008] Present day oceanic ecological resource management are being economically, geopolitically, and technologically constrained. Technological and political efforts have failed to combine a sufficiently multidisciplinary approach to successfully achieve substantial offshore ocean surface water fertilization, remediate oil spill residuals that escape the standard floating snake absorption schemes, or to remediate micro-plastic ocean pollutants. A multidisciplinary confluence of technology and methods of administration to recover the decline in oceanic biodiversity, reduce ocean acidity from carbon dioxide, recover from global warming effects, and sequester carbon dioxide, have yet to be discovered.

[0009] The method of the present invention aims to overcome multiple obstacles to climate change mitigation as well as to progress in oceanic ecological resource growth by providing methods and materials having multiple dimensions of relief at reasonable economic cost and considerable avoidance of the threat of war and social conflict, in a new ecological framework that identifies what is required to advance the social, political, and technological aspects of the present invention, each of which may be applied together to achieve the intended functional purpose. SUMMARY OF THE INVENTION

[0010] The present invention provides embodiments of a nanobiocomposite nutrient carrier, which can nourish aquatic organisms, remediate oil and plastics, sequester C02, increase 02 in an aquatic body, and provide reflective shading, leading to cooling of that body. The nanobiocomposite nutrient carrier can include a first phase containing a water- soluble biopolymer constituent having at least one preselected iron nutrient, in which the preselected iron nutrient nourishes at least one predetermined aquatic organism. The water-soluble biopolymer component can include a hydrogen-bonded interpenetrating polymer network entrapping the preselected iron nutrient, which can be an iron-rich, nutrient phase including one of iron oxide (Fe2+), iron oxide (Fe3+), iron sulfate, or an effective combination thereof. A particle size of the preselected iron nutrient can be less than or equal to about 100 nm, and the nutrient carrier is buoyant having a density of less than about 1.0 g/cm3. In some embodiments, there can be a second dispersed phase which may at least partially surround the first phase. A particle size of the second dispersed phase is less than or equal to about 100 nm. The second dispersed phase includes gas inclusion voids to allow the density of the second dispersed phase to be less than about 1.0 g/cm3. The outer silicate-rich second dispersion phase can include a cross- linked silica gel. The iron-rich nutrient first phase and silicate-rich second phase can be hydrogen bonded together as an interpenetrating polymer network (IPN). In certain embodiments, a nanocomposite dispersion morphology of the first phase and the second dispersed phase can be of a shell-and-core type, with either the first or the second dispersed phase serve as a shell or a core. Embodiments may include reflective particles which can be crystals of titanium dioxide of size less than or equal to about 0.15 millimeters. Embodiments also can include a second dispersed phase of soluble silicate- rich including one of a soluble silicate salt, fumed silica, or silicic acid. Further embodiments can include a reflective titanium dioxide component including a photoactive anatase crystal form. The reflective titanium dioxide component size can be between about 100 mesh (about 0.149 mm diameter) to about 250 mesh (about 0.053 mm).

[0011] Other embodiments provide a water remediation material, which can have a nutrient constituent with particles less than or equal to about 100 nm, and a density less than about 1.0 g/cm3. The nutrient constituent can include a first carbohydrate polymer network including a biopolysaccharide, at least one mineral nutrient coupled to the first carbohydrate polymer network, a second carbohydrate polymer network, a cross-linking agent bonding the first carbohydrate polymer network to the second carbohydrate polymer network, and a reflective mineral constituent intermixed with the first and second carbohydrate polymer networks. The bio-polysaccharide of the first carbohydrate polymer network is one of chitin, chitosan, or alginate. The second carbohydrate polymer network includes one of latex rubber, polyvinyl alcohol, ethyl vinyl alcohol, a polylactide, polyvinyl acetate, a polyhydroxyalkanoate, or a cellulose or lignocellulosic composite. The reflective mineral includes titanium dioxide and the cross-linking agent includes a reactive nitrogen source. The mineral nutrient can include one of Fe2+ iron oxide, Fe3+ iron oxide, iron sulfate, or magnesium sulfate. It also may include a soluble sulfate salt. The water remediation material can have a soluble silicate constituent with a particle size of less than or equal to 100 nm. The soluble silicate constituent containing a cross-linked soluble silicate which can be sodium silicate, potassium silicate, silicic acid, or fumed silica. The reactive nitrogen source includes at least one of urea, saltwater, or freshwater. The biopolysaccharide includes chitin, chitosan, alginate, urea, cellulosic fibers, or polyvinyl alcohol. Select embodiments can be a mixture of the nutrient constituent and the soluble silicate constituent, wherein the soluble silicate constituent at least partially covers the nutrient constituent. The mixture can be applied to an aquatic body and a predetermined aquatic organism can be nourished. The reflective mineral constituent can include a photoactive anatase crystal form of titanium dioxide, having a size between about 100 mesh (about 0.149 mm diameter) to about 250 mesh (about 0.053 mm). In further embodiments, the water remediation material can include the soluble silicate constituent which can be crosslinked silicates hydrogen-bonded to the nutrient constituent.

[0012] Embodiments of a method of preparing a nanobiocomposite nutrient carrier can include providing a nutrient constituent having particle size of less than or equal to about

100 nm and density of less than about 1.0 gm/cm3, providing a soluble silicate constituent having a particle size of between about 5 microns to about 10 microns, and density less than about 1.0 gm/cm3, and hydrogen bonding the nutrient constituent to the soluble silicate constituent. Providing a nutrient constituent can include providing a preselected nutrient constituent containing a preselected bioplastic, providing a preselected soluble silicate constituent which can include providing a preselected soluble silicate including fumed silica, or acidified sodium silicate or both, and combining the preselected nutrient constituent with the preselected soluble silicate constituent for a predetermined period forming an interpenetrating network, and achieving gelation after the predetermined period. Providing a nutrient constituent also can include providing a preselected nutrient constituent containing a preselected bioplastic, providing a preselected soluble silicate constituent, and combining the preselected nutrient constituent with the preselected soluble silicate constituent in water. The method also may include combining the preselected nutrient constituent with the preselected soluble silicate constituent for a predetermined period forming an interpenetrating network and achieving gelation after the predetermined period. The preselected nutrient constituent can be a soluble iron material including Fe3+ iron oxide, Fe2+ iron oxide, iron sulfate, or an effective combination thereof, in which the preselected soluble silicate constituent includes water-soluble silicates. Alternately, the preselected nutrient constituent can include a soluble sulfate, an anatase crystal form of titanium dioxide, or both. The silicate constituent includes a soluble silicate constituent having a density less than about 1.0 gm/cm3, and containing a cross-linked soluble silicate including sodium silicate, potassium silicate, silicic acid, or fumed silica. When the soluble silicate constituent is applied to an aquatic body, wherein a predetermined aquatic organism is nourished. [0013] These and other advantages of the present invention will be further understood and appreciated by those skilled in the art by reference to the following written specifications, claims and appended drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Preferred embodiments of the invention will now be described, by way of example, with reference to the accompanying drawings, in which:

[0015] FIG. 1 is an illustration of structural formulae for iron oxide-based nutrients, and sulfate free radical initiators, in accordance with the teachings of the present invention;

[0016] FIG. 2 illustrates the structural formulae of two water soluble nutrients, a reflective crystal, and an undesired water insoluble complex to be avoided by implementations of the remediation composition design, in accordance with the teachings of the present invention;

[0017] FIG. 3 illustrates the structural formulae for hydrogen bonding biological molecules, in accordance with the teachings of the present invention;

[0018] FIG. 4 illustrates the structural formula of gel- stabilized organic hydrogen bonded ocean remediation components with urea in accordance with the teachings of the present invention;

[0019] FIG. 5 illustrates the structural formula of gel stabilized chitosan ocean remediation components hydrogen bonded with iron nutrients and sulfate free radical initiators, in accordance with the teachings of the present invention; [0020] FIG. 6 is a view of the structural formula of polyvinyl alcohol gel stabilized with chitosan while also hydrogen bonded with iron oxide nutrients and urea, in accordance with teachings of the present invention;

[0021] FIG. 7 is an illustration of polyvinyl alcohol and chitosan encapsulated iron sulfate, surrounded by a shell of polymerized polyvinyl alcohol bonded with silicates in accordance with the teachings of the present invention;

[0022] FIG. 8 is a schematic of the core and shell nanobiocomposite structure of FIG. 7, in accordance with the teachings of the present invention;

[0023] FIG. 9 is a view of the material of FIG. 8 formed into a morphology containing a multiplicity of hollow closed cells as one method to create necessary buoyancy and resultant near-surface water flotation of the ocean remediation nanobiocomposite, in accordance with the teachings of the present invention;

[0024] FIG. 10 is a pictograph of the free radical initiated de-polymerization of ocean plastics and oil spill droplets, in accordance with the teachings of the present invention;

[0025] FIG. 11 is a schematic diagram of the synthesis of buoyant, reflective ocean fertilizer nanobiocomposite remediation material with a process to retain both air and flotation ability, resulting in a net material density of less than water, in accordance with the teachings of the present invention; and

[0026] FIG. 12 is a schematic diagram of the oceanic deployment method of buoyant nanobiocomposite remediation material, in accordance with the teachings of the present invention. [0027] FIG. 13 shows ocean surface water shade provided by buoyant nanobiocomposite discs floating over a coral reef.

[0028] Some embodiments are described in detail with reference to the related drawings. Additional embodiments, features and/or advantages will become apparent from the ensuing description or may be learned by practicing the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0029] The following detailed description, taken in conjunction with the accompanying drawings, is merely exemplary in nature and is not intended to limit the described embodiments or the application and uses of the described embodiments. Any implementation described herein as“exemplary” or“illustrative” is not necessarily to be construed as preferred or advantageous over other implementations. Furthermore, there is no intention to be bound by any expressed or implied theory presented in the preceding technical field, background, brief summary or the following detailed description. It is also understood that the specific devices, systems, methods, and processes illustrated in the attached drawings, and described in the following specification, are simply exemplary embodiments of the inventive concepts defined in the appended claims that there may be variations to the drawings, steps, methods, or processes, depicted therein without departing from the spirit of the invention. All these variations are within the scope of the present invention. Hence, specific structural and functional details disclosed in relation to the exemplary embodiments described herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriate form, and it will be apparent to those skilled in the art that the present invention may be practiced without these specific details.

[0030] The embodiments are directed to the technological development of ocean biodiversity starting with the remediation of ocean organic pollutants, wherein the pollution includes dissolved gaseous carbon dioxide, oil waste, and solid thermoplastics. The plastic pollutants especially refer to millimeter- to micron-sized plastics such as micro-fibers, and plastic micro-spheres. Transnational and global international oceanic resource development of oceanic biodiversity may use the specified buoyant nanobiocomposites as part of a multiple tiered administration of resources to mitigate and reverse undesirable economic pressures. These efforts can be in part directed at reversing the effects of acidified oceanic waters, therefore substantially enhancing the regional ability of oceanic life to flourish through the joint development and allocation of new biodi verse sources of shared food and raw materials. In technological aspects of the embodiments, the nanobiocomposite provides a source of cationic iron, which is useful for the fecundity of oceanic phytoplankton and diatoms in those regions having a deficit of this mineral in the surface waters where sunlight is otherwise able to allow phytoplankton growth. Embodiments also may provide a source of cationic silicate ions, which are useful for the fecundity of oceanic phytoplankton and diatoms in those regions having a deficit of this mineral cation in the surface waters where sunlight is able to allow their growth, being provided in a slightly water soluble and bioavailable form. [0031] An organic gel structure can be created and used to substantially limit the direct reaction of soluble silicates with soluble iron from reacting and forming substantially insoluble inorganic iron-silicates. This is accomplished by providing a structural framework of interposed and interpenetrating, slightly water soluble, organic media to favor the microbial ability of phytoplankton diatoms to easily catalyze the dissolution of iron separately and at a physical distance from the dissolution of silicates, wherein iron and silicate components are disposed at distinct morphological regions of a gelled matrix structure, or are otherwise deposed in spatially distinct and physically separated locations. The structure of the gelled medium is capable of retaining air inclusions in the form of air bubbles to provide buoyancy necessary to keep the nutrients of the present invention within about the first two centimeters of oceanic waters as required to perform maximum fertilization service to beneficial diatoms and surface phytoplankton in that region where dissolved carbon dioxide is maximal, and access to sunlight is also maximal. In one aspect of active ingredient utilization, the active ingredients mixed into the blended carrier polymer provide the inclusion of a water-soluble sulfate salt, where sulfur in the released sulfate ion is a necessary nutrient to promote the growth of algae and microalgae. Also, the active ingredients mixed into the blended carrier polymer, can provide a dissolved free radical generator in the presence of strong sunlight, herein again embodied by the water soluble sulfate salt, wherein high concentrations of sulfate are intended to achieve the solar depolymerization, photodegradation, or photolysis of oceanic plastic waste and oil spill residuals such as tars that float at or near to the ocean surface, especially as these wastes are concentrated in those oceanic regions known to collect such pollutants, such as the oceanic gyres, and oceanic regions where oil drilling platforms are located.

[0032] Also, the active ingredients provide a slightly soluble plastic carrier material forming a scaffolding substrate capable of being dissolved by ocean water, where the bioplastic content of this material is formed directly from saltwater harvested algae, phytoplankton, diatoms, or cyanobacteria being the wild type, or a domesticated microbial strain optimized for bioplastics production (herein parenthetically denoted by exemplary NC, CCALA, PCC, NIES, or other species strain number), such as, without limitation, the following species: Ankistrodesmus falcatus (NIES-2195), Chlamydomonas reinhardtii (strains DW15 and 11-32A), Chlorella sorokiniana (NIES-2173), Chlorella variabilis (NC-64A), Chlorella vulgaris (NIES-227), Parachlorella kessleri (NIES- 2152), Scenedesmus acutus (NIES-94), Scenedesmus obliquus (NIES-2280), cyanobacterium Synechocystis sp.(CCALA192, PCC 6803, MAI 9), Scenedesmus, Haloferax mediterranei, Arthrospira platensis, Spirulina maxima, Anabaena cylindrida, Spitulina platensis, and Aulosirafertilissima.

[0033] With the bioplastic carrier raw material source, the slightly soluble plastic carrier material forming a scaffolding substrate capable of being dissolved by ocean water, is obtained substantially from the growth and harvest of oceanic algae, phytoplankton, diatoms, cyanobacteria and the like, using a commercially available aerated photo-bioreactor. In this embodiment, the controlled growth conditions may be contained within flat or cylindrical sleeve-shaped containment vessels.

[0034] In particular embodiments of the soluble plastic or bioplastic carrier material forming a blended scaffolding substrate, the interpenetrating and copolymerized ingredients thereof contain a mixture of one or more of the slightly soluble plastics and bioplastics such as, without limitation, ethyl vinyl alcohol; polyvinyl alcohol (being a type of water soluble polyester); poly vinyl acetate; the class of polylactides such as more specifically polymerized lactic acid or PLA; the class of polyhydroxy alkanoates specifically including polyhydroxybutyrate or PHB, polyhydroxy valyrate or PHV and their copolymers, especially that of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) or (PHBV); cellulose and lignocellulosic composites; polymerized biopolymers such as starch, chitin, complex polysaccharides, and hyaluronic acid; and any interpenetrating combination of such polymers, and latex rubber. Also included are co-extrusions of such polymers and biopolymers, or mixture of such polymers to include like materials having the property of being slowly dissolved, digested, depolymerized, or disassembled in the natural process of eventual complete dissolution with the assistance of exposure to moving and flowing ocean water and the digestive fluids of marine life that contain or are exposed to ocean water. In a blended binding ingredient utilization, the soluble polymers can provide the containment and retention of gaseous inclusions such as air bubbles for conferring flotation and buoyancy of the embodiments of the present invention in water. [0035] The dual provision of both buoyancy and reflective properties to a material composition that eventually undergoes substantial dissolution allows the non-permanent geoengineering of the Earth by local treatment of oceans and waterways. These functions allow the material of the present invention to act as a fertilizer, a thermal barrier material, a light reflective material, and provides a means to remediate undesirable floating organic waste products from surface waters using the chemical energy of free radicals provided by solar irradiation. Enough deployment allows the reduction of the temperature of the oceans and waterways by reflecting sunlight and by providing shade to shelter diverse organisms from the sun. The local reduction in water temperature allows the retention of enough oxygen to be retained in regions that may otherwise be too warm to allow fish to breathe or corals to prosper. Particularly, surface water fertilization provides the growth of significant numbers of silicate containing diatoms, phytoplankton, and zooplankton of the type that are heavy enough to send their carbon containing carcasses down into the oceanic depths for sequestration periods of hundreds to as much as thousands of years depending on deep water conditions, as a primary means of capturing carbon dioxide from the atmosphere and the ocean. Significant economic prosperity and improvement to the human condition may be conferred by enough reflective floating fertilizer deployment, leading to more plentiful fish and oceanic foodstuffs, a reduced global average temperature, and a reduced carbon dioxide level in both the oceans and the atmosphere of the earth. [0036] The action of incident sunlight, especially the energetic ultraviolet portion of that sunlight, can generate free radicals, such as provided by a sulfate-containing salt able to dissolve in water and produce the sulfate ion upon irradiation by sunlight, thereby generating free radicals. The utilization of free radicals can perform de-polymerization of solid organic media, wherein such media include plastics, tars, oils, or any combination thereof. The utilization of the soluble properties of the plastic carrier materials form a scaffolding substrate, where the active ingredients thereof can be capable of becoming dislodged, dissolved, or otherwise broken up to avoid long term obstruction of the digestive tracts of shrimp or other tiny ocean creatures that live at or near the surface of the ocean. A founding substrate, onto which microorganisms and ocean plants can attach themselves, can stabilize their surfaces to a floating solid substrate. The creation of a floating substrate at a predetermined near-surface depth, e.g. about 2 cm, onto which microorganisms and plant life can perform photosynthesis for the purpose of generating oxygen and biomass. An iron- and nutrient-induced diatom bloom is severely restricted below the compensation depth due to both light limitation and ocean herbivore grazing pressure. The important creation of a storm resistant flotation matrix of nutrient supply can have a slow release of fertilizer, such that this infusion method is in contrast to the drop of natural, or native, dust and mineral concentrations after each storm to that of mixed ambient bulk ocean mineral concentrations without such a matrix flotation support. A founding substrate can be created onto which microorganisms and plant life can become anchored to enable better digestion and extraction of the nutritive fertilizer ingredients which have been de-incorporated from that founding substrate. In yet another embodiment, the provision of the key limited silicon micronutrient as nano-silicates overcomes the past inability of iron fertilization testing programs to promote the fecal drop of coastal diatom Phaeodactylum tricornutum, as well as other oceanic diatoms to sequester ocean bottom carbon, where increasing C02 and decreasing pH stimulates their photochemistry with synergistic effect, in the presence of the silicate nutrient.

[0037] The southern and Antarctic oceans substantially lack dissolved silicate surface nutrients for diatoms. Herein, an aqueous solution of sodium silicate can be acidified to produce a gelatinous precipitate. This precipitate can be sheared to incorporate air in at least one air bubble inclusion to result in a net density of less than 1.0 g/cm3 for any contiguous part of the crosslinked silicate gel, thereby enabling buoyancy of the silicon micronutrient in freshwater as well as in saltwater. It is desirable in some cases to only distribute the floating silicate and no other micronutrients. This may be important when dissolved iron and dissolved silicate react and precipitate without first being digested and incorporated into diatoms for carbon sequestration purposes.

[0038] In yet another embodiment, a source of free radicals is provided having the characteristic of being able to depolymerize organic hydrocarbon substances not only including the founding substrate, but also any foreign plastic or petrochemical based materials that may adhere to the founding substrate. The preservation of nontoxic cell forms of ocean algae which otherwise, by the limitation of iron mineral, can result indirectly to the decrease in chlorophyll and increase in the formation of the toxic proteins exuded by the bloom of the algae Alexandrium tamarense, also known as the red tide effect, causing widespread death to shellfish and fish in oceanic water. In some cases, the toxic algae bloom is colored green, where such algae blooms are associated with what is more commonly called a green tide effect.

[0039] The free radicals of the embodiments can be used to remediate toxic compounds arising from green or red tides, toxic compounds arising from leachates of plastics such as the phthalate esters, and microplastics requiring depolymerization by photolysis. These free radicals arise from the spallation of water by ultraviolet light in the presence of an appropriate catalyst. The active free radicals are (OH dot), where the dot represents a free radical of the hydroxyl group arising from ordinary water in the interaction with ultraviolet radiation from sunlight. A desired catalyst used to generate free radicals can be titanium dioxide microcrystals, in which the photoactive crystal is of the anatase form. Sulfate ions provide an alternative source of free radicals but are less preferred because they undesirably contribute to the overall acidity of the oceans. Titanium Dioxide (Ti02) catalyst particles can be micron sized, and are not nanometer sized, to reduce their long-term toxicity to ocean micro-organisms, and can be added as 0.1 to 1% by weight. The type of Ti02 particle has a size of about 100 mesh (0.149 mm) to about 250 mesh (0.053 mm). Titanium dioxide is commercially available as a cosmetic grade additive or as a food grade white color additive, where the latter has an international and European specification of coloring E171 (Pigment White 6 or Color Index number CI77891). In the US, Ti02 is specified by 21 C.F.R. §73.575. These specifications are of a variety of Ti02, which consists of a mixture of rutile, anatase, and brookite crystal forms. The anatase crystal is the photo-active form that generates the most hydroxyl free radicals in water on exposure to ultraviolet light from sunlight. The free radical forming effect is more generally known as the photolysis effect when the free radicals are generated to depolymerize liquid or solid organic pollutants. The photolysis function is a desired method of the present invention. Undesirable alternative forms of Ti02 raw material include those specifications calling out purified titanium dioxide rutile composition. Rutile is used to avoid photolysis while conferring a white color. The presence of anatase Ti02 is well known to break down the polymers that bind and cause yellowing of paints. While rutile is a form of titanium dioxide, or Ti02, that is equally reflective, rutile enriched Ti02 is less effective to promote the specified polymeric depolymerization of microplastics. Therefore, commercial specifications such as Pigment White 6 (PW6), or Cl 77891 enriched in rutile, may not enable the full utility of the pertinent embodiments herein, because they lack anatase crystals of titanium dioxide. The presence of natural anatase crystals in a normal mixture of refined Ti02 is required to allow the photo-active degradation of ocean microplastics and the remediation of oily floating films containing toxic compounds, as included in specified composition of the nanobiocomposite. These crystals may be deposed as inclusions to any part or portion of the biopolymeric component containing iron oxide nanoparticles, or may be deposed as inclusions to any part of the silicate phase of the composition, including those regions or particles enriched in silica gel, silicic acid, or fumed silicates.

[0040] The reflective properties of the titanium dioxide component in the ocean nanobiocomposite fertilizer can be optimized when the product of the embodiments is formed or agglomerated into pellets or chips having a flat nature, meaning they have a high aspect ratio (width divided by thickness), typically greater than about 1, as formed by a distinctive disc or ‘hockey puck’ shape. The disc thickness can be from 3 millimeters to about 1 centimeter, and the diameter can be as wide as desired without posing a hazard to shipping or to marine wildlife. Manufacturability of this shape will favor discs of about 1 cm to about 30 cm diameter, but other sizes and thicknesses are allowed without limit as depending to the local oceanic conditions and requirements. In some cases, great surface areas covered by such discs may be required to shade regions of the ocean to allow local cooling effects suitable to ensure the health of oyster beds and clams deposed beneath them. Such regions may benefit from floating snakes or other methods to constrain the floating discs to an aquaculture project or region. In other cases, a collection of floating discs is corralled, tied, or roped together to restrict the movement of large collections of reflective discs to ensure the targeted treatment of low temperatures and high oxygenation of local waters. This may be the goal of local fisheries dependent on these discs as sources of shade and maintenance of local biodiversity to ensure a healthy stock of fish for future harvesting. [0041] In addition, buoyant nanobiocomposite fertilizer can be applied as surface floating pellets or discs to bodies of water as part of the preservation of nontoxic cell forms of algae. Blocking access to light limits the growth of toxic algae. This is especially important in water regions polluted by agricultural runoff of dissolved nitrate and phosphate fertilizer from the land. Toxic proteins can be exuded by the microcystin production of the cyanobacteria Microcystis aeruginosa, which can cause widespread death to shellfish and fish in freshwater bodies, such as, without limitation, freshwater rivers and lakes, as well as by species of toxic algae arising in polluted ocean water regions close to the coastline.

[0042] Further, buoyant reflective nanobiocomposite fertilizer can be applied to bodies of freshwater as part of the preservation of nontoxic cell forms of freshwater algae which otherwise, by the limitation of the sulfur minerals, results indirectly to the decrease in chlorophyll and increase in the formation of the toxic proteins exuded by the bloom of the toxins exuded by the microcystin production of the cyanobacteria Microcystis aeruginosa, which can cause widespread death to shellfish and fish in freshwater bodies, such as, without limitation, rivers and lakes. The method of hyperspectral optical discrimination of phytoplankton community structure by correlation to the color of the ocean from orbit can be used as a remote sensing measure of the efficacy of oceanic fertilization. This will allow consideration of the additional deployment or possible relocation of the floating reflective oceanic nanobiocomposite to more appropriate regions as needed. Meteorological considerations of ocean temperature may require large scale deployment of floating reflective pellets or discs to equatorial regions to allow shading and cooling of ocean water to mitigate or eliminate El Nino or La Nina conditions. Such deployment could result in the reduction or elimination of severe typhoons, hurricanes, and atmospheric cyclones responsible for destructive storms, while still allowing the transport of shipping through these regions. This scale of deployment can have great value in climate change mitigation but will nevertheless require careful consideration of the size and shape of the individual nanobiocomposite fertilizer pellets or discs that are released into international oceanic surface waters. Ideally, the reflective floating fertilizer units will not significantly wear or damage boats, ships, and other international ocean transport. Potentially, this can be achieved by imposing limitations on the size and the shape of the deployed floating fertilizer units. This type of regulation is expected and encouraged, with eventual international consensus achieved through political forums suitable for such consideration, such as by the United Nations. Any manufacturable size or shape to the nanobiocomposite agglomerates or constructs is anticipated. Indeed, artificial floating islands of the materials used in the present invention are equally suitable. Larger objects can be provided, however they can also be marked or otherwise indicated by flashing lights, bright colors, radio beacons, or traditional means suited to the purpose of identifying a potential navigation hazard.

[0043] Referring now to the following drawings wherein like elements are represented by like numerals throughout: [0044] In FIG. 1, there is shown the structural formulas for inorganic fertilizer nutrients such as, for example, the iron oxides, ferrous oxide (Fe ₂ 0 ) 12 and ferric oxide (FeO) 14, the aqueous free radical initiator iron sulfate 16, and the aqueous free radical initiator magnesium sulfate 18. The particle sizes of substances 12, 14, 16, 18 can be 100 nanometers or less, because these nano-particulate minerals are most easily able to find biological uptake among oceanic phytoplankton, and because this size of particle also expedites their eventual dispersion or dissolution into oceanic surface waters (euphotic or epipelagic zone). In some cases, it may be desirable to use an additional mixture of larger sized micron particulates where slow dissolution rates are desirable, such as when the recurrence of fertilization deployment is to be reduced.

[0045] The iron cation arising from iron sulfate 16 functions as a nutrient in those surface ocean waters deficient in this mineral nutrient. A common oceanographic feature of surface waters well offshore of continental shelf and river plume supplies, is the dearth or limit of iron nutrients, being often less than one nano-molar concentration, while relatively enriched in nitrogen (N) and phosphorus (P), therefore requiring mineral sources of iron such as ferrous oxide 12, ferric oxide 14, or iron sulfate 16 to be deployed and released at these offshore regions to enable the growth of phytoplankton.

[0046] While magnesium cations arising from magnesium sulfate 18 are already sufficiently present in almost all surface ocean waters, the lability or ease of dissolution of magnesium ion makes it a rapid means to introduce a high concentration of sulfate anions by dissolution where required for remediation with very rapid deployment in regions that are suddenly heavily polluted with tars and oil from the remnants of an oil spill. However, proximity to a coastline and organic fecal waste discharge may incur the alternate danger of initiating a cyanobacteria bloom which can be detrimental to coastal ocean biodiversity, therefore the sulfur nutrient deployment benefit may be intentionally counterbalanced by the avoidance of risk of sulfate deployment at such locations. Sulfates are most suitable for regions of high surface water plastic content, such as at oceanic gyres far away from coastlines where plastics tend to accumulate. Iron sulfate 16, magnesium sulfate 18 or other functionally equivalent soluble sulfate salts, produce sulfate anions to serve as an inexpensive choice of free radical initiator on solar irradiation to depolymerize ocean surface plastic waste, when deployed well offshore from coastal areas, and used with proper care in accordance with the teachings of the present invention.

[0047] Referring now to FIG. 2, there is shown sodium silicate 22, also known as sodium metasilicate in the hydrated form, and silicic acid 23, where these silicates easily dissolve in water to create anions and cations. Additional soluble silicate salts such as potassium silicate can also be used instead of sodium silicate 22, or silicic acid 23, as a gelation agent. However, sodium silicates may be preferred because of low cost and readiest commercial availability. Upon dissolution in water, iron sulfate 24 produces ferrous (Fe2+) cation. The iron cations of iron sulfate 24 may then undesirably react with the silicate anions on dissolution of sodium silicate 22 and silicic acid 23 to form insoluble ferrosilicate products 26, depending on both pH and concentration effects. The presence of repeating molecular subunits within the structure of insoluble ferrosilicate product 26 are identified with the use of square brackets. The number of repeating units may vary, and that number is herein represented using a subscript lower-case letter‘n\ The substantially insoluble ferrosilicates 26 can fail to perform as nutrients in soluble form. It may be desirable to avoid excessive insoluble ferrosilicate formation in favor of producing a reversibly hydrogen bonded gel. It is desirable to avoid the formation of insoluble structures such as insoluble ferrosilicate products 26, by using a gel structure as a means to separate the positively charged cationic atomic iron species within the structure of iron sulfate 24 from reacting directly with the anionic silicate species arising directly from structure of sodium silicate 22, by interposing a multiplicity of other complexes having charge screening properties, or alternatively interposing physical space between the reactive anionic and cationic species, or achieving both objectives at once.

[0048] The provision of reflective titanium dioxide 28 may be arranged into native crystal forms brookite, rutile or anatase, where the anatase crystal form is necessary and required to provide free radicals in abutting materials by means of the sunlight-mediated photolysis effect. In certain embodiments, Ti02 can be added to the silicate phase. In some embodiments of floating oceanic floating fertilizer, titanium dioxide 28 can be the free radical initiator of choice for regions away from oceanic gyres requiring significant plastic remediation, and to exclude sulfates 24 from the floating fertilizer formulation in all other deployments. This choice is intended to ensure a reasonable limit to the undesirable acidification of the oceans by sulfates 24. [0049] Referring now to FIG. 3, there are shown several biodegradable and biocompatible, water soluble, carbohydrate polymers including chitin 31, alginate 32, chitosan 34, urea 36, and polyvinyl alcohol 38, where chitin 31, chitosan 34, and urea 36 also act as sources of nitrogen fertilizer nutrient. Urea 36 is most readily dissolved in water 32 and is therefore most biologically available. The less soluble and therefore less biologically available form of nitrogen in chitosan 34 (herein CS) follows, and then by the biological availability of nitrogen from the substantially insoluble chitin 31. Any of repeating subunits of carbohydrate polymers chitin 31, alginate 32, and chitosan 34, may form hydrogen bonds with any of the repeating subunits of polyvinyl alcohol 38 (herein PVA), and any number of urea molecules 36. PVA is a water-soluble poly hydroxyl polymer. Chitosan is a positively charged, polycationic, naturally occurring, bio degradable, non-toxic, non-allergenic biopolysaccharide extracted from chitin, which is the main structural polymer in arthropod exoskeletons, and which is found in abundance in nature. The presence of repeating molecular subunits within structures chitin 31, chitosan 34, and PVA 38 can be identified with the use of square brackets. The number of repeating units may vary, and that number is herein represented using a subscript lower-case letter‘n’, wherein the number represented by‘n’ can be a different number at each location where letter’n’ is indicated. It is to be understood that chitin 31, chitosan 34, urea 36, and PVA 38 are selected for their ability to form hydrogen bonds among and between each of their molecular structures in any ratio or combination to initiate and strengthen the formation of an interpenetrating polymer network, and also for their low cost and ease of commercial availability in bulk quantities. As used herein, a network is a highly branched structure in which essentially each constituent unit can be connected to another constituent unit and to the macroscopic phase boundary by many paths through the structure. An interpenetrating polymer network (IPN) is a polymer comprising two or more networks which are at least partially interlaced on a polymer scale but not covalently bonded to each other. The network cannot be separated unless chemical bonds are broken. Other biodegradable and water-soluble monomers and polymers are also possible, provided these achieve commercial viability for large area oceanic remediation and fertilization purposes.

[0050] In particular, chitin 31, chitosan 34, urea 36, and PVA 38 may function to form hydrogen bonds with water to allow the resulting IPN to swell and become sticky or tacky for the purpose of attracting bits of floating foreign matter which may also be present in the ocean surface waters, such as phytoplankton, or pollutants such as oil droplets, waste oil from oil spills, and waste organic matter, or micro-plastics such as micro-fibrils or micro-beads. In addition, the IPN formed from among any of chitin 31, alginate 32, chitosan 34, urea 36, or PVA 38, in any combination, may be highly suitable for mechanically imbedding or hydrogen bonding with any of nutrients such as ferrous oxide 12, ferric oxide 14, iron sulfate 16, or magnesium sulfate 18, as diagrammed in

FIG. 1, in and among the matrix of the resulting IPN. The substances chitin 31, alginate

32, chitosan 34, urea 36, and PVA 38 may be physically structured to maintain spatial distances as well as compatible nutrient release rates in accordance with the required separation of reactive silicates from reactive iron as described with respect to FIG. 2, such that the resultant composite of polymer and the nanometer sized minerals (herein nanobiocomposite) are applied in accordance with the teachings of the present invention.

[0051] Referring now to FIG. 4 there is shown a portion of an interpenetrating polymer network (IPN) 40. The presence of repeating molecular subunits within IPN structure 40 are identified with the use of square brackets, and the number of repeating units of IPN

40 may vary and that number is herein represented by the use of a subscript lower case letter‘n’, wherein the number represented by‘n’ can be a different number at each location where letter’n’ is indicated. IPN 40 is a single hydrogen bonded molecular ensemble shown to be composed with recognizable portions of at least one region of urea

41 and at least one region of chitosan (CS) 42 and at least five regions of polyvinyl alcohol (PVA) 43, where each molecular region of the IPN ensemble shown are separately illustrated as independent molecules in FIG. 3. Other embodiments of hydrogen bonded IPN are possible, when applied in accordance with the teachings of the present invention.

[0052] Referring now to FIG. 5 there is shown a portion of an interpenetrating polymer network (IPN) 50. The presence of repeating molecular subunits within IPN structure 50 are identified with the use of square brackets, and the number of repeating units of the

IPN 50 may vary and that number is herein represented by the use of a subscript lower case letter‘n’, wherein the number represented by‘n’ can be a different number at each location where letter‘n’ is indicated. IPN 50 is a single hydrogen bonded molecular ensemble shown to be composed with recognizable portions of at least one region of sulfate 51 and at least one region of chitosan (CS) 52 and at least two regions of ferrous oxide 53, at least one region of ferric oxide 54, and at least one region of ferrous ion complexed with six water molecules 55, where each molecular region of the IPN 50 ensemble shown is separately illustrated as independent molecules in FIG. 2 and FIG 3. Other embodiments of a hydrogen bonded IPN are possible.

[0053] Referring now to FIG. 6 there is shown a portion of interpenetrating polymer network (IPN) structure 60. The presence of repeating molecular subunits within IPN structure 60 are identified with the use of square brackets, and the number of repeating units of the IPN 60 may vary and that number is herein represented by the use of a subscript lower case letter‘n’, wherein the number represented by‘n’ can be a different number at each location where letter‘n’ is indicated. IPN 60 is a single hydrogen bonded molecular ensemble shown to be composed with recognizable portions of at least one region of sulfate 61 and at least one region of chitin 62, at least two regions of ferrous oxide 63, at least one region of ferric oxide 64, at least one region of ferrous ion complexed with water molecules 65, and at least one region of urea 66, where each hydrogen bonded molecular region of the IPN 60 ensemble shown is separately illustrated as independent molecules in FIG. 2 and FIG 3. Other embodiments of hydrogen bonded IPN are possible, when applied in accordance with the teachings of the present invention. [0054] Referring now to FIG. 7 there is shown a portion of an interpenetrating polymer network (IPN) 70. The presence of repeating molecular subunits within IPN structure 70 are identified with the use of square brackets, and the number of repeating units of the IPN 70 may vary and that number is herein represented by the use of a subscript lower case letter‘n’, wherein the number represented by‘n’ can be a different number at each location where letter‘n’ is indicated. IPN 70 is a single hydrogen bonded molecular ensemble shown to be composed with recognizable portions of at least one outer shell region 71 of crosslinked silicates 72 hydrogen bonded to regions of PVA 73, and in inner core region 74 of at least two regions of chitosan 75, at least one region of ferric oxide 76, and at least one region of ferrous ion complexed with water molecules 77, where each hydrogen bonded molecular region of the IPN 70 ensemble shown are separately illustrated as independent molecules in FIG 1, FIG. 2, and FIG 3. The presence of titanium dioxide crystals will appear as inclusions at any point within any of these molecular networks. The presence of gas filled voids required to confer buoyancy appear as bubbles, gaps, or regions deposed at any place within any of these molecular networks. Other embodiments of core and shell hydrogen bonded IPN are possible, having outer shell regions rich in silicates and having no iron containing regions, and paving inner core regions is composed with iron rich regions exemplified by IPN 40, or IPN 50, or IPN 60 as illustrated in FIG 4, FIG 5, or FIG 6 respectively, when the combined core and shell morphology is applied in accordance with the teachings of the present invention. [0055] Referring now to FIG. 8 there is shown a simplified schematic of a core and shell nanobiocomposite structure 80, designating outer silicate rich shell region 82, and inner iron rich core region 84, where the details of particular embodiments of the core and shell regions of the nanobiocomposite are also illustrated in FIG 7. Core 84 can be left out of some of the nanobiocomposite granules to allow greater physical distance in flotation deployment and therefore potential reactive combination of non-iron-containing silicate granules from other granules where both the outer shell 82 and iron containing core 84 are present. Some of the nanobiocomposite granule ensembles may leave out silicates in the composition of outer shell 82, thereby maximizing the hydrogen bonded and crosslinked IPN with iron enriched cores. This provides the opportunity for silicate- rich nanobiocomposite granule ensembles to be physically separated in space from iron- rich nanobiocomposite granules on flotation deployment, when any combination of such nanobiocomposite granule ensembles are used. In all cases, the presence of titanium dioxide provides reflectivity to the nanobiocomposite materials of shell 82, core 84, or disc 85. In certain cases where the primary objective is to reflect sunlight from the surface of the water in which the material of the present invention is floating, it is less desirable to have a round or low aspect ratio shape such as represented by shell 82 and core 84, and it is more desirable to have a flat shape as shown by the representative disc shape 85. The extended region of the flat shape of disc 85 is naturally deposed parallel to the surface of the water on which it floats because of buoyancy effects. This orientation allows maximal coverage of water surface area to enable greater reflectivity of light rays from that surface, as represented by the direction of the incident and reflecting arrows 86,

87. The effect of light ray reflection 86, 87 is to return incident solar radiation back towards outer space, away from the Earth, resulting in a net cooling effect. Unlike reflective ice that can only perform such a reflective function at the cold polar regions of

Earth, the materials of the present invention allow reflectivity to take place from the surface of waters at any part of the planet, including equatorial regions that receive the greatest amounts of direct solar irradiation. Sunlight reflection 86, 87 restores the ability of oxygen to dissolve into the waters disposed underneath a sufficiently large array of individual floating nanobiocomposite discs, where the multiplicity of such floating ocean reflective elements may be represented by an array of the singular material of disc 85, or by an array of the singular materials of shell 82 and core 84. It is understood that other manufactured shapes than those exemplary shapes shown herein are possible. It is also understood that the dissolution process in fresh water or salt-water will roughen, distort the shape of, and eventually dissolve or disperse the materials of shell 82, core 84, or disc

85. The material of the flat disc shape of“puck” 85, when partially dissolved, can have a shape represented by the cross section of the material shown in Fig. 9.

[0056] Referring now to FIG. 9, there is shown a nanobiocomposite IPN flotation particle 90 provided with multiple hollow cellular regions 91, all or many of which hollow air-filled regions. In some embodiments, hollow regions 91 are not interconnected or remain isolated in the process of synthesis to form air-filled buoyant voids in three dimensions throughout the solid substrate 94 of this structure. The material of substrate 94 may include reflective titanium dioxide particles, with molecular structure shown in Fig. 2. Large white arrow 95 indicates the reflection of incident light from the external surfaces of material of 94 having inclusions of reflective titanium dioxide. The slow dissolution of the solid and particulate contents of nanobiocomposite IPN flotation particle 90, maintain internal cavities having the ability to retain air for the purpose of providing buoyancy in water. In addition, air bubbles are often formed during wave action near to the ocean surface, and some of these air bubbles 92, 93 are shown adhering to the indicated regions having interstices and outer rough surfaces of nanobiocomposite IPN flotation particle 90, thereby providing additional flotation and buoyancy to nanobiocomposite IPN flotation particle 90 during the process of solubilization and dissolution. As well, oil particle waste from ocean shipping traffic, or from inadvertent petrochemical raw feedstock oil spills, indicated by vesicle 98, may be able to adhere to the outer regions of nanobiocomposite IPN flotation particle 90 having interstices and outer rough surfaces, when deployed in ocean surface waters in accordance with the teachings of the present invention.

[0057] Referring now to FIG. 10, an illustration of ocean remediation 1000 is shown.

In FIG. 10, there is shown one representative buoyant nanobiocomposite particle 1060, more than one of which are to be deployed as a multiplicity of such particles into ocean water and floating near to the ocean surface 1010. The design of porosity and buoyancy is to maintain flotation within a distance Dl, which may be, without limitation, about 2 centimeters in depth from ocean surface 1010. The proximity to ocean surface 1010 allows substantial daytime solar irradiation 1020, inclusive of ultraviolet portions of the solar spectrum, to penetrate into the waters of ocean surface 1010 proximal to floating masses of porous nanobiocomposite particles such as, for example, nanobiocomposite particle 1060, which can be a biodegradable nanobiocomposite IPN nutrient carrier. A bubble of oil 1090, and a plastic nano-fibril 1080 are shown in water attracted, and adhered, to the outer surface of a buoyant nanobiocomposite particle 1060. The action of energetic ultraviolet portions of solar irradiation 1020 interact with nearby sulfate ion 1022, released from nanobiocomposite particle 1060 by dissolution into seawater, to form dissolved free radical sulfate ion 1023, while the counter-ion of dissolved ferrous cation 1028 is simultaneously converted to a ferric cation 1027. Alternative free radicals may be initiated through the energy of ultraviolet light to result in the splitting of water 1035 to form free hydroxyl radical 1034, and by solvated chloride ions 1036 to form chloride free radicals 1033. The material of particle 1060 includes inclusions of the anatase crystal form of titanium dioxide, such that any of these crystals deposed at the surface of particle 1060 may interact with water molecules 1035 to form hydroxyl free radicals 1034 when provided with ultraviolet light energy from sunlight 1020. Any of these free radicals may then serve to depolymerize pollutant oil droplets or foreign ocean plastic detritus at the ocean surface. However, the reactivity of the free radicals of sulfate 1023 are much more rapid and effective at the performing of remedial de-polymerization reactions, yielding water and carbon dioxide 1040 as eventual end products of the decomposition of oceanic solid organic waste 1080, liquid organic waste 1090, and the biodegradable nanobiocomposite nutrient carrier 1060.

[0058] FIG. 11 is a flow chart S1100 outlining the steps that may be used to synthesize the buoyant nanobiocomposite ocean fertilizer and plastic or oil waste remediation nanobiocomposite of the present invention. In step SI 110, combine core materials containing a preselected biodegradable hydrogen bondable organic media (e.g., chitin, chitosan, alginate) with a preselected nutrient (e.g., Fe3+ iron oxide, Fe2+ iron oxide, iron sulfate), and titanium dioxide, into distilled water. In step SI 120 apply shear mixing at about 1000 revolutions per minute while heating gradually to about 90 degrees

C to help dissolve the water-soluble portions of this mixture. In step SI 130, add the soluble silicates (such as silicic acid, sodium silicate, potassium silicate, fumed silica) continuing to stir this mixture briefly to ensure a good mixture, then halt stirring and allow about 60 minutes to about 180 minutes to achieve gelation. At this point, proceed to step SI 170 if a low porosity closed cell nanobiocomposite is desired. Otherwise, if a significantly open cell nanobiocomposite is desired, then proceed to step SI 140, and drive off most of the water to gel the bulk sections of nanobiocomposite medium, using convective heat, inductive heat, microwave irradiation, laser heating, or other means to create a base material form or substrate useful to assist in building large cavities for improved floatation as desired. In step SI 150, apply additive manufacturing or adhesive processes to weld sections or optionally, to bond chemically different portions or phases having different densities together, especially if it is desired that a denser abutting phase be adhered. This construct may tend to orient a denser section towards the bottom of a less dense floating substrate. However, this step can also be used to seal any number of sections together, especially if large structural cavities are desired. In Step SI 160, allow the nanobiocomposite to air dry using forced convection at 120 degrees C. Apply UV light to the dry nanobiocomposite for enough time to allow densification and more complete polymerization of the nanobiocomposite, or apply microwave irradiation to accomplish a similar free-radical initiated polymerization. These methods impart energy to allow the chemical crosslinking to harden the nanobiocomposite while also imparting resistance to rapid dissolution, so that a desired slow dissolution rate can be achieved on long term ocean fertilizer deployment.

[0059] Referring now to FIG. 12 there is shown a schematic diagram of the deployment of ocean fertilization and remediation nanobiocomposite S1200. In step SI 210, the buoyant nanobiocomposite is loaded onto an oceangoing vessel for local distribution at the site selected for nutrient improvement. In step SI 220, the ocean vessel arrives at the designated site, and a conveyance is used to unload the nanobiocomposite from the hold or storage containment areas of the vessel, into the ocean at a rate that is metered in accordance with the vessel speed across the ocean surface. In step SI 230, the ocean surface waters are periodically sampled in front of the ocean vessel to ascertain the surface biodiversity with respect to small animals, diatoms, and other surface phytoplankton. Of interest are the characterization of the top 12 inches of ocean surface waters, to include dissolved mineral nutrients and dissolved gases, especially that of dissolved oxygen. In step S1240, the results of step SI 230 are used to calibrate or supplement the information obtained from fixed buoys or remote telemetry with respect to the same or similar types of information, especially with respect to dissolved oxygen content, dissolved carbon dioxide content, pH, temperature, and bioavailable nitrogen content. In step SI 250, the data from step SI 240 is used in conjunction with areas previously fertilized on initial deployment of the nanobiocomposite from the same oceangoing vessel, to estimate and project the time and dosage of the next required treatment. In step SI 260, regulated harvesting of the fertilized region for shrimp, floating kelp, or other ocean flora and fauna benefitting in biodiversity and bulk biomass growth are permitted as these become available at various depths in the ocean which benefit from the process of ocean surface fertilization. In step S1270, some of the economic proceeds from the harvesting in step SI 260 will then be set aside to allow for the purchase of more of the means to repeat the ocean remediation and fertilization efforts in the areas where significant improvement in carbon dioxide sequestration and growth in biomass is obtained. In step SI 280, the project can become expanded to test for efficacy in other oceans or at more distant regions having oceanic conditions that may differ from those where initial success was obtained.

[0060] Referring now to FIG. 13, there is shown a method of use of a multiplicity of nanobiocomposite discs 1320 floating on or near the surface of ocean water 1310 for the purpose of providing shade from sunlight to help shelter a multiplicity of corals in a coral reef 1330. This sheltering has the effect of reducing the ambient water temperature underneath the shaded region as indicated by the downward arrow and the degrees C symbols, 1350. Simultaneously, the reduction of the local water temperature allows the equilibrium dissolution of increased oxygen into the water as indicated by the upward arrow and the molecular symbol for oxygen, 1340. It is understood that only small reductions in temperature will provide a significant rise in dissolved oxygen content to allow for the protection of aquatic life requiring dissolved oxygen to survive in regions that are subject to undesirable climactic heating periods associated with climate change.

[0061] EXAMPLE: To make a test sample, begin with the core materials as follows:

14.35 grams latex rubber monomer, 0.51 grams FeS04, 2.04 grams preselected biopolymer (such as, without limitation, chitosan, polylactide, polyhydroxyalkanoates, cellulose fibers, or a functionally similar biopolymer), 0.5 grams mixed iron oxides (a mixture of Fe ₂ 0 and FeO), 2 grams of urea, 2 grams of titanium dioxide, 250 ml of distilled water, and heat at about 90°C with shear mixing for about 2 hours or until solution saturation is achieved. It is noted herein that the use of urea is optional to assist with the chemical crosslinking reaction, as the ocean normally has enough nitrogen.

[0062] Next, for an optional shell or phase of different density, prepare a saturated solution of sodium silicate containing up to about 70 percent glass bubbles or fumed silica, to about 20 percent titanium dioxide crystals containing enough anatase crystals to allow photo-activity and hydroxyl free radical formation on exposure to sunlight and water. Stir for 5 minutes to achieve a good mixture. Continuing, transfer this cloudy mixture to a flat bottom pan, and subject to about 2.45 GHz standard microwave irradiation until the steam has evolved and just before the smoke point initiates, which is about 1 minute for about 20 grams of sample substrate at about 750 watts. Alternatively, set into a convection oven equilibrated at about 110 degrees C to drive off water and initiate the formation of a foamed nanobiocomposite during the crosslinking reaction. Remove the hardened material from the oven. Peel the ocean nanobiocomposite from the bottom of the container, and place into distilled water to ensure this material floats for several days. It is noted that the presence of sodium chloride in ocean water may better maintain the gelled nanobiocomposite than distilled water, because of charge screening effects, therefore allowing more time for dissolution of the ocean nanobiocomposite than in fresh water.

[0063] In other embodiments, local economic availability permits the present invention to substitute an amount of ground shellfish waste such as chitin, dried phytoplankton, dried algae, cellulose fibers, or latex to be substituted for or diluted with the soluble biopolymer components. Notably, latex rubber which has not been vulcanized, is very able to decompose in sunlight and become digested by marine organisms to serve as one example of a biopolymer that is capable of complete dissolution.

[0064] It is notable that the use of sodium silicate treated with acid to form a gel, may be supplemented by hollow silicate glass microspheres to retain nanocomposite material buoyancy while causing the silicate spheres to adhere to each other. One vendor of hollow glass fumed silica microspheres is the commercially available product Cab-o-sil® fumed silica from the Cabot Corporation, Boston, MA, USA. A better-quality hollow glass product having less density with significantly more intact and enclosed microspheres is now commercially available through the 3M Corporation, under the recently introduced product, 3M™ Glass Bubbles. The addition of these or similar glass microspheres is an acceptable way to create the buoyancy requirement of less than about

1 gm/cm3 to enable long term floatation of the mixed nanobiocomposite, while also providing silicates to the ocean as a slowly dissolving nutrient fertilizer accessible to diatoms and silicate based phytoplankton. Biopolymers, alkali silicates, and iron particles in any combination may be added to these glass silicates. Any particle in the resulting floating fertilizer is to retain an ability to remain buoyant, regardless of the geometric distribution of the mixture components, or the addition of additional nutrient substances.

The addition of glycerol or polyethylene glycol (PEG) may be used as a plasticizer and processing aid if these materials are to be mechanically sheared in large twin-screw industrial plastic continuous processing equipment for foam extrusion at elevated temperatures. Hollow continuous extrusion shapes may be one preferred mass production method; other embodiments of production are possible and must be anticipated to meet a large-scale global demand to enable oceanic and atmospheric climate remediation.

[0065] As variations, combinations and modifications may be made in the construction and methods herein described and illustrated without departing from the scope of the invention, it is intended that all matter contained in the foregoing description or shown in the accompanying drawings shall be interpreted as illustrative rather than limiting. Thus, the breadth and scope of the present invention should not be limited by any of the above- described exemplary embodiments but defined in accordance with the foregoing claims appended hereto and their equivalents.